07.05.-11.05.

2012
Fuengirola, Spain
Invited Speakers
Takuzo Aida Moungi Bawendi
Jochen Feldmann Javier Garcia de Abajo
Hermann Gaub Lee Josephson
Nick Kotov Hedi Mattoussi
Paul Mulvaney Christopher Murray
Francesco Stellacci Paul Weiss
Itamar Willner

Nanognostics Speakers
Emmanuel Bois
Satelite Meetings Loïc Charbonnière
Piotr Cywinski
Nanognostics by A. Geßner James Delehanty
Herodot by D. Vanmaekelbergh Richard Dennis
Jens Dernedde
and W.v. Sark André Geßner
Dendreamers by J.L. Serano Harri Härma
and T.Sierra Niko Hildebrandt
Thomas Hug
Wolfgang Parak
Dendreamers Speakers Itamar Willner
Takuzo Aida Didier Astruc
Lluis Ballell-Pages Dick Broer
Pilar Calvo Carlos Cruz
Herodot Speakers
Bertrand Donnio Delphine Felder-Flesch
Efrat Lifshitz
Organisers
Alfonso Garcia-Benett Daniel Guillon
Juozas Grazulevicius Günter Lattermann Rolf Koole
Rainer Mahrt
Jesus de la Fuente
Georg H. Mehl Demetri Photinos
Joachim Stumpe Krim Talia Dries van Thourhout Luis Liz Marzan
Alexandros Vanakaras Sasha Efros Wolfgang Parak

www.nanax5.com
Dear participants of Nanax 5.

We are very happy to welcome you in Fuengirola! Please let us

welcome you to Nanax 5.

Best regards

Jesús M. de la Fuente, Luis Liz-Marzán, Wolfgang Parak

Nanoscience deals with phenomena and properties that are
characteristic of the nanosize regime. These may range from quantum
size effects in semiconductors to localized surface plasmons or Coulomb
blockade in metals, through a whole variety of exciting new effects that
are characteristic of nanoscale materials. Nanocrystals are the basic
units of Nanoscience and are often utilized as building blocks for the
construction of nanostructured materials. These topics are advancing at
an extremely fast rate and it is becoming increasingly difficult to keep
up with the most recent and exciting discoveries.

NaNaX 5 is the fifth international conference specifically dedicated to

discuss and share the most recent findings related to Nanoscience with
Nanocrystals. Topics will include the fabrication of nanocrystals, the
observation of novel phenomena, the assembly of nanocrystal building
blocks, individual and collective properties, as well as applications
arising from such novel materials and phenomena.

NaNax 5 will be organised by Luis Liz-Marzán, Jesús M. de la Fuente

and Wolfgang Parak

History of NaNaX: NaNaX was started in 2003 in Munich, Germany

and was organized by Jochen Feldmann, Hermann Gaub, Wolfgang
Parak, and Andrey Rogach. The series continued with NaNaX 2 which
was held in 2006 in Grenoble, France and which had been organized by
Peter Reiss and Andrey Rogach. NaNaX 3 took place in 2008 in Lecce,
Italy and was organized by Roman Krahne, Liberato Manna, and
Wolfgang Parak. The previous conference NaNaX 4 was in 2010 again in
Munich, Germany, and was organized by Jochen Feldmann, Peter
Reiss,and Andrey Rogach.

Satellite meetings: NaNaX has a history of combining the general

conference with satellite meetings. NaNaX 1 was joined by the SFB 486
Manipulation of Matter at the Nanoscale program from the German
Research Foundation (DFG), coordinated by Hermann Gaub. NaNaX 3
involved the project SA-Nano financed by the European Commission
which was headed by Liberato Manna. NaNaX 4 included the
Nanoinitiave Munich (NIM) funded by the German Research Foundation
(DFG) with Jochen Feldmann as chairman. The present conference
Nanax 5 will be joined by the Marie Curie Initial Training Network
'Herodot' funded by the European Commission and chaired by Daniel
Vanmaekelbergh and Wilfried van Sark, the European Commission
project Nanognostics, headed by Niko Hildebrandt, and by Dendreamers
which is funded by the European Commission and headed by Jose L.
Serrano.

Nanax 5 technical organization

Jesús M. de la Fuente Wolfgang Parak

Juan I. Gallego Beatriz Pelaz

Dorleta Jiménez de Aberasturi Andreas Rentzos

Luis Liz-Marzán Verena Wulf

Satellite meeting Nanognostics

About NANOGNOSTICS

6.1 million people currently live with a form of dementia in the

European Union with an addition of 1.4 million new cases every year.
Combination of psychological testing, brain-imaging and exclusion of
other neurological disorders makes the diagnosis of Alzheimer’s
disease (AD) complicated and time consuming (taking up to 20 months).
A rapid, sensitive and specific immunoassay for protein markers inside
blood would largely improve early diagnosis and lead to a better
treatment of dementia.

NANOGNOSTICS aims to implement a protein detection method based

on Förster Resonance Energy Transfer (FRET) between lanthanide
complexes (LCs) and quantum dots (QDs). This approach allows the
elimination of back-ground problems to a large extent and opens the
possibility of multiplexed detection.

NANOGNOSTICS will use antibodies and aptamers as recognition

reagents for multiplexed analysis of AD. However, the technology can be
adapted to any other diseases by simply changing the biomarker
binding reagents.

NANOGNOSTICS strives for a profound understanding of QD-based

FRET, the synthetic creation of highly efficient QD immune sensors for
detection of several AD-specific protein markers and the development of
a modular high-throughput-screening immunoanalyzer for the
integration of QD-based multiplexing immunoassays into early
diagnosis for improved patient outcome in dementia therapy.

The FP7 project NANOGNOSTICS, coordinated by André Geßner from

the Fraunhofer Institut for Applied Polymer Research in Potsdam

André Geßner (Frauenhofer Institut Potsdam, Germany)

[email protected]
Satellite meeting Herodot

Herodot: the Marie Curie training network project

Recent progress in the fabrication of colloidal semiconductor

nanocrystals has led to a wide range of quantum dots with a high
oscillator strength, photoluminescence efficiency and size-tunable
emission spectrum. The Herodot project (Heterogeneous quantum rod
and quantum dot nanomaterials) encompasses a comprehensive
research and training program on the opto-electronic properties of
heterostructured nanomaterials based on quantum rod and dot
building blocks.

In particular, material systems of study are quantum dot molecules,

binary quantum dot solids, superstructures of aligned quantum rods
and hybrid organic/inorganic systems with specific band alignment
(type-II heterostructures).

The optical properties of these systems, e.g. polarizability, exciton

lifetime and emission spectrum are determined by the delocalized,
indirect nature of the exciton, while optical anisotropy can be achieved
by alignment of quantum rods. Such systems can exhibit a large Stokes’
shift, enhanced nonlinear refraction, and an absorbance and emission
spectrum that can be tailored by the architecture of the superstructure
and external fields. This forms a direct route to applications of these
materials in optimizing light sources, next generation photovoltaics, and
realizing fast and compact optical modulators and switches.

The Herodot training network project started September 2008, and will
run for 4 years. In total 11 Ph.D. students and 4 Post Docs work
collaborate in 8 institutions and companies, see

http://www.herodot-mc.eu

Daniel Vanmaekelbergh (Utrecht University, Netherlands)

[email protected]

Wilfried van Sark (Utrecht University, Netherlands)

[email protected]
Satellite meeting Dendreamers

Project summary

Dendrimers are new materials obtained with a highly controlled

molecular structure in several space orientations. Liquid Crystals (LC)
Dendrimers are a part of them that incorporate directional properties to
these materials. If we append active molecules into these engineered
molecules, we can obtain multifunctional anisotropic molecules that
open the possibility of achieving a wide variety of physical properties
and new applications. Among the numerous possibilities to be explored
within this field, we have chosen two fundamental lines, which are
Biomedicine and Advanced Molecular Materials.

Training of multidisciplinary personnel in this field of research will

contribute to concentrate the knowledge spread in different countries
and to accelerate the development within Europe by means of industrial
collaboration. This collaboration will provide an up-to-date list of
requirements for better planning the research lines that ensure a rapid
evolution of the existing ones in Europe, all of which are oriented to the
synthesis of compounds easily transferable to industrial use. The aim is
to reduce the existing gap between academically developed new
materials and their industrial application. Multidisciplinary training will
include modelling of new materials, chemical synthesis and controlled
chemical orientation, structural functional studies, physical
characterization of structural properties, biological modelling, molecular
activity analyses, technology oriented samples and product escalation
towards industry processes. These training aspects will go parallel to a
research career, complementary formation and cooperation key-events.

DENDREAMERS HOME

Jose L. Serrano (University of Zaragoza, Spain)

Teresa Sierra (University of Zaragoza, Spain)

[email protected]
Invited Speakers

NaNaX 5

Takuzo Aida Moungi Bawendi

University of Tokyo MIT

Jochen Feldmann Javier García de Abajo

LMU CSIC

Hermann Gaub Lee Josephson

LMU Massachusetts General Hospital

Nicholas Kotov Hedi Mattoussi

University of Michigan Florida State University

Paul Mulvaney Christopher Murray

University of Melbourne University of Pennsylvania

Itamar Willner Paul Weiss

University of Jerusalem University of California

Nanognostics

Emmanuel Bois Harri Härma

Cezanne SA University of Turku

Loïc Charbonnière Niko Hildebrandt

CNRS Strasbourg Université Paris-Sud 11

Piotr Cywinski Thomas Hug

Universität Potsdam Charité Berlin

James Delehanty Wolfgang Parak

Naval Research Laboratory Philipps Universität Marburg

Richard Dennis Itamar Willner

Edinburgh Instruments University of Jerusalem

Jens Dernedde
Charité Berlin

André Geßner
Fraunhofer IAP
Herodot

Efrat Lifshitz Dries van Thourhout

Technion IMEC

Rolf Koole Alexander Efros

Philips Naval Research Laboratory

Rainer Mahrt
IBM

Dendreamers

Takuzo Aida Juozas Grazulevicius

University of Tokyo Kanuas University of Technology

Didier Astruc Georg H. Mehl

University Bordeaux University of Hull

Carlos Cruz Joachim Stumpe

Institute of Superior Technology Fraunhofer Institut

Frans Dekker Teresa Sierra

IDREALIZER University of Zaragoza

Demetri Photinos José Luis Serrano

University of Patras University of Zaragoza

Lluís Ballell-Pages Prof. Dirk J. Broer

GlaxoSmithKline University of Eindhoven

Bertrand Donnio
CNRS
PROGRAM
 PROGRAM
MONDAY Nanognostics MONDAY Herodot TUESDAY WEDNESDAY THURSDAY FRIDAY Dendreamer
9:00- 9:00- 9:00- 9:00- 9:00- 9:00-
Opening Opening Opening P. Mulvaney F. Stellacci Opening
9:05 9:15 9:15 9:45 9:45 9:05
9:05- Nanognostics 9:15- 9:15- 9:45- 9:45- 9:05-
E.Lifshitz T.Aida R. Levy A.G. Kanaras D. Astruc
9:15 Introduction 10:00 9:55 10:05 10:05 9:50
9:15- 10:00- 9:55- 10:05- 10:05- 9:50- J.L. Serrano / T.
E. Bois A. Houtepen V. Puntes Y. Vida A.Christofidou
9:45 10:45 10:15 10:15 10:15 10:20 Sierra
9:45- 10:15- 10:15- 10:15- 10:20-
J. Dernedde N.T.K. Thanh W.Heiss J. Stumpe G.H. Mehl
10:15 10:25 10:25 10:25 10:50
10:15-
I. Willner
10:45
COFFEE BREAK / COFFEE BREAK / COFFEE BREAK /
COFFEE BREAK COFFEE BREAK COFFEE BREAK
Posters Posters Posters
11:15- 11:15- 11:00- 11:00- 11:00- 11:20-
L.Charbonniere R.Koole N. Kotov H.Mattousi L.Josephson B. Donnio
11:45 12:00 11:45 11:45 11:45 11:50
11:45- 12:00- D. 11:45- 11:45- 11:45- 11:50-
W. Parak A.Cabot K. Yu W.H. Evers J.Grazulevicius
12:15 12:20 Vanmaekelbergh 12:05 12:05 12:05 12:20
12:15- 12:20- 12:05- 12:05- 12:05- 12:20-
P. Cywinski Y. Justo Z. Hens L. Siebbels M. Kovalenko C. Cruz
12:45 12:40 12:25 12:25 12:25 12:50
12:40- 12:25- 12:25- 12:25-
A. Hassinen A.Laromaine K.Manthiram A.K. Herrman
13:00 12:35 12:35 12:35
12:35- 12:35- 12:35-
P. Reiss H. Virieux C. Giansante
12:45 12:45 12:45
12:45- 12:45- M.J. Ruedas 12:45-
J.J. Eilers A. Mews
12:55 12:55 Rama 12:55

LUNCH LUNCH LUNCH LUNCH LUNCH LUNCH

14:00- 14:00- 15:00- 15:00- 15:00- 13:50-

A. Geßner R.Mahrt C. Murray H. Gaub I. Willner J. Stumpe
14:30 14:45 15:45 15:45 15:45 14:20
 MONDAY Nanognostics MONDAY Herodot TUESDAY WEDNESDAY THURSDAY FRIDAY Dendreamer
14:30- 14:45- 15:45- 15:45- 15:45- 14:20-
H. Härma S. Carillo J. Veinot C. Rehbock L. Carbone D. Photinos
15:00 15:05 16:05 15:55 16:05 14:50
15:00- 15:05- 16:05- 15:55- 16:05- 14:50-
R. Dennis B.Siebers B.H. Juarez N. Waiskopf C. Klinke D. Broer
15:30 15:25 16:25 16:05 16:25 15:35
15:25- 16:25- 16:05- 16:25- 15:35-
D.v.Thourhout R.Krahne A. Ponti D. Meng-Qiao L. Ballell
16:10 16:35 16:25 16:35 16:05
16:25- 16:05-
A. Rogach F. Dekker
16:35 16:35
16:35-
J.L. Serrano
16:40
COFFEE BREAK / COFFEE BREAK /
COFFEE BREAK COFFEE BREAK COFFEE BREAK COFFEE BREAK
Posters Posters
16:00- 16:40- 17:30- 17:30- 17:00-
N. Hildebrandt D. Grodzinska J. Feldmann P. Weiss M. Bawendi
16:30 17:00 18:15 18:15 17:45
16:30- 17:00- 18:15- 18:15- 17:45- J. García de
J. Delehanty A. Khetubol P. Borri T. Kipp
17:15 17:20 18:25 18:25 18:30 Abajo
17:20- 18:25- 18:25- 18:30- Presentation
17:15 Closing A. Efros C.Sangregorio K. Boldt
18:05 18:35 18:35 18:40 NANAX 6
ACS Poster
17:30- NANOGNOSTICS 18:40-
18:05 Closing Awards &
19:30 internal Meeting 18:50
Conclusions
Closed meeting
Herodot partners
18:15
(practical
matters)
19:30- 19:30- 19:30- 19:30- CONGRESS 19:30-
DINNER DINNER DINNER DINNER 20:30 DINNER
22:30 22:30 22:30 22:30 DINNER 22:30
 MONDAY NANOGNOSTICS
9:00-9:05 Opening
9:05-9:15 Nanognostics Introduction
9:15-9:45 E. Bois Quantum dots for multiplexed diagnostics - An industrial perspective
9:45-10:15 J. Dernedde Evaluation of Biomarkers for Alzheimer’s Disease by a FRET-based Detection System
10:15-10:45 I. Willner Quantum dot-based sensing platforms
10:45-11:15 COFFEE BREAK
Luminescent Lanthanide complexes for antibody labelling and detection of Alzheimer disease
11:15-11:45 L. Charbonnière
biomarkers
11:45-12:15 W. Parak Optical Sensing of Small Ions with Colloidal Nanoparticles
12:15-12:45 P. Cywinski Lanthanide-to-Quantum Dot Förster Resonance Energy Transfer in protein detection
12:45-14:00 LUNCH
14:00-14:30 A. Geßner Highly sensitive FRET-immunoassays for multiparameter detection
Multitask Mix-and-Measure Luminescence Nanoparticle Methods for Sensitive Quantification and
14:30-15:00 H. Härma
Aggregation of Biomaterial and Polymers
15:00-15:30 R. Dennis Design and Applications of a Universal, Multi-Modality Fluorescence Reader
15:30-16:00 COFFEE BREAK
Terbium to quantum dot FRET in homogeneous sandwich immunoassays. Toward multiplexed early
16:00-16:30 N. Hildebrandt
diagnostics of Alzheimer’s disease.
16:30-17:15 J. Delehanty Cellular Applications of Semiconductor Quantum Dots:From Cytosolic Delivery to Multicolor Labeling
17:15 Closing
17:30-19:30 NANOGNOSTICS internal meeting
 MONDAY HERODOT
9:00-9:15 Opening
Multiple exciton fine structure in a single core/shell dot and rod, studied by magneto-optical micro-
9:15-10:00 E. Lifshitz
photoluminescence spectroscopy
10:00-10:45 A. Houtepen Photogeneration, difussion and decay of charge carriers in quantum-dot solids
10:45-11:15 COFFEE BREAK (Zona Andalucía)
11:15-12:00 R. Koole Quantum dots for lighting applications
12:00-12:20 D.Vanmaekelbergh Nanocrystal self-assembly: from hard spheres to particles with reactive bonding sites
12:20-12:40 Y. Justo Multiple dot-in-rod PbS/CdS heterostructures with high photoluminescence quantum yield in the near infrared
12:40-13:00 A. Hassinen In Situ Analysis of Ligands - The Solution NMR Toolbox for Nanoparticles
13:00-14:00 LUNCH (Comedor Doña Lola)
14:00-14:45 R. Mahrt Colloidal Quantum Dots and Organics: Towards Hybrid Nanostructures
14:45-15:05 S. Carillo Electronic structure and optical properties of PbSe/CdSe core-shell quantum dots
15:05-15:25 B. Siebers Spin Dynamics in CdSe/CdS colloidal nanocrystals
15:25-16:10 D. van Thourhout Quantum dots in silicon photonics
16:10-16:40 COFFEE BREAK (Zona Andalucía)
16:40-17:00 D. Grodzinska Two-Fold Emission From the S-Shell of PbSe/CdSe Core/Shell Quantum Dots
17:00-17:20 A. Khetubol Hole Mobility in Polyvinylcarbazole Doped with CdSe:ZnS Core-Shell Quantum Dots
17:20-18:05 A. Efros Efficiency of Multi-exciton Generation in Quantum Confined Nano-structures
18:05 Closing
18:15 Closed meeting Herodot partners (practical matters)
20:00 Sangría (Zona Andalucía)
19:30-22:30 DINNER (Comedor Doña Lola)
 TUESDAY
Session I: Chairman: Dr. P. Rivera-Gil
9:00-9:15 Opening
9:15-9:55 T. Aida Advanced Molecular Assembly for Functional Materials
9:55-10:15 V. Puntes Carving at the Nanoscale: Galvanic Replacement versus Kirkendall Effect at Room Temperature
10:15-10:25 N.T.K. Thanh Next Generation of Magnetic Nanoparticles for Biomedical Applications
10:25-11:00 COFFEE BREAK + POSTERS (Salón Real)
11:00-11:45 N. Kotov Self-assembly of Nanoparticles
11:45-12:05 A. Cabot Bottom-up processing of nanocomposites for thermoelectric applications
12:05-12:25 Z. Hens Absorption enhancement in colloidal quantum dot monolayers through coherent dipolar coupling
12:25-12:35 A. Laromaine Peptides on gold as protease sensors and for supramolecular stamping
12:35-12:45 P. Reiss Charge transport in conjugated polymer/semiconductor nanocrystals hybrid thin films
12:45-12:55 J.J. Eilers Synthesis and characterisation of Mn-doped ZnTe Magic Size Nanocrystals
12:55-15:00 LUNCH (Comedor Doña Lola)
Session II: Chairman: Dr. S. Carregal-Romero
15:00-15:45 C. Murray Synthesizing multi-component nanocrystal superlattices and fabricating multifunctional nanocrystal devices
Silicon Nanocrystals: Why do some colloidal Si-NCs exhibit size dependent photoluminescence while others simply
15:45-16:05 J. Veinot
have the blues?
Thermo-responsive Platforms with Quantum Dots and Au Nanoparticles Trapped by Optical Tweezers; Synthesis and
16:05-16:25 B.H. Juarez
Optical Studies
16:25-16:35 R. Krahne Charge Transport in nanoscale “all-inorganic” networks of CdSenanorods linked by Au domains
16:35-17:30 COFFEE BREAK + POSTERS (Salón Real)
Session III: Chairman: Dr. V. Grazú
17:30-18:15 J. Feldmann Focusing Light on Gold Nanoparticles
18:15-18:25 P. Borri Spin-flip limited exciton zero-phonon line dephasing in CdSe colloidal quantum dots
18:25-18:35 C. Sangregorio Nanostructures for Magnetic Imaging and Therapy
19:30-22:30 DINNER (Comedor Doña Lola)
 WEDNESDAY
Session I: Chairman: Dr. V. Puntes
9:00-9:45 P. Mulvaney CdTe Nanocrystal based Solar Cells
9:45-10:05 R. Levy Photothermal microscopy as a new imaging tool for visualisingthe cellular uptake of iron oxide nanoparticles
10:05-10:15 Y. Vida JOINING nanomaterials AND DENDRIMERS: applications in diagnostics
From a high precision synthesis of monodisperse Indium, Tin, and Indium-Tin colloidal nanocrystals to transparent
10:15-10:25 W. Heiss
Indium-Tin-Oxide nanoelectrodes
10:25-11:00 COFFEE BREAK + POSTERS (Salón Real)
Session II: Chairman: Dr. N. Gómez-Bastús
11:00-11:45 H. Mattousi Functional nanocrystals as tunable platforms for chemical reactions, sensing and imaging
11:45-12:05 K. Yu CdSe Magic-Sized Nuclei, Magic-Sized Nanoclusters and Regular Nanocrystals: Monomer Effects on Nucleation and Growth
12:05-12:25 L. Siebbels Formation and dynamics of multiple electron-hole pairs in quantum dot arrays and nanorods
12:25-12:35 K. Manthiram Tunable Localized Surface Plasmon Resonances in Tungsten Oxide Nanocrystals
Surface and Interface Chemistry of InP/ZnS Nanocrystals Unraveled by Coupling X-RayPhotoelectron and NMR
12:35-12:45 H. Virieux
Spectroscopies
M.J. Ruedas
12:45-12:55 Applications of the photoluminescence lifetime of Quantum Dot to sensing
Rama
12:55-15:00 LUNCH (Comedor Doña Lola)
Session III: Chairman: Dr. A. Guerrero Martínez
15:00-15:45 H. Gaub Functional Surface Assembly by Single-Molecule Cut-and-Paste
15:45-15:55 C. Rehbock Protein conjugation of ligand-free gold nanoparticles by laser ablation in liquid flow
15:55-16:05 N. Waiskopf LABELING CHOLINESTERASES USING SEMICONDUCTOR NANOPARTICLES FOR BIOLOGICAL APPLICATIONS
16:05-16:25 A. Ponti Pebbles: A Software for Accurate, Unbiased, and Fast Measurement of Nanoparticle Morphology from TEM Images
Hierarchical Structures of SnO2-based Nanoparticles of Different Morphologies for Gas-Sensing, Lithium Ion Batteries,
16:25-16:35 A. Rogach
and Photocatalysis
16:35-17:30 COFFEE BREAK + POSTERS (Salón Real)
17:30-18:15 P. Weiss Precise Assemblies, Clusters, Superatoms, and Cluster-Assembled Materials
18:15-18:25 T. Kipp Optical Spectroscopy of Single Semiconductor Nanocrystals Close to Gold Nanoparticles
18:25-18:35 K. Boldt Characterization of Quantum Dot PEO Ligand Shells by Fluorescence Quenching
19:30-22:30 DINNER (Comedor Doña Lola)
 THURSDAY
Session I: Chairman: Dr. P. del Pino
9:00-9:45 F. Stellacci From striped to Janus particles: characterization and applications
9:45-10:05 A.G. Kanaras Advanced colloidal nanoparticles control cellular functions.
10:05-10:15 A. Christofidou Bioactive nanoparticle targeting of neurons
10:15-10:25 J. Stumpe Holographic patterning of organic-inorganic nanocomposites
10:25-11:00 COFFEE BREAK + POSTERS (Salón Real)
Session II: Chairman: Dr. D. Alcántara
11:00-11:45 L. Josephson MR and magnetic particles: imaging viscosity, reactive antibodies, and the ongoing PCR reaction
11:45-12:05 W.H. Evers Entropy and energy driven self-assembly of semiconductor nanocrystals.
12:05-12:25 M. Kovalenko Novel Strategies for Combining Nanocrystals, Molecules and Clusters, into Functional Inorganic Solids
Structural aspects and application perspectives of highly porous metallic aerogels produced by template-free 3D self
12:25-12:35 A.K. Herrman
assembly
12:35-12:45 C. Giansante Hybrid Organic/Inorganic Colloidal Quantum Dots for Improved Photoconductivity
12:45-12:55 A. Mews Optical and electrical properties of individual CdSe nanowires
12:55-15:00 LUNCH (Comedor Doña Lola)
Session III: Chairman: Dr. A. Kanaras
Programmed Nanostructures of Metal and Semiconductor Nanoparticles: From Molecular Machinery Topologies to
15:00-15:45 I. Willner
Sensor Applications
15:45-16:05 L. Carbone Phase- and Size-Controlled Synthesis of CuxS Colloidal Nanocrystals with Tunable Near-IR Plasmonic Properties
16:05-16:25 C. Klinke Truly two-dimensional colloidal nanocrystals
Synthesis and Characterization of Widely Tunable Photoluminescence Emission CdTe/CdS Core/Shell Quantum
16:25-16:45 D. Meng-Qiao
Dots under Fully Ambient Atmosphere
16:45-17:15 COFFEE BREAK (Zona Andalucía)
17:15-18:00 M. Bawendi TBA
J. García de
18:00-18:45 Graphene plasmonics
Abajo
18:45-18:55 Presentation NANAX6
18:55-19:05 ACS Poster Awards & Conclusions
20: 30 CONGRESS DINNER (Salón Real)
 FRIDAY – DENDREAMER
9:00-9:05 Opening
9:05-9:50 D. Astruc Nanoparticles and Metallodendrimers as Sensors and Catalysts
J.L Serrano/T.
9:50-10:20 Liquid Crystal Dendrimers Based Functional Systems: From Conductive Materials to Gene Carriers
Sierra
10:20-10:50 G.H. Mehl The design and control of the self-assembly behaviour of liquid crystal froming gold nanoparticles
10:50-11:20 COFFEE BREAK (Zona Andalucía)
11:20-11:50 B. Donnio Fullerene liquid-crystal dendrimers and core-shell nanohybrid liquid crystal dendrimers: towards new applications
11:50-12:20 J. Grazulevicius Functional electroactive dendrimers for (opto)electronic and applications
12:20-12:50 C. Cruz NMR relaxation studies of liquid crystal dendrimers
12:50-13:50 LUNCH (Zona Andalucía)
13:50-14:20 J. Stumpe Light-induced orientation and mass transport of dendritic materials
14:20-14:50 D. Photinos Modeling of Dendromesogens: Self Organisation and Phase Transitions, Alignment and nanoconfinement
Liquid crystal networks and self-organizing hydrogels: nanotechnology towards soft actuators and nanoporous
14:50-15:35 D. Broer
systems
15:35-16:05 L. Ballell Research career and drug attrition
16:05-16:35 F. Dekker Additional skills development in scientific projects (beyond the ITN)
16:35-16:40 J.L. Serrano Closing
16:40-17:10 COFFEE BREAK (Zona Andalucía)
19:30-22:30 DINNER (Comedor Doña Lola)
ABSTRACTS


$%675$&76
 Tuningthepostfocusedsizeofcolloidalnanocrystals
bythereactionrate:fromtheorytoapplication.
SofieAbé1,RichardK.apek2,BramDeGeyter1andZegerHens1
1
PhysicsandChemistryofNanostructures,GhentUniversity,Krijgslaan281ͲS3,9000Gent,Belgium
andCenterforNanoandBiophotonics
2
SchulichFacultyofChemistry,RussellBerrieNanotechnologyInstitute,Technion,Haifa32000,Israel

The synthesis of colloidal semiconductor nanocrystals or quantum dots (QDs) with sharp size
distributions at a desired mean size is of fundamental importance for the characterization of their
materials properties and their use in applications. Size control by adjusting the reaction time is
frequentlyusedandsuccessful,butimpliesareducedreactionyieldforsizesreachedbeforetheend
of the size distribution focusing. Here, we show that adjusting the reaction rate in a hot injection
synthesis is a viable strategy to tune the diameter of colloidal nanocrystals at the end of the size
distribution focusing, i.e., the postfocused diameter. Our approach is introduced by synthesis
simulations, which describe  nucleation and growth of colloidal nanocrystals from a solute or
monomer that is formed in situ out of the injected precursors. These simulations, which yield
experimentally meaningful quantities such as diameter, time and concentration, indicate that the
postfocused diameter is reached at almost full yield and that it can be adjusted by the rate of
monomerformation.

We implement this sizeͲtuning strategy using a particular CdSe quantum dot synthesis that shows
excellentagreementwiththemodelsynthesis.Afterdemonstratingthatthereactionratedependsin
first order on the Cd and Se precursor concentration, the proposed strategy of size control is
exploredbyvaryingtheprecursorconcentration.Thisenablesthesynthesisofcolloidalnanocrystals
withapredefinedsizeatalmostfullyieldandsharp sizedistributionswithdiametersrangingfrom
2.8to4.1nm.Inaddition,wedemonstratethatthesametuningstrategyappliestothesynthesisof
CdSquantumdots. This result ishighly relevantespecially inthe context ofreaction upscaling and
automation. Moreover, the results obtained challenge the traditional interpretation of the hot
injection synthesis, in particular the link between hot injection, burst nucleation, and sharp size
distributions.

reference:

Abe,S.;apek,R.K.;DeGeyter,B.;Hens,Z.,TuningthePostfocusedSizeofColloidalNanocrystalsby
theReactionRate:FromTheorytoApplication,ACSNano,2012,6(1),42–53
 Usingtheacidconcentrationandchainlength
asatuningstrategyinthehotinjectionsynthesis,
anexperimentalandtheoreticalanalysis.
SofieAbé1,RichardK.apek2,BramDeGeyter1andZegerHens1
1
PhysicsandChemistryofNanostructures,GhentUniversity,Krijgslaan281ͲS3,9000Gent,BelgiumandCenter
forNanoandBiophotonics
2
SchulichFacultyofChemistry,RussellBerrieNanotechnologyInstitute,Technion,Haifa32000,Israel

Inmanyhotinjectionsynthesesforcolloidalnanoparticles,sizecontrolisachievedbystoppingthe
reactionduringgrowth.Thisgivesaccesstohighlymonodispersesamplesofnanoparticles,butoften
implies a reduction of the synthesis yield. Here, we discuss how the concentration of excess
carboxylic acid and the acid chain length affects the mean size of an ensemble of colloidal
nanoparticlesattheendofthereactiondrivengrowthregime(postfocuseddiameter)andtowhat
extentadjustingitcanbeusedforsizetuning.WeshowthatforaparticularCdSequantumdot(QD)
synthesis,anincrease inthiscarboxylicacidconcentrationordecreaseinthechainlength leadsto
largerpostfocuseddiametersoftheQDsandviceversawhilenothavinganyeffectontheformation
rateofCdSe.Furthermore,weobservedadecreaseinthenumberofQDsthatareformedwithan
increasing amount of acid or reduced acid chain length, indicating that the change in postfocused
diameteroriginatesfromadistributionofthemonomeroveradifferentnumberofparticles.

These experimental results are compared to a comprehensive computational model of nucleation
andgrowthwedevelopedearlier1andwhichshowsgoodagreementwiththeabovementionedCdSe
QD synthesis. We find that our observations can be explained theoretically by a variation of the
solubility of the monomer as this directly affects the balance between nucleation and growth and
therefore changes the amount of QDs that are formed during a hot injection synthesis. This
interpretationhelpsinunderstandingliteratureresultsonotherQDsyntheses2Ͳ4suggestingthatour
discussiongoesbeyondthisparticularCdSesynthesis.Whenconsideringsizetuning,ourexperiments
andexamplesinliteratureindicatethatthepostfocusedsizecanbetunedbytuningthemonomer
solubility, however, the approach has limited use for reaction upscaling or automation. The
importantdisadvantageistheincreaseinsizedispersionforhighcarboxylicacidconcentrationsand
shortchainlengths,whichisofsuchmagnitudethatthesynthesizedQDsarenotusefulforhighend
applications.Thismakessizetuningofthepostfocuseddiameterbyadjustingtheacidconcentration
orchainlengthnotaviablestrategy,opposedtoourpreviouslyreportedtuningbythereactionrate1.

references:

1. Abe,S.;apek,R.K.;DeGeyter,B.;Hens,Z.,TuningthePostfocusedSizeofColloidalNanocrystalsbytheReaction
Rate:FromTheorytoApplication,ACSNano,2012,6(1),42–53.
2. Yu,W.W.;Peng,X.G.,FormationofhighͲqualityCdSandotherIIͲVIsemiconductornanocrystalsinnoncoordinating
solvents:Tunablereactivityofmonomers.AngewandteChemieͲInternationalEdition2002,41(13),2368Ͳ2371.
3. Bullen,C.R.;Mulvaney,P.,NucleationandgrowthkineticsofCdSenanocrystalsinoctadecene.NanoLetters2004,4
(12),2303Ͳ2307.
4. Owen,J.S.;Chan,E.M.;Liu,H.;Alivisatos,A.P.,PrecursorConversionKineticsandtheNucleationofCadmium
SelenideNanocrystals.JournaloftheAmericanChemicalSociety2010,132(51),18206Ͳ18213.
 Multifunctional Radioactive 111In Decorated Radioactive Au-198 Nanoparticles
A. M. A. Ahmed, Z. Ali, J. M. Montenegro, N.C. Bigall, W. Parak,
Philipps-Universität Marburg, Marburg, Germany

Nanosytems which combine different functionalities/modalities within a single system

known as multifunctional nanomaterials offer exceptional opportunities in many fields
especially fundamental biology, imaging and biomedical applications diagnosis. A variety
of theragnostic nanomaterials is under current investigation, for example ones combining
several diagnostic and therapeutic features such as contrast enhancing properties for
magnetic resonance imaging and hyperthermia, radioactivity and fluorescence.
In this work, gold nanoparticles were synthesized in a non-polar solvent and coated with
an amphiphilic polymer in order to transfer them into aqueous solution. By
electrophoresis and PD-10 column the nanoparticles were purified. Subsequently, neutron
198
irradiation was applied in order to yield radioactive Au nanoparticles. In the next step,
198
the as-synthesized Au Nanoparticles were decorated with radioactive In111. The
resulting nanoparticles were characterized by optical spectroscopy, transmission electron
microscopy, gamma ray spectroscopy and dynamic light scattering.

1. Ali, Z., et al., Multifunctional Nanoparticles for Dual Imaging. Analytical Chemistry.
2011, 83(8): p. 2877.
2. Pellegrino, T., et al., Hydrophobic nanocrystals coated with an amphiphilic polymer
shell: a general route to water soluble nanocrystals. Nano Letters. 2004, 4(4): p. 703.
3. Brust, M., et al., Synthesis of thiol-derivatised gold nanoparticles in a two-phase
liquid-liquid system. J. Chem. Soc., Chem. Commun. 1994, 1994: p. 801.
 Geometry effects of linear and nonlinear optical properties in
0D-2D II-VI semiconductor nanocrystals

A. Achtstein1,+, J.Hennig1, A. Schliwa2, A. Prudnikau3, M. Hardzei3, M. Artemyev3, U. Woggon1

1
Institute of Optics and Atomic Physics, Technical University of Berlin, Berlin, Germany
2
Institute of Solid State Physics, Technical University of Berlin, Berlin Germany
3
Institute for Physico-Chemical Problems, Belarussian State University, Minsk, Belarus


Semiconductor nanoparticles have unique properties due to spatial confinement and shape control
affecting the exciton wave function in the linear as well as in the nonlinear optical regime. The
electronic structure of strongly confined semiconductor materials with high nonlinear coefficients
makes them ideally suited for two-photon absorption (TPA) based effects, e.g. for 3D optical data
storage elements or biological cell imaging. The highly localized two-photon excitation and the
nanometer size of colloidal semiconductor nanoparticles allow for their application for storage media
of Tbits/cm3. Other applications include optical switching in communication networks, optical limiting
for damage prevention in fiber networks and high resolution two-photon luminescence (TPL) in
biology.

In this work we study optical nonlinearities and exciton-phonon coupling in colloidal 0D to 2D zinc-
blende-type (ZB) and wurtzite-type (WZ) semiconductor nanocrystals, i.e. spheres, rods and platelets.
Compared to conventional hexagonal nanoparticles (NPs), ZB NPs exhibit a much smaller electron
phonon interaction associated with less phonon broadening at room temperature. This makes them
very attractive for narrow band emitters or gain media. Single particle spectroscopy is applied to
overcome inhomogeneous broadening in ensembles and reveals an excitonic substructure in the
photoluminescence emission spectra (PL). Temperature-dependent measurements of the PL spectra
show a small exciton-LO-phonon coupling strength in confined ZB systems and therefore a small
phonon broadening in the single CdSe platelet emission. We present numerical calculations of the
platelets quantum well exciton energies including Coulomb interaction and compare the obtained
energies with experiments. The performed calculations aim is to understand the influence of thickness
quantization and lateral size variation on the excitonic states of 2D-nanoplatelets. Due to a large
surface to volume ratio, the exciton energies show a strong impact of dielectric confinement. Coulomb
interaction corrected numerical simulations reproduce this effect. The thickness quantization to integer
monolayers leads to an only lateral size distribution, resulting in narrow PL emission.

To understand the nonlinear effects at a nanoscale, it is necessary to study the spatial confinement and
its influence on the nonlinear optical properties. The expected strong geometry and size dependence of
the TPA cross section and refractive index has been tested by measuring a series of colloidal CdS dots
and rods starting from a near 0D system to long 1D nanorods. A pronounced change of volume
normalized TPA absorption cross sections at the transition from dots to elongated rods has been
found. While the bulk TPA coefficient of CdS is 17GM/nm3, it grows in spherical CdS nanocrystals to
1.4x102 GM/nm3 and becomes 2.3x103 GM/nm3 in elongated CdS nanorods of diameter of 3 to 4 nm
and aspect ratio from 1:3 to 1:10. The contributions of spatial confinement and local field effects of
the dielectric environment are evaluated separately to get a deeper insight in the pure confinement
effect on TPA. Additional Two-Photon Luminescence Excitation (TPLE) measurements reveal the
spectral dependence of the TPA coefficients in those nanosystems for both resonant and non resonant
excitation. The results obtained from all three different methods show good agreement and support
the obtained values and size and geometry dependence of the TPA coefficients of CdS dots and rods.

+ Author for correspondence: [email protected],

 Advanced Molecular Assembly for Functional Materials

Takuzo Aida

Department of Chemistry and Biotechnology, School of Engineering

The University of Tokyo and Riken Advanced Research Institute
[email protected]

Owing to a tremendous progress in

supramolecular chemistry, one can now
construct and tailor a variety of desired
nanostructures, where assembling events
involved mostly operate thermodynamically.
On the other hand, if one may consider
developing materials for practical applications,
we certainly need to design kinetically
preferred hierarchical structures. However,
there is no rational molecular design strategy
for this issue.
Here we report some of our recent achievements related to this issue. The first
topic focuses on how one can translate a tiny molecular motion into a macroscopic
motion.[1] We found that, by hot pressing using unidirectionally drawn Teflon sheets,
a polymer brush containing triply connected azobenzene units in its side chains form
a hierarchically ordered bimorph film, where all the cylindrical brush objects align
homeotropically with respect to the film plane, and the film shows a macroscopic
photomechanical motion. The second topic features the development of 'aqua
material', characterized by an ultralow content of organic components and an
ultrahigh content of water.[2] This material can be prepared by mixing in water clay
nanosheets and a dendritic molecular binder with sticky guanidinium ion
functionalized dendron wedges on both sides of a poly(ethylene glycol) spacer, giving
rise to the formation of a well-developed 3D network over a macroscopic length scale.
The third topic features our quite recent achievement on the formation of a linear
semiconducting heterojunction by stepwise supramolecular polymerization.[3], [4]

This sequential control in supramolecular polymerization gives a clue for how to

escape from a thermodynamic equilibrium.

[1] Wang et al., Nature 2010, 463, 339. [2] Hosono et al., Science 2010, 330, 808.
[3] Wei et al., Science 2011, 334, 340. [4] Aida et al., Science 2012, in press.
PCR monitoring by MR: an ultrasensitive method for DNA detection with magnetic
nanoparticles.
David Alcantara1,2, Yanyan Guo1, Hushan Yuan1, Lee Josephson1.
1)Center For Translational Nuclear Medicine and Molecular Imaging, MGH-Harvard Medical School, 149 13th
Street, Charlestown, MA 02129. Phone: 781:726-6478 FAX: 617-643-7212.
2)Centro Andaluz de Nanomedicina y Biotecnologia, Parque Tecnologico de Andalucia, c/Severo Ochoa 35,
29590 Campanillas, Spain. E-mail: [email protected]

Abstract: We hypothesized that a magnetic nanoparticle (NP) surface functionalized

with multiple DNA binding fluorochromes might react with DNA through a multivalent,
avidity-type reaction and yield a highly sensitive method for detecting DNA by the T2
relaxation time of water protons measured by Magnetic Resonance (MR) techniques.
Although oligonucleotides have been used to target NP’s to specific sequences on
nucleic acids123, the considerable literature on fluorochrome/nucleic
acid interactions has not been mined for potential nanoparticle (NP) targeting strategies.
Our study showed how a NP displaying a DNA-binding fluorochrome, bind in a
multivalent fashion to yield a highly sensitive, T2-based method of detecting DNA.
We synthesized the DNA-binding NP by attachment of the DNA-binding fluorochrome
TO-PRO 1 to the Feraheme (FH) NP using a “TO- PRO1 NHS ester”. TO-PRO 1
fluoresces when bound to DNA by intercalation. The resulting NP, termed FH-TO, had
9.9 TO-PRO 1’s per NP attached through a 6-carbon, flexible linker. FH-TO had r1 and r2
relaxivities of 23.3 and 122 (mM Fe sec)-1, respectively, and a size of 59.8±3.4 nm. The
parent FH nanoparticle had a zeta potential of -37.8±3 mV (pH 6) that was largely
preserved with the attachment of 9.9±1.4 TO-PRO 1's per NP; FH-TO’’s zeta potential
was still highly negative at -28.3±0.8 mV.
FH-TO was incubated with a wide range of DNA concentrations (0-10 ȝg/mL), and the
reaction monitored by a fluorescence increase, by a decrease in the T2 relaxation time,
and by an increase in aggregate size by light scattering. The hyperbolic curves obtained
with by fluorescence were fit to a single site-binding model, yielding apparent Kd’s of
5.86±1.20 ȝg/mL and of 3.62±0.25 ȝg/mL for TO-PRO 1 and FH-TO, respectively. Both
Kd’s by fluorescence were far higher than the Kd from T2 (0.0379±0.007 ȝg/mL).
Aggregate size exhibited a hook effect with a maximum size at 0.25 ȝg/mL.
Either light scattering or relaxometry can be used to determine aggregate formation in the
low DNA concentration range. However, relaxometry has two advantages: T2 is a
hyperbolic function of DNA concentration (no hook effect) and T2 is a radiofrequency-
based method (no light based interferences). With light scattering and hook effects, some
aggregate sizes (e.g. 200 nm) can reflect low or high concentrations and additional
measurements with diluted samples are required. The estimated sensitivity of DNA
detection by T2 was 27 fM DNA per a T2 change of 2.6 msec.
The high sensitivity of DNA detection, the thermal stability of FH-TO, and the broad
high dose plateau seen with T2 measurements (no hook) suggested FH-TO were used for
monitoring a PCR reaction, broadly expanding the scope of these preliminary results.

1
Josephson, L., Perez, J.M. & Weissleder, R.W. Angew.Chem. Int. Ed. 40, 3204-3206 (2001).
2
Perez, J.M., Josephson, L., O'Loughlin, T., Hogemann, D. & Weissleder, R. Nat Biotechnol 20, 816-820 (2002).
3
Rosi, N.L. et al. Science 312, 1027-1030 (2006).
 ZnO nanowires functionalized with chalcopyrite nanocrystals in ETA solar cells
Dmitry Aldakov*, Sylvia Sanchez, Valentina Ivanova and Peter Reiss
Laboratory of Molecular, Organic and Hybrid Electronics, INAC/SPrAM and
LETI/DTSI/SDEP/LDJ, CEA-Grenoble, France. E-mail: [email protected]

Extremely thin absorber (ETA) solar cells represent one of the most promising types of
semiconductor nanocrystals (NCs) photovoltaics. They are based on a nanostructured material
(typically a metal oxide) with a thin layer of deposited nanocrystals that efficiently absorb light. The
resulting cell is cheap because it uses only low-cost materials and processing steps by wet methods;
at the same time it is robust owing to the absence of liquid electrolytes. In the proposed talk we use
arrays of electrochemically synthesized ZnO nanowires as a nanostructured electrode.
In the majority of reported ETA solar cells the deposition of the NCs is carried out non-specifically, i.e.
either by their in situ synthesis or by adsorption, which considerably limits the organisation,
transport and hence the performance. Our alternative approach is to use tailor-made chemical
linkers to graft the NCs in the most controlled and homogeneous manner. These linkers were
designed to specifically functionalise the surface of ZnO, while avoiding its corrosion as observed in
the case of carboxylic acids. Such functionalisation of the electrode surface opens a versatile way to
deposit different types of NCs without the need of using a preliminary ligand exchange step. We
successfully grafted CuInS2 and CuInSe2 NCs, which have the advantages of high absorption
coefficients and appropriate band gap values (1-1.5 eV). Our method leads to a perfect
homogeneous coating of the ZnO nanowires by the NCs (Fig. 1). Thickening the NCs’ layer using layer-
by-layer deposition permits to enhance and adjust the light absorption. Furthermore, the charge
transfer at the NC / ZnO interface is optimized by varying the length and nature of the organic linker.
Solar cells obtained after deposition of a CuSCN (hole transport) layer and a metal electrode clearly
exhibit the photovoltaic effect under simulated solar light. Finally, we illustrate pathways for the
performance improvement of ETA solar cells.

500 nm

Fig. 1: ZnO nanowires covered with a monolayer of CuInS2 nanocrystals.

 Adsorption Study of QDs in Self- assembled Polymer and Surfactant Films

T. Alejo, M. D. Merchán, and M. M. Velázquez

Departamento de Química Física, Universidad de Salamanca, Plaza de los Caidos

s/n,Salamanca 37008, Spain

[email protected].

The study of the adsorption of nanomaterials onto surfaces has attracted extensive interest
considering the importance of the interactions of nanoparticles with polymeric or biological templates.
Thin polymer and surfactant films are used for applications as microelectronic devices, solar cells,
sensors, biomaterials or as adhesives, lubrication and membranes. For nanocomposite material
applications is necessary to control the incorporation of nanoparticles into the polymer films, the surface
chemistry, spatial patterning and physical properties. Quantum dots (QDs) nanocrystals are particularly
interesting for its applications in bioanalytics and optoelectronics [1]. In this work, cationic gemini
surfactant C18H37 (CH3)2N+-(CH2)2-N+(CH3)2 C18H37, (18-2-18) and the Poly Anhydride Maleic
Octadecane (PMAO) polymer are used as self-assembled monolayers to anchor the QDs onto solid
substrates. Highly ordered films are built for these systems using the Langmuir–Blodgett (LB) technique
[2]. Previous to deposition, the thermodynamic properties of the Langmuir monolayers precursors of the
LB films were investigated by surface pressure-area ( -A) isotherms of the QDs monolayers and the
morphology of these films was observed by Brewster Angle Microscopy (BAM). Langmuir-Blodgett films
of QDs on solid substrates were characterized by Atomic Force Microscopy (AFM), Scanning Electron
Microscopy (SEM) and Transmission Electron Microscopy (TEM).

To understand the role of the interactions in the LB structures obtained, we have also studied
the adsorption of QDs on films of polymer, surfactant and on polymer–surfactant mixtures. Thus, Quartz
Cristal Microbalance with Dissipation monitoring (QCM-D) technique was employed to investigate the
thermodynamic parameters of nanoparticles self-assembly processes, measure the resulting thickness
and mass of the films and compare the self-assembly process under the different pattern systems
employed.

References

[1] Somers, R.C.; Bawendi, M.G.; Nocera, D.G. Chem Soc Rev; 36, (2007) 579.
[2] Alejo,T. ; Merchán, M.D.; Velázquez, M.M Thin Solid Films, 519 (2011) 5689–5695.

Acknowledgement:

The authors thank financial support from ERDF and MEC (MAT 2010/19727). T.A. wishes to
thank European Social Fund and Junta de Castilla y León for the FPI grant. The authors want to thank
especially to Drs J.A. Pérez-Hernández and J. Hernández-Toro for the AFM measurements and
C.L.P.U. (University of Salamanca) for the AFM facility.
 Proton NMR study on the Nu-Nx phase transition in CB-C9-CB liquid crystal
A. Aluculesei1, 2, C. Cruz1, 2, P. J. Sebastião1,2, F. Vaca Chavez1,2, M. G. Tamba3, A. Kohmeier3,

G. H. Mehl3
1
IST, Technical University of Lisbon, Av. Rovisco Pais, 1, 1049-001 Lisboa, Portugal
2
CFMC, Av. Prof. Gama Pinto, 2, 1649-003 Lisboa Portugal
3
Dep. of Chemistry, University of Hull, Cottingham Road, Hull, HU6 7RX, United Kingdom

Dendrimers are synthetic supermolecules with regular, hyperbranched architectures,

typically monodisperse [1]. Those molecules have become the most promising class of
synthetic materials for gene transfection and are promising as drug delivery agents,
nanocatalysts, magnetic resonance imaging [1, 2]. Liquid crystal dendrimers combine the
properties of dendrimers with the anisotropic characteristics of mesogenic molecules [3].
The dimer ensemble model of dendromesogens focuses on the sub-dendritic units that give
rise to the mesomorphic behaviour of the dendrimers. The theoretical and experimental
study of interacting LC dimers with spacers of different lengths is an important step to the
understanding of the behaviour of the more complex dendritic structure [4]. In the present
work, the compound CB-C9-CB (a dimer composed by two cyanobiphenyl (CB)
mesogenic units linked by C9 alkyl chain) was studied by a combination of conventional
and fast field-cycling NMR techniques. This compound was studied before by different
techniques namely: POM, DSC, and XRD that revealed a phase transition between two
different nematic phases [6]. The system was investigated by proton NMR spectroscopy
and relaxation in order to understand the relation between phase structure and molecular
dynamics in the two mesophases. Angular dependent proton spectra were collected at the
frequency 15.13 MHz by rotating the sample perpendicular to the magnetic field, for
different angles. From the first analysis a clear difference between the molecular dynamics
in the two mesophases due to the respective specific molecular packing becomes evident.
Acknowledgments: This work was partially supported by the European Comission under
7th Framework Programme through project PEOPLE-2007-1-1-ITN-215884
(Dendreamers)

References
[1] G. R. Newkome, C. N. Moorefield, and F. Vögtle, Dendrimers and Dendrons: Concepts, Syntheses,
Applications Wiley-VCH, Weinheim, (2009).
[2] Istvan J. Majoros, James R. Baker JR Dendrimers-Based Nanomedicine. 27 Warren Street, Suite 401-402,
Hackensack, NJ 07601: Pan Stanford Publishing Pte. Ltd., (2008).
[3] V. Percec, W. D. Cho, and G. Ungar, J. Am. Chem. Soc. 122, 10273 (2000); J.-M. Rueff, J. Barbera, B.
Donnio, D. Guillon, M. Marcus, and J. L. Serrano, Macromolecules 36, 8368 (2003).
[4] A. G. Vanakaras, D. J. Photinos, J. Mater. Chem. 15, 2002 (2005).
[5] Ronald Y. Dong, Nuclear Magnetic Resonance Spectroscopy of Liquid Crystals, Ed. British Library
Cataloguing, (2010).
[6] V. P. Panov, M. Nagaraj, J. K. Vij, Yu P. Panarin, A. Kohlmeier, M. G. Tamba, R. A. Lewis and G.H.
Mehl, Phys. Rev. Lett. 105, 167801 (2010); V. P. Panov, R. Balachandran, M. Nagaraj, J. K. Vij, M. G. Tamba,
A. Kohlmeier, G. H. Mehl, Appl Phys. Lett. (2011), 99, 261903
Fluorescence of Surface-Charged CdSe/ZnS Quantum Dots in Apolar Solvents

Nicole Amecke and Frank Cichos

Molecular Nanophotonics Group, University of Leipzig, Germany

In several studies permanent dipoles and charges have been found on single colloidal quantum dots
(QDs), some of which are even present in apolar solution [1,2,3]. The influence of charges in and
close to the QD is generally predicted to be crucial to its fluorescence, introducing spectral shifts and
fluctuations in both radiative and non-radiative decay rates (stark shift, blinking, flickering). A direct
comparison of the fluorescence of these identified charged and neutral QDs, however, is still missing.
With a confocal microscope and an electrophoretic cell we are able to detect and separate charged
CdSe/ZnS QDs in apolar solvents when applying an electric field. Via spatially resolved fluorescence
detection and current measurements we can determine their charge polarity and the charged fraction
depending on size, surrounding solvent and ligand (hexadecylamine) excess. Also manipulation of this
charge at the electrodes is possible.
Charged and neutral QDs can be spatially separated and their fluorescence and spectra detected. As
differences are little, we suggest that the charge of the QD is located at some position at its outer
surface.

Left: Sketch of the electrophoretic cell on the objective.

Right: Time and voltage dependent fluorescence at a distance d from the ITO-electrode in toluene.
Positively charged particles are moving in the applied electric field.

[1] M. Cirillo, F.Strubbe, K.Neyts, Z. Hens, ACS Nano 5 (2), 1345-1352 (2011)
[2] E.V. Shevchenko, D.V. Talapin, N.A. Kotov, S. O’Brien, C.B. Murray, Nature 439, 55-59 (2006)
[3] M. Shim, P. Guyot-Sionnest, Journal of Chemical Physics 111 (15), 6956-6964 (1999)
 Environment sensitive fluorophore - A universal tool to chronicle dye location
on colloidal nanoparticle surface
Faheem Amin1, Dmytro Yushchenko2, Jose M. Montenegro1, Wolfgang J. Parak1,3*
1
Fachbereich Physik, Philipps Universität Marburg, Renthof 7, Marburg 35032,Germany.
2
Max Planck Institute for biophysical Chemistry, Emeritus Group Laboratory of Cellular
Dynamics, Am Faßberg 11, D-37077 Göttingen
3
Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps Universität
Marburg, Marburg, Germany

* Corresponding author: [email protected]

KEYWORDS: Nanoparticles, Polarity, sensor, fluorescence

Inorganic hydrophobically capped nanoparticles can be modified to make them water-soluble by

their embedding in an amphiphilic polymer shell. This polymer shell can be pre-functionalized
by the integration of organic fluorophores, which allows the observation of the nanoparticles
with fluorescence based techniques. The fluorophore could be either located more in the
hydrophobic part of the inner polymer shell, or on the hydrophilic surface pointing towards
solution. In this work we prepared gold nanoparticles decorated with the organic fluorophore FE,
4'-N,N-diethylamino-3-hydroxyflavone (FE), which possesses fluorescence sensitive to the
polarity and hydrogen-bonding properties of the surrounding local environment. Based on the
response of FE in the polymer shell to isopropanol, and CTAB compared to the response of free
FE we conclude that the FE fluorophore is situated within the inner polymer shell. Nevertheless
the fluorophore in the polymer shell can still sense polarity changes in solution. In order to keep
the fluorophore outside polymer shell i.e. to expose the fluorophore to bulk environment
polyethylene glycol was used as a linker. The resulting nanoparticles were found to remain
innocuous to additives such as isopropanol and CTAB due to hydration of fluorophore.
 Nanoparticles and Metallodendrimers as Sensors and Catalysts

Didier Astruc,
ISM, UMR CNRS N° 5255, University Bordeaux I, 33405 TALENCE Cedex, France,
e-mail: [email protected]

In this lecture, we will discuss how the interplay between dendrimers1 and Au2 or Pd3
nanoparticles provides the basis for new applications in redox sensing,4 catalysis,5 and
nanomedicine.6

Arene-cored dendritic cores, dendrons and dendrimers were first assembled using organiron
chemistry with 1 3 connectivity, then used as templates for Au and Pd nanoparticles.
Dramatic dendritic effects were disclosed for the redox-recognition and sensing of oxo-anions
including ATP2- and transition-metal cations. Such dendrimers were used as molecular
micelles for nanoparticle catalysis as well as molecular catalysis, and finally for drug
delivery.
Fe Fe
Fe
Fe
Fe Si Si
Si Si Fe

Fe Si Fe
Si
Si Si
Fe
Si Fe
O
Si
Fe Si O Fe
O Si
Si Si
Si
Fe
Si O
Si Fe ATP Sensing
O

Fe
Si O Fe
Si
Si NH2
Si S S N
Fe S SS S
S SS
Si S S
O
Si O Si Fe O O O N N
S O P O P O P O CH2
O SS S S S S O N
Si O Si S S Si
Fe
Si O OH OH
Fe
O HO OH
Si
Si O
Fe
Si Fe

O Si
Si
Fe Fe
O
Si Si Si Si
O Si
Fe
Si O Fe

Si
Fe
Si Fe

Si Si
Fe Si Fe
Si Si Si
Fe
Si Fe
Fe Fe
Fe Fe

References
1. D. Astruc, E. Boisselier, C. Ornelas, Chem. Rev. 2010, 110, 1857-1959.
2. a) M.-C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293.
b) E. Boisselier, A. K. Diallo, L. Salmon, C. Ornelas, J. Ruiz, D. Astruc , J. Am. Chem. Soc. 2010, 132,
2729–2742.
3. D. Astruc, F. Lu, J. Ruiz, Angew. Chem. Int. Ed. 2005, 44, 7852.
4. D. Astruc, L. Liang, A. Rapakousiou, J. Ruiz, Acc. Chem. Res. 2012, ASAP DOI: 10.1021/ar200235m
5. a) Nanoparticles and Catalysis, D. Astruc, VCHc Ed., Wiley, Weinheim, 2007
b) A. K. Diallo, E. Boisselier, L. Liang, J. Ruiz, D. Astruc, Chem. Eur. J. 2010, 16, 11832 – 11835.
c) V. Polshettiwar, J.-M. Basset, and D. Astruc, ChemSusChem 2012, 5, 6-8.
6. a) A. François, A. Laroche, N. Pinaud, L. Salmon, J. Ruiz, J. Robert, D. Astruc, ChemMedChem 2011,
6, 2003-2008.
b) Llevot, D. Astruc, Chem. Soc. Rev. 2012, 41, 242-257.
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Mostafa Baghbanzadeh,a Zorica Crnjak Orel,b and C. Oliver Kappe*,a

a
Christian Doppler Laboratory for Microwave Chemistry (CDLMC) and Institute of Chemistry, Karl-Franzens-
University Graz, Heinrichstrasse 28, A-8010 Graz, Austria, E-mail: [email protected]. bNational Institute
of Chemistry, Hajdrihova 19

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 “Researchcareeranddrugattrition”

Dr.LluísBallellͲPages
ChiefScientist/OpenLabManager
DiseasesoftheDevelopingWorld
GlaxoSmithKline
[email protected]

Drug discovery and development encompasses a myriad of disciplines that have
traditionally demanded large capital investments in terms of human talent, facilities
and equipment. Until recently, the main players in this industry, pharmaceuticals
companies, have focused their efforts on creating complex structures, in which
thousands of employees try to cooperate in projects ranging from early screening
activitiestolatestageclinicaltrials.Whileforatimethesestructureswereprovedto
be effective, financially sustainable medicineͲproducing systems, recent evidence
seemstoindicateanaltogetherdifferentreality.Infact,thehighdrugdiscoveryand
developmentattritionrateisthesinglemostimportantcontributingfactortospiralling
costs and low productivity within the pharmaceutical industry as a whole. Is
Nanotechnologylikelytochangethistrendinthefuture?Whatisthebalanceinthe
fieldbetweenhopeandhype?Thespeaker,asawellseasonedattritionsufferer,will
try to present a Pharma perspective that could hopefully help guide DENDREAMERS
fellows through a complex industry where, despite this introduction, plenty of
opportunitiesstillexist.
 Synthesis and Catalytic Properties of Metal-Cerium Dioxide Hybrid
Nanostructures.
Neus G. Bastus*, Eudald Casals*and Victor Puntes*

* Institut Català de Nanotecnologia (ICN), Campus UAB, 08193 Bellaterra, Barcelona, Spain

Email: [email protected]

Well-defined hybrid metal nanocrystals (NCs) with core-shell or heterodimeric structures have attracted
enormous attention because of their unique optic, magnetic, electric and catalytic properties that cannot be
obtained in monometallic nanocrystals1. Among them, metal NCs supported on cerium dioxide are
specially interesting since they are expected to exhibit improved catalytic activity and selectivity. Such
catalytic enhancement is attributed to the synergetic effect that occurs at the interface of metal and oxide
support2. It is believed that the electronic structures of both the metal and the oxide support are modified
by electron transfer across the interface, giving rise to oxygen vacancies on the interfacial oxide support
that become active sites for oxygen absorption and activation. Despite recent advances achieved on the
obtainment of metal-metal oxide hybrid NCs (HNCs) by calcination methods, a long-standing barrier has
been the developed of synthetic protocols leading their routinely production with precise control of their
morphology and crystallinity.

Herein, we present new wet-chemistry synthetic strategies for the design of both cerium dioxide and
hybrids metal-cerium dioxide catalysts. As a result, monodisperse spherical CeO2 nanocrystals with sizes
ranging from 3 to 15 nm, stamps and belts were obtained by fine tuning the concentration of reagents,
temperature and solvent. Using these particles as nucleation centers, metal-metal oxide (Au-CeO2 and
Ag-CeO2) HNCs were obtained following a seeded-growth method, obtaining a quasi core-shell structure,
consisting of a central metal core and a CeO2 shell, and with dimensions that can be control by varying
synthetic parameters. In both cases, the overall synthetic procedure is simple and readily scalable. The
catalytic properties of both types of structures were studied, showing the possibility to use these NCs as a
new type of catalysts with improved durability and reusability.

Synthesis of CeO2 belts and Ag-CeO2 hybrid nanocrystals

(1) Lee, Y.; Garcia, M. A.; Frey Huls, N. A.; Sun, S. Angewandte Chemie International Edition 2010, 49, 1271-
1274.
(2) Yu, T.; Zeng, J.; Lim, B.; Xia, Y. Advanced Materials 2011, 22, 5188-5192.
Ligand effects on electrical transport of individual colloidal semiconductor
nanocrystals

Brandon Beberwyck†§, A. Paul Alivisatos†‡§

Colloidal nanocrystal arrays are incorporated into an ever-increasing number of

electrical devices; however, charge transport across these films varies
dramatically based upon the nanocrystal’s ligand. To date, the role of ligands on
electrical properties and device performance has been limited to measurements
of ensemble arrays of nanocrystals that are complicated by film variations and
ligand length constraints. Single nanocrystal-based electrical devices overcome
the aforementioned complications, offering a model system with which to probe
ligand effects on transport properties. Here we present the tuning of the carrier
type, carrier concentration, and mobility of individual nanocrystals via surface
treatments to create two rectifying device architectures. Furthermore, we
demonstrate the preliminary application of the Hall effect to individual colloidal
nanocrystals to investigate the quantitative impact of surface treatments on
electrical properties. Our results emphasize the importance of the surface-ligand
interface on electrical transport properties and demonstrate the advantages of
this adjustability.
†
Department of Materials Science and Engineering and ‡Department of
Chemistry, University of California, Berkeley, California 94720, United States
§
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley,
California 94720, United States
Synergistic and anomalous electrical properties in the tunneling spectra
of inorganic cage-like quantum-dots
Yehonadav Bekenstein1,2,3, Kathy Vinokurov2,3, Uri Banin2,3, Oded Millo1,3
1
Racah Institute of Physics, The Hebrew University of Jerusalem
2
Institute of Chemistry, The Hebrew University of Jerusalem
3
The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem
ABSTRACT

Hybrid nanoscale inorganic cages, comprising a semiconducting Cu2S quantum-dot (QD)

core encapsulated by a metallic Ru cage-like shell, and each of their individual components, are
studied via scanning tunneling spectroscopy. The bare Cu2S QDs show reproducible
semiconducting-like I-V characteristics with a bandgap of ~1.5 eV similar to the reported values.
The spectra acquired on the Cu2S/Ru hybrid QDs largely varied with tip position along a single
dot, evolving from semiconducting-like characteristics with in-gap states to metallic-like single
electron tunneling effects (SET). Statistical analysis of bandgap values unveils the hybrid QDs
synergistic electrical properties which originate from the combination of semiconducting and
metallic cage regions. Most intriguing are the tunneling spectra measured on the empty Ru
cages. In addition to the expected SET features, the Coulomb blockade and staircase, the I-V
characteristics exhibited, in many cases, negative differential conductance features with
periodicity corresponding to the Coulomb staircase. The conventional SET evolved, with
increasing tunneling conductance, into a set of negative differential conductance peaks. Such a
unique behavior can be accounted for by considering the multiply-connected geometry of the
Ru cage-like QD.
Amelie Biermann, Raquel Gomes, Karel Lambert,Alexander Achtstein, Holger Lange, Ulrike
Woggon, Zeger Hens, and Christian Thomsen
Institute of Solid State Physics, Technical University of Berlin, Berlin Germany
Physics and Chemistry of Nanostructures, Ghent University, Belgium
Institute of Optics and Atomic Physics, Technical University of Berlin, Berlin, Germany

Exciton-phonon coupling in zincblende and wurtzite CdSe-CdS heteronanocrystals

CdSe based heteronanocrystals offer a wide range of potential applications in the field of
optoelectronics. Especially CdSe-CdS core-shell nanocrystals are currently of high interest. The
possibility to synthesize defined nanocrystals with a precise control over their size enables the
use in systems like biological sensors, LEDs, lasers and solar cells.
The magnitude of the coupling of excited carriers to phonons in the CdSe contributes to the time
scales of different photophysical processes of high significance for those applications. These
processes include for example carrier multiplication rates, and relaxation times.
In our contribution we present a systematic study of the exciton-phonon coupling in CdSe/CdS
core-shell structures. We employ a combined approach of two spectroscopic techniques, Raman
spectroscopy and photoluminescence and compare the results to General Utility Lattice Program
simulations (GULP). Huang-Rhys factors between 0.01 and 0.13 are obtained, in agreement with
previous publications. We find a systematic decrease of the coupling with increasing shell
thickness. For the first time we analyze the coupling in the zinc blende and the wurtzite lattice
configuration. We find a larger Huang-Rhys factor in wurtzite than zinc blende CdSe
nanocrystals. These results can be used to optimize the synthesis parameters to the specific needs
of different optical applications.
 Nanoparticles for Light-Triggered Sensors
Nadja-C.Bigall, Wolfgang J. Parak

PhilippsUniversität Marburg, Germany

There are numerous fields of applications for colloidal nanoparticles from biomedical
imaging and medical treatment, catalysis and data storage to solar cells, light emitting
diodes and sensors. In the field of sensoric applications, recently,light-driven sensors for
redox molecules such as hydrogen peroxide or biomolecules have attracteda lot of
attention.A specific type of these sensors consists of semiconductor nanoparticles
immobilized on a conductive (e.g. gold) layer. When this device is illuminated, a
photocurrent can be detected which is dependent on the chemical environment of this
sensor [1]. Successful approaches so far includenanoheterodimers consisting of a
semiconducting part for the above mentioned photo induced charge carrier generation, and
a catalytic part which induces a chemical reaction of a certain molecule whose reaction
products subsequently change the photocurrent. Based on these results, new systems are
currently being developed exploiting the unique advantages of colloidal nanochemistryto
synthesize tailored nanosystems consisting of two or more compartments with the desired
multifold chemical and physical properties.

For this purpose, a good control over the nanoparticle quality and their assembly is
desirable. Nanoheterostructures are synthesized following the common novel routes of
selective growth and seeded growth [2], core-shell growth with successive annealing to
separate the two systems and cation exchange reactions [3]. For the arrangement of the
nanoparticles ordered assemblies like e.g. entropy driven ones, normal spin- or dipcoated
films, or supra molecular assembly template assisted superstructures [4] will be
investigated.An alternative route of nanoparticle arrangement to be discussed includes non-
ordered superstructures [5,6] like e.g. hydro- and aerogels from nanocolloids.

In the present work, these three steps to achieve light-triggered sensing are presented and
discussed, starting by synthetic routes to tailored nanoparticles followed by some strategies
of nanoparticle assembly and its impact on the stability and reproducibility of the
photocurrent signal. Furthermore, sensing experiments with electrodes made from the new
nanoheterostructureswill be presented.

[1] J. Tanne, D. Schafer, W. Khalid, W.J. Parak, F. LisdatAnalytical Chemistry 2011,83,

7778.[2] N.C. Bigall, T. Härtling, M. Klose, P. Simon, L.M. Eng, A. EychmüllerNano Letters2008,
8, 4588.[3] D. Dorfs, T. Härtling, K. Miszta, N.C. Bigall, M.R. Kim, A. Genovese, A. Falqui, M. Povia, L.
MannaJournal of the American Chemical Society2011, 133, 11175.
[4] B. Nandan, E.B. Gowd, N.C. Bigall, A. Eychmüller, P. Formanek, P. Simon, M. StammAdvanced
Functional Materials 2009, 19, 2805.
[5] N.C. Bigall, M. Reitzig, W. Naumann, P. Simon, K.H. van Pée, A. EychmüllerAngewandte Chemie
International Edition 2008, 47, 7876.
[6] N.C. Bigall, A.K. Herrmann, M. Vogel, M. Rose, P. Simon, W.C. Cabrera, D. Dorfs, S. Kaskel, N.
Gaponik, A. EychmüllerAngewandte Chemie International Edition2009, 48, 9731.
In situ determination of band offsets in quantum dot
heterojunctions for photovoltaic application

S.C. Boehme, H. Wang, D. Vanmaekelbergh, L.D.A. Siebbeles and A.J. Houtepen

(TU Delft, Chemical Engineering, Optoelectronic Materials, Julianalaan 136, 2628 BL Delft,
The Netherlands)

Charge separation is crucial for the generation of photocurrent in heterojunction solar cells[1, 2]. The key
parameters driving charge separation, the band offset and the density of states of the different
components of the heterojunction, both depend strongly on their (dielectric) environment[3]. Here we
present a technique to determine in situ the density of states and energy level positions of
heterojunctions based on two types of colloidal quantum dots (QDs). We apply a combination of
electrochemical charging and optical and electrical detection of the occupation of energy levels. As a
proof of concept, the electron occupation in CdSe and CdTe QDs at different Fermi levels is monitored
optically by an induced absorption bleach and electrically by an electrochemical charging current (see
Figure 1). In alternating stacks of these materials their relative band offset can be determined. We show
that electrons can be injected into both 1Se and 1Pe electron levels with a maximum occupation of ~ 6
electrons per QD. Such high charge densities are achieved only for sufficient screening of the Coulomb
repulsion between injected charges. We demonstrate that the screening can be optimized by controlling
both film morphology and electrolyte composition[unpublished]. The presented findings highlight the
large influence of the direct environment of QDs on their energy level positions.

Figure 1. a) Schematic representation of energy levels in a QD. Filling of energy levels results in absorption
bleaches of the involved transitions. b) Absorption bleach in a film of 8nm CdSe QDs at different potentials. The
lowest energy transitions involving the 1Se and 1Pe electron level are indicated by dashed lines. c) Simultaneous
electrochemical and optical determination of the density of states of the first two electron levels by differential
capacitance (filled symbols, left axis) and differential absorption bleach (open symbols, right axis).

REFERENCES

1. Pijpers, J.J.H., et al., Spectroscopic Studies of Electron Injection in Quantum Dot Sensitized Mesoporous
Oxide Films. The Journal of Physical Chemistry C. 114(44): p. 18866-18873.
2. Talgorn, E., et al., Photoconductivity Enhancement in Multilayers of CdSe and CdTe Quantum Dots. ACS
Nano. 5(5): p. 3552-3558.
3. Wang, C., M. Shim, and P. Guyot-Sionnest, Electrochromic Nanocrystal Quantum Dots. Science, 2001.
291(5512): p. 2390-2392.
Characterization of Quantum Dot PEO Ligand Shells by Fluorescence Quenching

Klaus Boldt1,2, Marc Thiry1, Horst Weller1

1
Department of Chemistry, University of Hamburg, Hamburg, Germany.
2
School of Chemistry, University of Melbourne, Melbourne, Australia.

CdSe/CdS/ZnS semiconductor core/shell/shell nanoparticles (quantum dots) are a relatively new class
of fluorescent dyes, which exhibit high photostability, a broad absorption spectrum and an emission
wavelength that can be controlled by the particle size. This makes them interesting candidates for
biolabeling. In order to provide solubility in aqueous media and to introduce functional groups
quantum dots are routinely submitted to a ligand exchange procedure. Several approaches exist, many
of which employ poly(ethylene glycol) as the water-soluble moiety.[1-3] Due to swelling and coiling
of the polymer the characterization of the quantum dots' organic shell is not straight-forward.
We present a method to determine the size of the nanostructure and the ligand shell permeability by
simple fluorescent quenching experiments.[4]
Both electron scavengers and FRET acceptors have been employed as probes. It could be shown that
particles capped with long polymer ligands are quenched by a dynamic mechanism, while those with
short thiol ligands are statically quenched. The method gives insight into the ligand packing of PEG-
capped particles, which comprise of a densely packed inner shell and a loosely packed outer shell in
which metal ions diffuse relatively unhindered.
Fluorescent dye molecules of low solubility in water were used to characterize the PEG volume by
quantitative uptake into the ligand shell, where they act as FRET acceptors. Förster's theory allows
relating the quenching efficiency to the acceptor concentration and calculating the particle diameters,
which show very good agreement with the hydrodynamic radii determined independently by dynamic
light scattering.

>@07KLU\.%ROGW061LNROL F)6FKXO]0,MHK$3DQLFNHU79RVVPH\HU+:eller,
“Fluorescence Properties of Hydrophilic Semiconductor Nanoparticles with Tridentate Polyethylene
Oxide Ligands,” ACS Nano 5, 4965 (2011).

[2] M. Stewart, K. Susumu, B. Mei, I. Medintz, J. Delehanty, J. Blanco-Canosa, P. Dawson, H.

Mattoussi, “Multidentate Poly(ethylene glycol) Ligands Provide Colloidal Stability to Semiconductor
and Metallic Nanocrystals in Extreme Conditions,” J. Am. Chem. Soc., 132, 9804 (2010).

[3] E. Pöselt, S. Fischer, S. Förster, H. Weller, “Highly Stable Biocompatible Inorganic Nanoparticles
by Self-Assembly of Triblock-Copolymer Ligands,” Langmuir 25, 13906 (2009).

[4] K. Boldt, S. Jander, K. Hoppe, H. Weller, “ Characterization of the Organic Ligand Shell of
Semiconductor Quantum Dots by Fluorescence Quenching Experiments,” ACS Nano 5, 8115 (2011).
Spin-flip limited exciton zero-phonon line dephasing in CdSe
colloidal quantum dots
N. Accanto1, F. Masia1 I. Moreels2, H. Zeger2, W. Langbein1, and P. Borri1
1
School of Physics and School of Biosciences, Cardiff University, The Parade, Cardiff, CF24
3AA,
2
Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, Ghent
B-9000, Belgium
E-mail: [email protected]

Semiconductor quantum dots (QDs) exhibit a peculiar coupling of excitons with phonons as a result
of the local lattice distortion associated with the excitonic excitation. This coupling gives rise to a
strongly non-Lorentzian excitonic homogeneous lineshape at low temperatures consisting of a
Lorentzian zero-phonon line (ZPL) superimposed onto a broad acoustic phonon band, and in turn a
strongly non-exponential dephasing. Extensive work has been reported on the ZPL dephasing of
ground-state excitons in epitaxially grown InGaAs QDs. Importantly, it was shown that the ZPL
dephasing at low temperature is limited by the ~1ns exciton radiative lifetime [1]. The picture is much
less clear for colloidal QDs which have stronger confinement and longer radiative lifetimes. While a
ZPL ~ 10PeV was reported in large core CdSe colloidal QDs at low temperature via spectral hole
burning and single-dot spectroscopy experiments (corresponding to ~100ps exciton dephasing much
shorter than the ~10ns radiative lifetime) [2], its physical origin remained an open question also
because these experiments were limited by spectral diffusion.
In this work we have measured the exciton dephasing time using a sensitive three-beam transient four-
wave mixing (FWM) technique in heterodyne detection, unaffected by spectral diffusion, in high-
quality CdSe/ZnS wurtzite colloidal QDs (nominally identical to those in [2]) and in a series of
CdSe/CdS zincblende QDs with variable core diameter and shell thickness (see figure). From the
temperature dependence of the ZPL dephasing and the exciton lifetime, as well as a direct
measurement of the exciton thermalisation within its fine structure, we show unambiguously that the
ZPL dephasing of the lowest bright state originates from the phonon-assisted spin-flip to dark exciton
states. Moreover, in our sample series, we tailor the exciton fine structure by changing the core size
and crystal structure, and the shell material and thickness. The ZPL dephasing in this series changes
as expected from the spin-flip mechanism.
We find the longest ZPL dephasing time of
~110ps at 5K in QDs with the largest core
size and the thickest CdSe shell. These QDs
have a quasi type II band alignment resulting
in an extension of the electron wavefunction
into the shell, reducing the electron-hole
exchange interaction and thus the bright-
dark splitting. At the same time, increasing
the size of the exciton wavefunction also
increases the ZPL weight and decreases the
width of the phonon broad band.
Our results give an unambiguous evidence
of the physical origin of the exciton
dephasing in CdSe nanocrystals and
demonstrate its control by engineering the
excitonic fine structure.

References
[1] P. Borri et al. Phys. Rev. Lett. 87, 157401 (2001); W. Langbein et al. Phys. Rev. B 70, 033301 (2004).
[2] L. Biadala, et al., Phys. Rev. Lett. 103, 037404 (2009).
 NANOPARTICLES AND THE RESPIRATORY SURFACE:
EXPOSURE OF PULMONARY SURFACTANT AND PNEUMOCYTES TO
GOLD NANOPARTICLES
V. Bouzas1, N. Hobi2, T. Haller2, L.M. Liz-Marzán3, J. Pérez-Gil1, I. Pastoriza-Santos3
1.- Dpto. Bioquímica y Biología Molecular I, Facultad de Biología, Universidad Complutense de Madrid
2.- Dpto. Physiology and Medical Physics. Division of Physiology Innsbruck Medical University
3.- Dpto. Química-Física, Facultad de Químicas, Universidad de Vigo

Lungs are one of the most difficult organs to be diagnosed or treated due to their
anatomical complexity and inaccessibility. Nowadays the new discipline known as
nanomedicine is acquiring a large projection in the design of new strategies intended for
the study of respiratory diseases.
The pulmonary route of nanoparticles (NPs) administration is increasing interest
because it reduces systemic effects and extends the pharmacological potential. By
inhalation any NP (with size smaller than 500nm) takes in directly to the deep
respiratory tract, the alveoli. The alveolar space is coated by a complex lipid-protein
system, the Pulmonary Surfactant (PS), which main role is to reduce the surface tension
at the air-water interface to prevent the collapse during breathing, and it is also
responsible for innate defence mechanism. PS complex is released by the Alveolar Type
II (ATII) ephitelium cell, the pneumocytes. Thus, PS and ATII are the initial contact
structures where NPs impinge.

The aim of our work is to synthesize LS-NPs complex because it may be a viable
strategy to develop diagnosis and treatments of respiratory diseases. Therefore we have
simulated the real biological conditions and studied the effects of:
x The Gold NPs interaction with Native PS complexes.
x The exposure of ATII primary cells to Gold NPs.

Specifically, we want to probe whether the inclusion of Gold NPs alter either the
biophysical properties of PS, or the morphological appearance and basic vital
parameters of lung cells.
The key point for using Gold Nanostructures is they have excellent features that make
them unique for biomedical applications. They are highly biocompatible elements, very
easy to functionalize and have optical properties due to the Surface Plasmon Resonance
which allow detecting them in the VIS-NIR range.

The effect of NPs on the NPS interfacial activity has been carried out using a
biophysical in vitro method, the captive bubble surfactometer (CBS) which permit
simulate breathing dynamics. Besides, we have also investigated whether the effect of
NPs on surfactant depends on the particle size, shape and surface coating.
On the other hand, in order to evaluate the effect of NPs on ATII cells we have analyzed
the cell viability (toxicity), their morphology and their functional competence to secret
surfactant.
 Studying Charge Transport using Quantum Dot Capacitors

Deniz Bozyigit, Olesya Yarema, and Vanessa Wood

Laboratory for Nanoelectronics

Department of Information Technology and Electrical Engineering
ETH Zurich
Gloriastrasse 35 ETZ J86
8092 Zurich, Switzerland

Semiconductor nanocrystals (NC) solids are viewed as promising materials for next
generation lighting and photovoltaic applications. While the optical properties of NCs
are well understood, electronic transport is still a topic of investigation. Most of what
is known about electronic transport of these materials today is based on measurements
of (photo-) conductivity. To complement these studies, we investigate the dielectric
properties of NC-solids in capacitive structures by impedance spectroscopy and
transient spectroscopy measurements. We show that the intricate interdependence
between dielectric and conductive effects can be investigated from a different
perspective due to the absence of charge injecting interfaces.

The capacitive structures we investigate consist of a thin film of QDs placed between
two dielectric layers as shown in Figure 1. Under alternating field excitation charges
are locally generated in the QD-film which then exhibits electroluminescence (EL)
(Figure 2). By measuring the polarization in the QD-film we can identify charge
trapping as one of the limitations for light generation.

Figure 1. Schematic of device studied and Figure 2. QD capacitor under

experimental setup. alternating current excitation.

Furthermore, we have used these structures to demonstrate that the PL-

quantum yield of CdSe/ZnS NC-solids decreases under very high fields
(> 1MV/cm). Using the electrical measurements we were able to show that
neither exciton dissociation nor Auger-type processes can account for this
process.
 Liquid crystal networks and self-organizing hydrogels:
nanotechnology towards soft actuators and nanoporous systems
D.J. Broer
Eindhoven University of Technology, The Netherlands
e-mail: [email protected]

In-situ photopolymerization of liquid crystalline (LC) monomers has proven to be a valuable technique for
the formation of well-ordered polymer networks. Their anisotropic properties led to a variety of
applications in optics, electronics and mechanics. The use of light to initiate polymerization enables
lithographic approaches for patterning. The LC behaviour enables formation of complex morphologies on
molecular level. Controlling the director profile of an LC network film in transversal direction gives
geometrical morphing upon minor changes in order parameter. Examples of suited profiles of molecular
orientation are twisted or splayed director configurations tied up in the network configuration. Reversible
order parameter changes can be induced by a variety of means. It can be simply induced by temperature
changes resulting in gradients in thermal expansion over the cross-section of the film. But more
sophisticated and of interest for applications is a light induced change as a result of the E-Z isomerization of
a built-in azo group.
Rather than composing the monomers of covalent bonds alone, one can chose to replace some bonds
by secondary interactions such as hydrogen bridges, thus providing responsive molecularly organized
hydrogels. We applied the H-bridge based dimerization of benzoic acid to form nematic LC acrylate
monomers. By a controlled and reversible rupture of the H-bridges mechanical responses can be initiated.
Photopolymerization of smectic LC monomers lock in structures of different length scales. The first
length scale is the resolution of lithography, and goes down to a few micrometers. The second length scale
is set by the spacing of smectic layers and is typically a few nanometers. The third length scale is the
intermolecular distance in the layers, usually around 1 nm or below. By modifying smectic molecules with
H-bridges the smectic periodicity can break-up into separated layers with a well-defined spacing, also in the
nanometer range. The nanopores form by breaking the H-bridges at elevated temperatures or by contact
with an alkaline solution. The integrity of the film is maintained by copolymerizing with fully covalent
smectic crosslinkers.
 Influence of Alloying on the Optical Properties of IV-VI Nanorods

Anna Rubin Brusilovski, Georgy I. Maikov, Dikla Kolan, Roman Vaxenburg, Jenya Tilchin, Aldona
Sashchiuk and Efrat Lifshitz

Schulich Faculty of Chemistry, Russell Berrie Nanotechnology Institute, Solid State Institute, Technion, Haifa 32000,
Israel

Variation of electronic properties of semiconductor nanostructures by a change of their

size has been a topic of special interest for more than two decades. The potential applications
of these materials oppose stringent demands, which shifted recently the effort to explore new
nanostructures, gaining additional degrees of freedom in the tunability of the electronic
properties by incorporation of alloy composition, or developing elongated nanostructures such
as wires, rods or polypods, that demonstrate polarization-sensitive light emission, significant
absorption cross section, efficient charge separation and transport along the major growth axis,
as well as possible efficient multiple exciton generation. The present work demonstrates the
use of combined strategies, developing colloidal elongated nanostructure - the nanorods,
joined with alloy composition from the IV-VI semiconductor compounds.

We report the synthesis, characterization and modeling of ternary IV-VI nanorods (NRs)
with general chemical formulas PbSexS1-x and PbSe/PbSexS1-x (0dxd1), diameter of 2 nm to 4.5
nm and length of 12 nm to 40 nm. The energy band-gap of these nanorods exhibits a
pronounced variation upon the change in their width and composition, with a minor influence
on a length less than 10 nm. The photoluminescence spectra of the nanorods are comprised of
two band-edge exciton band, showing a small band-gap temperature coefficient and a mild
extension of the radiative lifetime at cryogenic temperatures - all in comparison with
photoluminescence processes in PbSe nanorods, as well as in PbSexS1-x quantum dots, with
similar absorption band-edge energy. An electronic-band theoretical model, using effective
mass approximation, associates the experimental observations to the occurrence of
independent transitions from either degenerate or non-degenerate band-edge valleys in the
mentioned nanorods, each of which possessing a relatively small electron-hole exchange
interaction.


Synthesis and Characterization of new Liquid
Crystal Dendrimers with Porphyrin Core





Madalina Bucosa, Joaquín Barberáb, Mercedes Marcosb, Pilar Romerob, José-Luis Serrano*a



a) Quımica Organica, Instituto de Nanociencia de Aragon,Universidad de Zaragoza, 50009 Zaragoza, Spain

b) Quımica Organica, Facultad de Ciencias-Instituto de Ciencia de Materiales de Aragon,Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain

The induction and the control of mesomorphic properties in dendrimers can be achieved by a
delicate molecular design, which depends on the chemical nature and structure of both the
functional groups and the dendritic matrix.1 Dendrimers are generally prepared using either a
divergent method or a convergent one.2

The objective of the present work is to synthesizes and characterize new liquid crystal
dendrimers with via covalent interactions Figura 1. (a) or via H-bonding interactions Figura 1.
(b) between a porphyrin core and dendritic acids derived from 2,2-bis(hydroxymethyl)propionic
acid (bis-MPA).

The covalent compounds were synthesized using the two methods for the synthesis of the
dendrimers, divergent and convergent methods.

The H-bonding complexes consisting on a H-acceptor 5,10,15,20-tetra(4-pyridyl)porphyrine
(TPyP) core surrounded by four dendritic acids were carried out following the strategy described
in previous works3.

The formation of the complexes was evidenced by infrared an NMR techniques. All the
liquid crystalline materials were studied by polarizing optical microscopy, differential scanning
calorimetry and small-angle X-ray diffraction.







(a) O O (b)
X O H
N

O O
NH N N N
X X O H N M N H O

N N N
HN O
O

O X H
X= O, NH M= H, Zn
O O
O

O O O
O
= O
O
O
O O
O

O

Figura 1. General structure of coumpound formed via covalent bonding (a) and via H-bonding TPyP (b) with first generation of bis-MPA

References:

mesogenic dendrons

1. Bertrand Donnio; Daniel Guillén, Adv Polym Sci (2006) 201: 45–155

2. Hodge, P. Polymer science branches out. Nature (1993) 362, 18–19.

3. Alvarez, L.; Barbera, J.; Puig, L.; Romero, P.; Serrano, J. L.; Sierra, T. J. Mater. Chem. 2006, 16, 3768-3773.

Acknowlodgements: This work wos suported by the MICINN, Spain, under the porject CTQ2009-0930 and MAY2009-14636-CO3-01, FEDER
funding EU and the Marie Curie Action ITN, No. 215884-2 and by the Gobierno de Aragon (Research Group 04). M. Bucos acknowledges to
ESR contract within the Marie Curie Action
 Parallel Quantum Dot arrays for fast and efficient
photodetection
M. Buscema,1 F. Prins,1* J. S. Seldenthuis,1 S. Etaki,1 G. Buchs,1 M. Barkelid1, V.
Zwiller,1 Y. Gao,2 A. J. Houtepen,2 L. D. A Siebbeles,2 H. S. J. van der Zant1*
1. Kavli Institute of NanoScience, Delft University of Technology, PO Box 5046, 2600 GA, Delft, The Netherlands.
2. Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.

Photodetection based on colloidal quantum dots (CQDs) usually makes use of multi-layered
film structures [1], in which the charge transport is limited by interparticle hopping barriers.
We exploit a new fabrication technique [2] that allows us to place a one-dimensional parallel
array of lead selenide (PbSe) quantum dots in direct contact with metallic electrodes thereby
ensuring an efficient carrier extraction, since hopping does not play a role any more in this
geometry. Furthermore, the geometry of the device gives rise to an enhancement of the
optical field between the electrodes, increasing the effective optical cross section of the
device. Both effects together yield an external quantum efficiency as high as 30 electrons
per photon and response time shorter than 300 ns. Moreover, as the device architecture can
host a variety of QD types, it is a promising architecture to open up the path for new studies
of exciton generation and charge carrier dynamics in nanoscale systems.

References:
[1] G. Konstantatos, I. Howard, A. Fischer, S. Hoogland, J. Clifford, E. Klem, L. Levina, E. H.
Sargent, Ultrasensitive solution-cast quantum dot photodetectors, Nature, vol. 442, pp. 180-
183, 2006
[2] F. Prins, M. Monrabal-Capilla, E. A. Osorio, E. Coronado and H. S. J. van der Zant, Room-
temperature electrical addressing of a bistable spin-crossover material, Advanced Materials
23, 1545, 2011

Acknowledgements:
This work was supported by Stichting FOM under the programs 86 and 111, and through the
FP7-framework programs ELFOS.
Nanotoxicity studies of four synthesized silver nanoparticles complexes
for future biological applications
E.Caballero-Díaza,b, Christian Pfeifferb, Lena Kastlb, Bartolome M. Simoneta, Miguel
Valcarcela, Pilar Rivera Gilb, Wolfgang J. Parakb
a
Department of Analytical Chemistry, Campus de Rabanales, University of Cordoba, 14071 Cordoba, Spain
b
Fachbereich Physik, Philipps Universität Marburg, 35037 Marburg, Germany

Silver nanoparticles are widely used currently in industry, mainly because of their anti-bacterial
properties, with applications in cosmetics and as bacteriocides in fabrics and other consumer
products [1]. Its anti-microbial characteristic makes that Ag can be especially toxic when comes
into contact with the organisms. For this reason and for its increasing popularity, the silver
nanoparticles toxicity must be assessed and new synthesis methods must be developed in order
to reduce its impact.

The cytotoxicity of four different types of silver nanoparticles has been compared. The
nanoparticles were synthesized from a same silver core which was capped with different
superficial agents. The studies of cytotoxicity were carried out incubating the nanoparticles with
NIH/3T3 cells for 24 hours.

Silver nanoparticles were coated firstly with an amphiphilic polymer to make them stable in
aqueous solution. Later, different capping agents were added in order to evaluate their relevance
in the cytotoxicity of the nanoparticles. Among the added capping agents were, 11-
mercaptoundecanoic acid and poly (ethylene glycol) (PEG). In this last case, we did the study
for PEG-saturated silver nanoparticles and also for silver nanoparticles with only one PEG
molecule in the surface. The study was completed comparing the obtained results with the
cytotoxicity of nanoparticles only coated with the amphiphilic polymer and also with the
toxicity of silver ions (silver nitrate was used as a source).

In order to carry out the nanotoxicity assessment, we used a resazurin based-cell availability
assay. Resazurin is a non-fluorescent dye which, only in viable cells, can be reduced to other
metabolite, resorufin, which produces a very bright fluorescence. In this way, we can evaluate
the cell viability of the cells exposed to the nanoparticles as a function of the observed
fluorescence after 3 hours of incubation with the dye.

The results showed differences in the cytotoxicity depending on the superficial coating of silver
nanoparticles. The different molecular assembly on a same silver core affects to the stability of
the nanoparticles in solution as well as the internalization of the nanoparticle into the cell. The
highest toxicity was observed for silver nitrate due to the silver ions release that is strongly
harmful for the cells. PEG saturated and amphiphilic polymer coated-silver nanoparticles
showed the lowest cytotoxicity, these results were attributed to a reduction of the release of
silver ions to the medium thanks to the protective coatings as well as a lower internalization of
the nanoparticle into the cells due to its larger size.

[1] I.Römer, T.A.White, M. Baalousha, K. Chipman, M.R.Viant, J.R.Lead, Journal of Chromatography A, 1218
(2011) pp.4226-4233
Abstract for Nanax 5, Fuengirola, Spain

Bottom-up processing of nanocomposites for thermoelectric applications

Doris Cadavid, Maria Ibáñez, Andreu Cabot*

Catalonia Institute for Energy Research, IREC, Sant Adria del Besos, Barcelona, 08930, Spain

Departament Electronica, Universitat de Barcelona, Barcelona, 08028, Spain

*[email protected]

Thermoelectrics, allowing the solid-state conversion between thermal and electrical energy, have
long been considered an attractive technology for cooling and waste heat recovery. Today’s main
strategy to produce materials with high thermoelectric figures of merit is to trigger phonon scattering
at multiple length scales without disturbing the charge carrier transport. The goal is to minimize the
lattice thermal conductivity in highly electrically conductive materials; the so-called electron-crystal
phonon-glass paradigm. This strategy is implemented by two main approaches: i) the scattering of
phonons at the atomic length scale by the synthesis of complex crystal phases that include 1D phonon
scattering centers, such as vacancies or rattling atoms, and/or 2D layered crystallographic structures;
ii) the scattering of phonons at the 1-100 nm scale by reducing the crystal domain dimensions to the
nanoscale. An additional advantage of the confinement of the lattice dimensions to the nanometer
scale is the potential decoupling of the Seebeck coefficient from electrical conductivity. In this regard,
the increase of the electronic density of states near the Fermi level in quantum confined
nanostructures has been predicted to enhance the Seebeck coefficient. At the same time, energy
filtering at nanocrystal interfaces may further enhance the thermopower of nanostructured material by
selectively scattering low energy charge carriers.
In this scenario, colloidal synthesis routes are particularly well suited for the production of
thermoelectric materials. Solution-processing methods have a high potential for the production of
low-cost, high-yield, large-scale, high-output and shape-adaptable devices. Moreover, bottom-up
approaches allow to directly obtain nanocomposites with reduced crystal domain size and controlled
geometry. Solution processing methods enable the production of nanocomposites by simply mixing
two solutions containing nanoparticles of the each of the components of the final nanocomposite. The
synthesis of heterostrauctures is even a more elegant approach to the production of nanocomposites.
Solution processed heterostructures are unique building blocks for the preparation of nanocomposites
in a highly controlled manner. Our results in the chemical, structural and thermoelectric
characterization of nanocomposites obtained from colloidal nanoheterostructures and from mixtures
of colloidal nanoparticles with different compositions will be presented. The advantages and
disadvantages of this bottom-up approach to produce nanocomposites will be discussed.
 Phase- and Size-Controlled Synthesis of CuxS Colloidal Nanocrystals with Tunable Near-IR
Plasmonic Properties
L. Carbone,* Y. Xie, C. Nobile, V. Grillo, C. Giannini, B. Antonazzo, F. Della Sala, Carola Kryschi and P.D. Cozzoli
* Istituto Nanoscienze CNR Via Arnesano Km 5 73100 Lecce (Italy)
email: [email protected]

Almost all transition-metal sulphide minerals are crystalline solids exhibiting a wide spectrum of topological arrangements of
metallic cations and sulfide anions in the lattice cell, mostly depending on the metal multiple valence states. It is not uncommon that
a specific chalcogenide compound shows numerous cation to anion molar-ratios-depending crystal forms.[1, 2]
Binary copper sulfides CuxS, exhibit a complex mineralogy due to a plethora of non-stoichiometric crystalline phases co-existing at
room temperature, between the two well-known stoichiometric forms of CuS (covellite) and Cu2S (chalcocite).[1, 3] From the point of
view of lattice ions’allocation, all those phases can be sorted into two broad classes: crystal structures in which S2- ions are positioned
according to hexagonal close packing and those in which sulfurs occupy sites characteristics of a cubic close packing. Cu+/Cu2+ ions,
on the contrary, show many-fold disordered sublattices due to their high diffusion rates in the interstices of the S2- close-packed
frameworks, a tendency decisively facilitated by the disparate coordination numbers that copper can assume[1, 4, 5] and the high
ions’mobility.[6-8] The main effect of the existence of multiple crystal phases is primarily a marked band gap variation from ~1.2eV in
the case of Cu2S to ~2.2 eV for CuS, as well as a series of interesting composition-related opto-electrical properties.[9-11] These may
be further biased when copper-based chalcogenides are approached at the nanoscale level as, with respect to their corresponding bulk
counterpart, a dependency on the particle size and shape is introduced as well.[12, 13] With a noticeable emphasis on nanostructures, a
voluminous literature has been earlier developed for the solvothermal synthesis of copper sulfides under the assistance of complexing
agents and/or surfactants.[14]
We report a one-pot solution-phase preparation of size monodisperse hexagonal-shaped CuxS nanodisks whose different crystal
habits and Cu to S chemical compositions have been temperature-tailored. In a copper-deficient growth environment (Cu:S=1:4), a
reactive copper complex is, at first, formed upon reaction of CuCl with oleylamine (OLAM) and octadecene (ODE) and the
assistance, merely restricted to a few examples, of oleic acid (OLAC). Following the copper complex formation, particle growth is
rapidly induced by injection of a reactive S-OLAM solution employed as a sulfur precursor. A change of the growth temperature
drastically influences the reaction outcomes thus promoting compositional and crystal phase transitions from pure covellite (CuS),
when T is 180°C, to a mixture of digenite (Cu9S5) and low-chalcocite (Cu2S) at 270°C. In fact the rate of structural transformation
from CuS towards Cu2S as well as the size and shape control are heavily dominated by ODE to OLAM molar ratios and OLAC
presence. Specifically, whether low values of ODE:OLAM molar ratios preserve the covellite phase even at high synthesis
temperatures, high molar values foster a phase change already at low temperatures. The development of crystal phases
thermodynamically less privileged indicate a reaction system under kinetic control reasonably ascribable to coordinating ability of
molecular ligands. This is distinctly validated by the existence of twinned particles showing two domains with the same crystal habit.
Spectroscopic studies have demonstrated two indicative light absorptions respectively in the UV and near-IR region: whereas the
former is assigned to interband transitions, the latter, earlier identified with a localized surface plasmon band (SPR),[15-17] is herein
demonstrated to be actively size- and phase-dependent. Related to nanocrystal anisotropic shape, the extent of surface to volume
development and the growth conditions, SPR dynamics either show wavelength red-shifts upon increasing nanodisks’ diameter or
plasmon damping when the system undergoes polymorphic transformations from covellite (Cu:S=1:1) to low-chalcocite (Cu:S=2:1).
Femtosecond transient absorption spectroscopy experiments displayed a radial breathing mode whose oscillation is directly
proportional to the radius of the nanodisk, whereas the extensional mode could be neglected because of the larger extension of
nanodisk’s radius compared to corresponding thickness.

1. Vaughan, D.J. and J.R. Craig, Mineral chemistry of metal sulfides. Cambridge Earth Science Series. 1978: Cambridge
University Press.
2. Chen, C.-C., A.B. Herhold, C.S. Johnson, and A.P. Alivisatos, Science, 1997, 276, 398.
3. Hans, R., J. Phys. Chem. Solids, 1967, 28, 903.
4. Buerger, M.J. and B.J. Wuensch, Science, 1963, 141, 276.
5. William R. Cook, J., L. Shiozawa, and F. Augustine, J. Appl. Phys., 1970, 41, 3058.
6. Furer, J., M. Lambertin, and J.-C. Colson, Corros. Sci., 1977, 17, 625.
7. Evans, H.T.j., Am. Mineral., 1981, 66, 807.
8. Dzhafarov, T.D., M. Altunbas, A.I. Kopya, V. Novruzov, and E. Bacaksiz, J. Phys. D Appl. Phys., 1999, 32, L125.
9. Reijnen, L., B. Meester, A. Goossens, and J. Schoonman, Chem. Vapor Depos., 2003, 9, 15.
10. Wu, Y., C. Wadia, W. Ma, B. Sadtler, and A.P. Alivisatos, Nano Lett., 2008, 8, 2551.
11. Setkus, A., A. Galdikas, A. Mironas, I. Simkiene, I. Ancutiene, V. Janickis, S. Kaciulis, G. Mattogno, and G.M. Ingo, Thin
Solid Films, 2001, 391, 275.
12. Lou, Y., A.C.S. Samia, J. Cowen, K. Banger, X. Chen, H. Lee, and C. Burda, Phys. Chem. Chem. Phys., 2003, 5, 1091.
13. Xia, Y., P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim, and H. Yan, Adv. Mater., 2003, 15, 353.
14. Zhao, Y. and C. Burda, Energy & Environmental Science, 2012, 5,
15. Luther, J.M., P.K. Jain, T. Ewers, and A.P. Alivisatos, Nat. Mater., 2011, 10, 361.
16. Dorfs, D., T. Ha‫ޠ‬rtling, K. Miszta, N.C. Bigall, M.R. Kim, A. Genovese, A. Falqui, M. Povia, and L. Manna, J. Am. Chem.
Soc., 2011, 133, 11175.
17. Silvester, E.J., F. Grieser, B.A. Sexton, and T.W. Healy, Langmuir, 1991, 7, 2917.
 NIR-light triggered delivery of macromolecules into the cytosol
Susana Carregal-Romeroa, Markus Ochsa, Pilar Rivera-Gila, Carolin Ganasa, Anton
M. Pavlovb, Gleb B. Sukhorukovb, Wolfgang J. Paraka.
a
Department of Physics and WZMW, Philipps Universität Marburg, D-35037, Marburg, Germany
b
School of Engineering & Materials Science Queen Mary University of London Mile End Road, L E1
4NS, London, United Kingdom

Light-responsive microcapsules constructed by layer-by-layer self-assembly are used as

microcarriers to deliver different macromolecules inside cells.1 The microcapsules carry the
macromolecules as cargo in their cavity, while their walls are modified with agglomerated
gold nanoparticles. Microcapsules are incorporated by living cells and are then located in
lysosomal compartments. Controlled release of the encapsulated material from the interior of
the capsule to the cytosol is possible upon NIR-light irradiation. This is based on local heating
of the gold nanoparticles upon NIR light and disruption of the capsule wall, what results on
release of encapsulated materials. We illustrate several key advances in controlled release
induced by light. First, we demonstrate that capsules can be opened individually, which
allows for sequentially releasing cargo from different capsules within one single cell. Second,
by using a pH-indicator as cargo the claim of release from the acidic lysosomal compartments
to the neutral cytosol is experimentally evident which until now has been only speculated.
Third, green fluorescent protein (GFP) is released to the cytosol while retaining its
functionality. This demonstrates that proteins can be released without destruction by the local
heating. Fourth, GFP is also administered in biodegradable capsules, which leads to a
different release mechanism compared to externally triggering for light-responsive
microcapsules.

1. Carregal-Romero, S. et al.,NIR -light triggered delivery of macromolecules into the cytosol.

J.Controlled Release 2012, (accepted).
 Electronic structure and optical properties of PbSe/CdSe core-shell quantum
dots

S. Carrillo and C. Delerue

Institut d'Electronique, de Microélectronique et de Nanotechnologie, IEMN-CNRS, Département ISEN, 41 bd Vauban,
59046 Lille-Cedex, France

Semiconductor nanocrystals (NCs) are found to be attractive and promising structures for light-
emiting based applications. The effect of confinement on the band gap gives the possibility to adjust
the emission color changing the size of the crystal. Core-shell nanostructures can be an alternative
to enchance brightness stability in low quantum yield compounds, as it's the case embedding PbSe
NCs in a CdSe shell. This is a special type of heterostructure, since the crystalline structure changes
from rock-salt to zinc-blende, even if the two compounds share a common Se fcc matrix, and some
interesting issues arrive for the study of the electronic structure, as the gap for the bulk in IV-VI
rock-salt structures is usually at the L point and for II-VI compounds it's at * point. Ab initio LDA
calculations on these systems have been published recently1, but LDA has the disadvantage of
underestimating the value of the band gap. Here we use semi-empirical tight-binding (TB), that
gives a better estimation of this gap and presents some advantages since the parameters from the
bulk system can be used without change on the case of quantum confined systems2, where the
electronic structure turns to discrete energy levels.

In this work, TB is used to calculate the electronic structure of PbSe, CdSe and PbSe/CdSe core-
shell quantum dots. The relation between band gap and size of the core-shell structure is shown to
be dominated by the contribution of the PbSe core in agreement with experiments3. From the
knowledge of electronic structure, optical properties like the oscillator strength, the absorption
spectrum and the optical cross section are calculated for each compound, starting from the ground
state and then simulating the creation of an electron-hole pair by exchange of the energy values on
the extremes of the conduction and valence band, thus obtaining intraband transitions that go from
the edge of each band to higher energy levels. All these quantities appear to be in agreement also
with photoinduced absorption experiments.

References

1. Leitsmann, R., Bechstedt, F. Ab initio characterization of the electronic properties of PbTe

quantum dots embedded in a CdTe matrix. Semiconductor Science and Technology 26,
014005 (2011).
2. Allan, G., Delerue, C. Confinement effects in PbSe quantum wells and nanocrystals.
Physical Review B 70, 245321 (2004).

3. T. H. Nguyen et al. Charge carrier identification in tunneling spectroscopy of core-shell

nanocrystals. Physical Review B 84, 195133 (2011)
 rThe Inorganic Nanoparticle Biomolecular Corona.
Formation, Evolution and Biological Impact
Eudald Casals1, Tobias Pfaller2, Albert Duschl2, Gertie J. Oostingh2, Víctor F. Puntes1,3
1. Catalan Institute of Nanotechnology, Campus UAB, Q-building, 08193 Bellaterra (Barcelona), Spain
2. Department of Molecular Biology, University of Salzburg, Salzburg, Austria
3. Institut Català de Recerca i Estudis Avançats (ICREA), Barcelona, Spain.
Email: [email protected]

Physicochemical changes of inorganic nanoparticles (NPs) in biological environments determine their

effects. Blood, lymph, mucus, complete cell culture media, and other biological fluids contain a large
amount and variety of different molecules. Nanoparticles dispersed in these fluids are sensitive to such
environment [1]. One of the most significant alterations is the formation of the NP Protein Corona (PC) as
a result of the adsorption of proteins onto the inorganic surface. Currently, there is an increasing
awareness of the importance of the NP-PC in the field of inorganic NPs, which is reflected in the
increasing number of recent publications that cover different aspects of this topic [2-4]. Largely, this is
because this spontaneous coating provides the biological identity to the composite NP-PC and determines
the interactions between the NPs and the host in living systems. As a result, the proper understanding of
the NP-PC formation has emerged as a crucial aspect to study the evolution, biodistribution and reactivity
of NPs in organisms and, therefore, for the safe design of engineered NPs [2].

Our studies aim to understand PC formation on model NPs, comprising metal (Au, Ag) and metal oxide
(Fe3O4, CeO2 and CoO), with sizes ranging from 7 to 20 nm and dispersed in commonly used cell culture
medium supplemented with serum. As a result, we have observed that all tested NPs adsorb proteins onto
their surface, thereby forming a PC through a dynamic process. Remarkably, an evolution from a loosely
attached PC (soft PC) towards an irreversible PC (hard PC) have been observed over time. Despite
studied NPs have similar characteristics (i.e., hydrophobicity and surface charge), different temporal
patterns of PC formation have been observed, which can be considered as a fingerprint for NP
classification and identification [5, 6]. Moreover, different PC formation processes have been observed
which depend on the NPs composition, size and surface state. All this aspects are of special relevance
since interactions and interference of inorganic NPs with cells and tissues take place at different time
scales. Similarly, biodistribution and residence times in different biological environments depends on the
NP surface characteristics. Importantly, some fundamental questions are still unclear such as the format
of presentation of the proteins in the PC, the role of the ubiquitin proteasome system (which identify and
"tag" proteins the body no longer need, as aged proteins, denaturated and aggregated) and the metabolic
degradation of the corona after extended period of time. All of this aspects need to be analyzed and
resolved aiming to design nanomaterials to be applied safely.

NP-protein interactions. The process of conjugation of the NP when inserted in biological media takes few minutes in
the working conditions (I), which evolves to a NP coated with protein in equilibrium with the proteins in the medium
(II), then later evolves towards an irreversible protein corona with proteins that are no longer in equilibrium with
their in-solution counterparts (III) [6].

---------------------------------
[1] Rivera-Gil, P. et al. Acs Nano 2010, 4 (10), 5527-5531.
[2] Faunce, T.A. et al., Nanomedicine, 2008, 3, 859-866.
[3] Rocker, C. et al. Nature Nanotechnology, 2009, 4, 577-580.
[4] Monopoli, M.P. et al. Journal of the American Chemical Society, 2011, 133, 2525-2534.
[5] Casals, E. et al. Acs Nano, 2010, 4, 3623-3632.
[6] Casals E., et al. Small, 2011 7(24), 3479-3486.
 Optimization in the synthetic routes of water-dispersable iron oxide
nanoparticles for magnetic hyperthermia.
I. Castellanos Rubio, E. Garaio, M. Insausti, I. Gil de Muro, F. Plazaola.
Dpto. Química inorgánica, Facultad de Ciencia y Tecnología, UPV/EHU, Bº Sarriena,
48940 Leioa, Spain
[email protected]

Iron oxides nanoparticles have acquired great relevance in the area of biomedical diagnostics
and therapy. Among many others they include magnetic separation, magnetic resonance
imaging (MRI) contrast agents, targeted drug delivery or magnetic hyperthermia1. Hyperthermia
applications are based on the exothermic properties of magnetic materials under the influence of
an alternating current magnetic field and require water dispersible and biocompatible systems in
the 15-50 nm range.2,3

In this research we report the preparation and characterization of Fe3O4 water soluble
nanoparticles by precipitation from iron (II) chloride in basic solution under mechanical stirring
and ultrasonic irradiation. Synthetic parameters as temperature, stirring or coating agents have
been changed in order to obtain nanoparticles surrounded by 6-aminohexanoic acid,
poly(acrylic) acid, 3-hidroxybutanoic acid and amylose with controlled sizes. The samples have
been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetry
and magnetic measurements. The specific absorption rate (SAR) was calculated to compare the
efficiency of heating each sample for the various applied magnetic fields.

Colloidal solutions of the nanoparticles were analyzed by means of TEM microscopy and
distributions of NPs with average sizes from 13 to 34 nm were observed depending on the
surrounded ligand. Broader distributions have been obtained for samples without coating agent
synthesized without ultrasonic irradiation. In solid samples, magnetite structure was
corroborated by X ray diffraction. In order to know the proportion of organic matter
thermogravimetric measurements were performed in argon atmosphere and different contents
(from 4% to 60%), depending on the sample preparation, have been obtained.

Magnetization measurements in function of magnetic field performed at 300 K, have revealed a

ferromagnetic character in which hysteresis loops with coercive fields from 45 Oe to 90 Oe can
be observed. The maximum value for saturation at 300K is achieved at 84emu/g. Also we
report specific absorption rate (SAR) trends of the magnetite NPs versus frequency and intensity
of the applied field. The values increase with the intensity and the frequency of the magnetic
field, although they are lower than those obtained in related materials. This fact could be
explained because of the particle size, size distribution and measurement conditions. It is to
notice that SAR values clearly vary from one sample to another which could be attributed to the
different functionalization.

(1) Belousov, A. N. The use of magnetite nanoparticles in applied medicine. Materials Science
Forum 2011, 694, 205-208.

(2) Pankhurst, Q.; Connolly, J.; Jones, S.; Dobson, J. Journal of Physics D: Applied Physics 2003,
36, R167-R181.

(3) Banerjee, R.; Katsenovich, Y.; Lagos, L.; McIintosh, M.; Zhang, X.; Li, C.-Z. Current Medicinal
Chemistry 2010, 17, 3120-3141.
 Nanostructures for Magnetic Imaging and Therapy

Paula M. Castilloa, Elvira Fantechib, Alessandro Lascialfaric, Andrea Sbarbatid, Claudia Innocentib ,
Maria F. Casulaa,*, Claudio Sangregoriod,*

a
INSTM and Dip. di Scienze Chimiche e Geologiche, Univ. di Cagliari, I-09042 Monserrato (Ca), Italy
b
INSTM and Dip. di Chimica ‘U. Schiff’, Univ. di Firenze, I-50019 Sesto Fiorentino (Fi) Italy
c
CNR and Dip. di Scienze Molecolari Applicate ai Biosistemi, Univ. di Milano, I-20134 Milano, Italy
d
Dip. di Scienze Neurologiche, Neuropsicologiche, Morfologiche e Motorie, Univ. di Verona, I-37134, Verona, Italy
d
CNR-ISTM Milano and INSTM UdR Firenze, I-20133 Milano Italy
*tel: +390554573270; fax: +390554573372; e-mail: [email protected]

Composite nanostructures containing a superparamagnetic material represent a versatile platform

for the design of multifunctional tools for biomedicine, ranging from cancer therapy, cell imaging
and magnetic separation.

In this work, multifunctional ultrasmall superparamagnetic iron oxide (USPIO) coated by either
biopolymers, non-toxic commercial dispersants, silica or gold were tested as contrast enhancers in
magnetic resonance imaging (MRI) and as magnetic hyperthermia mediators.
XRD, TEM, FT-IR, TGA, N2-Physisorption and DLS techniques were used to gain insights on the
structural and morphological features of the materials as well as on the features of the coating.
SQUID magnetometry has been used to investigate the magnetic behaviour of the nanoparticles by
zero field cooled-field cooled measurements as well as the field dependence of the magnetization at
low temperature. NMR-Dispersion (NMRD) profiles, i.e., the measurements of proton nuclear r1
(longitudinal) and r2 (transverse) relaxivities as a function of frequency were collected in order to
gain insights on the ability of the materials to act as contrast agents for MRI. Specific Absorption
Rate (SAR) measurements were performed to test the potential of the nanostructures in magnetic
hyperthermia.

Acknowledgements

P.M.C. thanks the Junta de Andalucia through the Fundación Progreso y Salud for a mobility
fellowship.
 Metal Oxide Carbon Nanotube Composites for Electronic Devices
Alina Chanaewa1, Beatriz H. Juárez3, Christian Klinke2, and Horst Weller2
(1) Institute of Physics, University of Freiburg, Hermann-Herder-Str. 3, 79104 Freiburg,
Germany
(2) Institute of Physical Chemistry, University of Hamburg, Grindelallee 117, 20146 Hamburg,
Germany
(3) IMDEA Nanociencia,Avda. Fco. Tomás y Valiente 7, 28049 Madrid, Spain
Email: [email protected]

In the recent years, the development of several low cost preparation techniques such as
colloidal synthesis, led to a boost of new technological developments on the nanometer
scale. The field of nanoelectronics, where the wires or contacts have the dimension of few
nanometers, expands rapidly due to the possibility of the nanomaterial combination. The
advantage of so called composites is the synergetic effects deriving from different
nanomaterials, which were combined.
We present the non-covalent attachment of semiconducting metal oxide nanoparticles (MeO-
NP) to untreated carbon nanotubes (CNTs) using wet chemistry methods.[1] This
methodology yields uniformly covered composite materials. It allows synthesis of individual
MeO-NP-CNT in suspensionsas well asof completely covered three-dimensional NP-CNT-
arrays. Due to quantum confinement, semiconductor nanoparticles can act as tunable light
absorbers while CNTs are considered as supporting material for quantum dots and charge
transport medium since theCNTs reveal mechanical stability, chemical inertness and provide
ballistic transport.Assuming close interaction RIWKH&17ʌ-system with the individual particle,
a gapless interface for charge transfer is created.
The light absorbing and charge conducting properties of described composites are
considered advantageous for sensing as well as photovoltaic applications. Therefore,
individualMeO-CNTs were used as field-effect transistor channels. The resulting devices
were shown to exhibit UV-light sensitivity which was not observed for NP-free devices.[2]
Furthermore, we succeeded in assembling a hybrid solar cell based on a three-dimensional
electrode consisting of a CNT array and a metal oxide hole blocking layer. The network was
directly grown on a transparent conductive layer via chemical vapor deposition in a novel
steady-state reactor.To proof the principle photocurrent generation was demonstrated by
integrating the 3D electrode into a typical organic solar cell based on P3HT/PCBM.[3]
The integration of composite materials into two different electrical devices demonstrates the
potential of application-oriented material design on the nanometer scale.

[1] B. H. Juarez, M. Meyns, A. Chanaewa, Y. Cai, C. Klinke, H. Weller, J. Am. Chem. Soc.
130 (2008) 15282.
[2] A. Chanaewa, B. H. Juarez, H. Weller, C. Klinke, Nanoscale4 (2012) 251.
[3] H. Borchert, F. Witt, A. Chanaewa, J. Dorn, T. Dufaux, M. Kruszynska, A. Jandke, M.
Höltig, T. Alfere, F. Werner, J. Böttcher, C. Gimmler, C. Klinke, M. Burghard, A.Mews, H.
Weller, J.Parisi,J. Phys. Chem. C, accepted.
 pH titration: a fruitful toolbox for optimization of conjugation
reactions on colloidal nanoparticles
Gaëlle Charron,1,2*# Dominik Hühn,3# Aurélie Perrier-Pinault,1 Christopher J. Pickett,2 Thomas
Nann,4 and Wolfgang J. Parak2*#

1
Univ Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR CNRS 7086, 15 rue J-A de Baïf, 75205 Paris
Cedex 13, France
2
University of East Anglia, School of Chemistry, Energy Materials Lab., NR47TJ – Norwich, UK.
3
Fachbereich Physik and WZMW, Philipps Universität Marburg, Marburg, Germany
4
Ian Wark Research Institute, University of South Australia, Mawson Lakes Campus, Mawson Lakes
South Australia 5095.
* corresponding authors: [email protected], [email protected]
marburg.de

Efficient and controlled conjugation of molecules to nanoparticles (NPs) can be tedious on

charged NPs. This is particularly problematic when working with expensive biomolecules or high
value NP core materials. These difficulties stem from the fact that there is a general lack of
quantitation of surface functionalities in the sample. The knowledge of the amount of reactive
material would enable the estimation of reaction yield and benefit the optimisation of the reaction.
Another pitfall lies in the fact that classical bioconjugation methods are optimised for proteins. The
physicochemical properties of NPs can however markedly differ from those of proteins, in particular
with regard to the charge distribution, which can affect the efficiency of bioconjugation reactions. In
this work, we aim at promoting the use of pH titrations to optimise conjugation reactions on colloidal
NPs. The method is hereafter applied to carboxylate bearing NPs and leads to information on both
the amount of reactive molecules, their density on the surface and their physicochemical properties
through the determination of the pKa. This last parameter enables the prediction of the feasibility of
EDC-activated amide bond formation, a reaction that is notoriously challenging.
 Bioactive nanoparticle targeting of neurons

AgathiChristofidoua, Tracey A. Newmanb, and Antonios G. Kanarasa*

a
School of Physics and Astronomy, The University of Southampton, Southampton, UK
b
School of Medicine, The University of Southampton, Southampton, UK

Corresponding author: [email protected]

Abstract
Numerous diseases and pathologies affect the central nervous system (CNS), but the number
of effective treatments and early prognosis for these conditions is negligible. The CNS has a
series of elaborate barriers, the blood brain barrier (BBB), which limit the influx and efflux of
various macromolecules. Drug delivery to the brain is hindered by the BBB which acts as a
selective filter for the controlled movement of molecules from the peripheral blood
circulation into the brain1,2. Hence, the need for development of new strategies to deliver
drugs into the brain and/or get a deeper understanding regarding the biological processes
associated with a disease is rising.
Gold nanoparticles(NPs) are promising candidates in achieving such goals3,4. This is due to
their ease of preparation, well understood surface chemistry, intrinsic optical and thermal
properties as well as good biocompatibility.
In this poster we present the effect of gold NPs on the physiology of PC12 neuronal cell line
and primary neurons, in terms of uptake, cytotoxicity and axonal transport. The surface
chemistry of the NPs was engineered so that they can gain entry into cells in a specific and
controlled manner (their diameters are 15 nm and 80 nm for nanospheres and nanoshells,
respectively). The entry into the neurons is achieved by the adherence of specific
biomolecules (PEG and tet-peptide) on them, which form an organic corona around the NPs’
metal core5. The uptake of NPs was studied by exposing the cells at NP concentrations that
were not cytotoxic to them- identified by cytotoxicity studies (including compromise of cell
membrane and caspases formation).
References:
[1]. EORTC [European Organisation for Research and Treatment of Cancer, NCI [National
Cancer Institute], AACR [American Association for Cancer Research]
[2]. Roney, C.; Kulkarni, P.; Arora, V.; Antich, P.; Bonte, F.; Wu, A.; Mallikarjuana, N.N.;
Manohar, S.; Liang, H.-F.; Kulkarni, A. R.; Sung, H.-W.; Sairam, M.; Aminabhavi T. M.,
Journal of Controlled Release, 2005, 108, 193-214.
[3]Bartczak, D; Muskens, O L; Millar, T M; Sanchez-Elsner, T; Kanaras, AG, Nanoletters,
2011,11, 1358-1363
[4]Chen, J; Yang , M; Zhang , Q; Cho , E- C; Cobley, CM; Kim, C; Glaus, C; Wang , LV;
Welch, MJ; Xia, Y, Advanced Functional Materials, 2010, 20, 3684–3694
[5] Choi, H. S.; Ipe, B. I.; Misra, P.; Lee, J. H.; Bawendi, M. G.; Frangioni, J. V. Nano Lett. 2009, 9, 2354-2359.
 Auger recombination suppression in nanocrystals with
asymmetric electron-hole confinement
J I Climente1, J L Movilla1 and J Planelles1
1
Department of Physical and Analytical Chemistry, Universitat Jaume I, Castelló, Spain, E-12080

In the last years, one of the most successful techniques to reduce the intermittency of nanocrystal
emission (blinking) is the use of core/shell structures with type-II or quasi-type II band alignment.
[1,2] There is increasing evidence that blinking is associated with non-radiative Auger processes
of charged excitons.[3,4] Building on this knowledge, we carry out a numerical study of Auger
recombination in such nanostructures. The contributions of volume scaling, electron-hole overlap
and interface smoothness are compared[5]. A number of experimentally relevant results are
found, namely:

i) we predict that in core/shell nanocrystals where electrons and holes have different spatial
location, there are magic shell thicknesses which lead to very slow Auger relaxation regardless of
the core size. An example can be seen in the contour figure below, highlighted by dashed lines.
These critical thicknesses arise from quantum destructive interferences between electron and hole
wave functions but, contrary similar suppressions reported for core sizes[4], they are robust
against potential fluctuations. This, alongside with the availability of precise shell growth
techniques suggests the possibility of synthesizing ensembles of nanocrystals with minimal Auger
recombination.

ii) In relation to recent experiments with CdSe/CdS nanocrystals, we confirm that few-monolayer,
spontaneous interface diffusion suffices to reduce Auger rates by one-two orders of magnitude.[2]

iii) We show that the saturation of Auger recombination rates observed for large shell
thicknesses[1,2] can be explained as a consequence of interband coupling.

Fig.1 – Core/shell nanocrystal and the Auger process under study.

The contour plot shows Auger relaxation rates vs. core size (Lc) and shell size (Ls).

References
[1] Mahler B, Spinicelli P, Buil S, Quelin X, Hermier JP and Dubertret B, 2008 Nat. Mater. 7 659; Osovsky R, Cheski
D, Kloper V, Saschiuk A, Kroner M and Lifshiftz E, 2009 Phys. Rev. Lett. 102, 197401.
[2] Garcia-Santamaria F, Brovelli S, Viwanatha R, Hollingsworth JA, Htoon H, Crooker SA and Klimov VI, 2011 Nano
Lett. 11, 687; Vela J., Htoon H, Chen Y, Park YS, Ghosh Y, Goodwin PM, Werner JH, Wells NP, Casson JL and
Hollingsworth JA, 2010 J. Biophotonics 3, 706.
[3] Efros AL, 2008 Nat. Mater. 7, 612.
[4] Cragg GE and Efros AL, 2010 Nano Lett..10, 313.
[5] Climente JI, Movilla JL and Planelles J, 2011 Small (in press); Climente JI, Movilla JL and Planelles J, J. Appl.
Phys. (in press).
 Surface Modification of Anatase Nanoparticles: A Combined DFT and Experimental
Study of Optical Properties

7DWMDQD'6DYLüa,YDQD$-DQNRYLüa=RUDQ9âDSRQMLüa, 0LUMDQD,ýRPRU a, Dušan Ž.

9HOMNRYLüb6QHåDQD'=DULüb-RYDQ01HGHOMNRYLüa
a
8QLYHUVLW\RI%HOJUDGH9LQþD,QVWLWXWHRI1XFOHDU6FLHQFHV
P.O. Box 522, 11001 Belgrade, Serbia
b
Department of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11001
Belgrade, Serbia

Surface modification of nanocrystalline TiO2 particles (45 Å) with catecholate-type ligands

consisting of extended aromatic ring system, that is, 2, 3-dihydroxynaphthalene and
anthrarobin was found to alter optical properties of nanoparticles similar to catechol (Figure
1). The formation of the inner-sphere charge-transfer (CT) complexes results in a red shift of
the semiconductor absorption compared to unmodified nanocrystallites and the reduction of
the band gap upon the increase of the electron delocalization on the inclusion of additional
rings. According to Job’s method of continuous variation, for chosen enediol modifiers,
binding was found to be through bidentate binuclear (bridging, catecholate type) complexes
leading to restoration of six-coordinated octahedral geometry of surface Ti atoms. From the
Benesi-Hildebrand plot, the stability constants in methanol/water = 90/10 solutions at pH 2 of
the order 103 M-1 have been determined.

Fig. 1 Absorption spectra of surface modified 45 Å TiO2 nanoparticles (19 mM,

methanol/water=90/10, pH 2) with different ligands (0.3 mM): A-bare TiO2; B-catechol; C-2,
3-dihydroxynaphthalene; D-anthrarobin.

The binding structures were investigated by using FTIR spectroscopy. Also quantum
chemical calculations on model systems using density functional theory (DFT) were
performed to obtain vibrational frequencies of charge transfer complexes, and the calculated
values were compared with the experimental data. DFT calculations of Ti2OL(OH)4
(bridging) vibrational frequences show better agreement with experimental data in
comparison to TiL(OH)2 (chelating) frequencies. It is obvious that the extension of the
aromatic ring system in modifier molecules opens up the possibility for fine-tuning of the
electronic properties of TiO2 nanoparticles.
 NMR relaxation studies of liquid crystal dendrimers

Carlos Cruz

Instituto Superior Técnico – Technical University of Lisbon, Physics Department, Av. Rovisco Pais, 1,
1049-001 Lisboa, Portugal

Dendrimers are hyperbranched molecules with well defined nanometer-scale dimensions associated with
the degree of branching (generation) [1]. Important potential or actual technological applications of these
systems, both in biomedicine and materials science, have been presented in the literature [2]. Typically, a
dendrimer includes an inner branched section, irradiating from a central core, and a shell of functional
groups. External groups with mesogenic properties may induce anisotropic molecular packing of the
dendrimers, giving rise to dendritic liquid crystalline (LC) phases [3]. The self-organizing characteristcs of LC
phases associated with molecular mobility and peculiar tunable surface interaction, combined with the
properties of multifunctional dendrimers opens new perspectives for technological applications [4].
Understanding the anisotropic physical properties of these materials (electromagnetic, optical, viscoelastic,
...) and their dependence on temperature is very important for their characterization. In particular, NMR
provides valuable tools for the study of molecular order and dynamics in these systems. In the last years, a
number of LC dendrimers of different generations, exhibiting mesophases of different types, have been
studied by NMR relaxation [5]. A theoretical approach to the description of LC dendrimers properties may be
achieved by means of the ensemble dendrimer model. This theory describes the LC dendrimers as a
combination of interacting dimers with different spacers, corresponding to the different branching paths
between pairs of mesogenic units [6]. Taking that model into account, we focused our recent NMR
investigations on LC dimers, searching for the relation of the dimers’ conformations in the mesophases with
the phase structure and molecular movements. Besides the fundamental interest of these studies, the fact
that these systems exhibit different nematic phases with peculiar properties [7] can be important for
technological applications as the nematic phase is widely used in LC display technology.

Acknowledgments: This work was partially supported by the European Comission under 7th Framework
Programme through project PEOPLE-2007-1-1-ITN-215884 (Dendreamers)

[1] G. R. Newkome, C. N. Moorefield, and F. Vögtle, Dendrimers and Dendrons: Concepts, Syntheses,
Applications Wiley-VCH, Weinheim, (2009).
[2] Jean M. J. Frechet and Donald A. Tomalia Dendrimers and Other Dendritic Polymers, J. Wiley & Sons
(2001); Istvan J. Majoros, James R. Baker JR Dendrimers-Based Nanomedicine. 27 Warren Street, Suite 401-
402, Hackensack, NJ 07601: Pan Stanford Publishing Pte. Ltd., (2008); C. Ornelas, J. Ruiz; C. Belin, D. Astruc, J.
Am. Chem. Soc. 131 , 590 (2009).
[3] V. Percec, W. D. Cho, and G. Ungar, J. Am. Chem. Soc. 122, 10273 (2000); J.-M. Rueff, J. Barbera, B.
Donnio, D. Guillon, M. Marcus, and J. L. Serrano, Macromolecules 36, 8368 (2003).
[4] M. W. P. L. Baars, M. C. W. van Boxtel, C. W. M. Bastiaansen, D. J. Broer, S. H. M. Söntjens, E. W. Meijer,
Adv. Mater., 12, 715 (2000); M. Marcos, R. Martin-Rapun, A. Omenat, J. Barbera, and J. L. Serrano, Chem.
Mater., 18, 1206 (2006); E. Terazzi, T. B. Jensen, B. Donnio, K. Buchwalder, C. Bourgogne, G. Rogez, B.
Heinrich, J. Gallani, and C. Piguet Dalton Trans., 40, 12028 (2011).
[5] P.J. Sebastião, C. Cruz, A.C. Ribeiro, Advances in Proton NMR Relaxometry in Thermotropic Liquid Crystals
in Nuclear Magnetic Resonance Spectroscopy of Liquid Crystals, pag. 129-167, Ed. R. Dong, World Scientific
Co., (2009); D. Filip, C. Cruz, P. J. Sebastião, M. Cardoso, A. C. Ribeiro, M. Vilfan, T. Meyer, P. H. J. Kouwer,
and G. H. Mehl, Phys. Rev. E, 81, 011702 (2010).
[6] A. G. Vanakaras, D. J. Photinos, J. Mater. Chem. 15, 2002 (2005).
[7] V. P. Panov, M. Nagaraj, J. K. Vij, Yu P. Panarin, A. Kohlmeier, M. G. Tamba, R. A. Lewis and G.H. Mehl,
Phys. Rev. Lett. 105, 167801 (2010); V. P. Panov, R. Balachandran, M. Nagaraj, J. K. Vij, M. G. Tamba, A.
Kohlmeier, G. H. Mehl, Appl Phys. Lett., 99, 261903 (2011).
FRET-based H1N1 nucleoprotein determination in anti-influenza virus
vaccines
P. J. Cywinski1, L. Olejko1, L. J. Charbonnière2, K. Nchimi Nono2, C. Dahmen3, A. Kage3, and
H.-G. Löhmannsröben1
1
Department of Physical Chemistry, Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam-Golm,
Germany

2
Laboratoire d'Ingénierie Moléculaire Appliquée à l'Analyse (LIMAA) IPHC - UMR 7178 - CNRS ECPM, 25 rue Becquerel, Strasbourg, France

3
APTARES AG, Am Scheunenviertel 1, 15749 Mittenwalde, Germany

In anti-influenza virus vaccines, H1N1 nucleoprotein is considered as a contaminant protein coming

from the vaccine preparation. Major concern is associated with the fact that after vaccination this
protein may induce severe hypersensitive reactions among persons with egg allergy. Conventionally,
this nucleoprotein can be detected using SDS-PAGE, blot dot assays or surface plasmon resonance
techniques. Those methods, however, suffer from reduced sensitivity or high complexity. In our
approach, two different nucleoprotein-specific aptamers were conjugated to terbium complexes and
quantum dots (QDs), respectively. Förster Resonance Energy Transfer (FRET) from Tb-complex to QD
was observed upon binding of the aptamers to H1N1 nucleoprotein, as demonstrated both by
steady-state and time-resolved luminescence spectroscopy. We used this sandwich aptamer-based
homogenous FRET assay (SABA FRET) to determine nucleoprotein in three vaccines, namely Influsplit
SSW® 09/10, 10/11 and 11/12. We have chosen Influsplit SSW® since it is the seasonal anti-influenza
vaccine most often applied to patients in Germany. Using the SABA FRET assay, nucleoprotein
concentrations were found to be 10μg/ml, 3 μg/ml and 1μg/ml in Influsplit SSW® 2009/2010,
2010/2011 and 2011/2012, respectively. The presented SABA FRET assay allowed detecting
nucleoproteins down to 5ng/ml (LOD (3V). This highly specific and sensitive SABA FRET assay
constitutes a novel promising approach that has great potential to be extended to early detection of
severe medical conditions e.g. Alzheimer’s disease. Moreover, it can be used to control vaccine
quality in-line as well as serve to practitioners as tool in diagnostics.
Title: Synthesis of Luminescent Silicon Nanomaterials via Magnesiothermic Reduction

Authors: Mita Dasog and Jonathan G. C. Veinot

Affiliation: Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada,

T6G2G2

Abstract: The chemistry, physics and electronics applications of bulk silicon have been widely
studied and are well understood and in this context Si is the workhorse material of the electronics
industry. Of late, silicon nanocrystals (Si NCs) have received substantial attention because of
their potential commercial viability in numerous economic sectors (e.g., biomedical imaging,
catalysis, solar energy conversion and storage). While much has been achieved, many hurdles
must be overcome if these nanomaterials are to be integrated into practical devices. A very
attractive application of silicon nanocrystals is integrating silicon nanocrystal luminescence (i.e.,
photonics) with silicon electronics. An attractive method for doing this involves thermally
annealing silicon rich oxide precursors at temperatures as high as 1100oC in reducing
atmosphere. Unfortunately, this is processing temperature far exceeds established thermal
budget of electronic devices (i.e., 425oC). In this regard, it is necessary to explore methods to
lower the processing temperature necessary for preparing NCs. Here in we report synthesis of
mono-disperse oxide embedded and freestanding Si and Si3N4 NCs at 500oC using sol-gel
polymer precursors and metal reductants. This new approach offers a convenient method that
could facilitate interfacing of luminescent silicon-based materials with on-chip applications.
 Surface oxidation of tin chalcogenides nanocrystals revealed by Mössbauer spectroscopy
a,b a a a a b c a
A. de Kergommeaux , A. Fiore , J. Faure-Vincent , F. Chandezon , A. Pron , R. de Bettignies , B. Malaman and P. Reiss
a
DSM/INAC/SPrAM (UMR 5819 CEA-CNRS-UJF), Laboratoire d’Electronique Moléculaire, Organique et Hybride, CEA
Grenoble, 17 rue des Martyrs, 38054 Grenoble cedex 9, France. E-mail: [email protected]
b
INES, CEA-DRT/LITEN/DTS/LMPV, Institut National de l’Energie Solaire, Le Bourget du Lac, FRANCE
c
LCSM, Institut Jean Lamour, Dept P2M, équipe 103, CNRS (UMR 7198)-Nancy Université, B.P. 70239, 54506 Vandoeuvre-
les-Nancy Cedex, FRANCE
Semiconductor nanocrystals (NCs) can be used as light-harvesting materials in solution processed solar
cells. With PbS NCs power conversion efficiencies up to 6% have recently been reported, higher than for any
other type of NCs studied to date.1 Due to the risks for the environment and for human health, however, lead
based materials are not acceptable for a broad use and therefore NCs of alternative semiconductor materials
have to be developed. Tin chalcogenides, in particular SnS and SnSe appear as good candidates, due to their
low band gap (1.3 eV for SnS and SnSe), large earth abundance and environmentally benign character.
Although synthesis methods for tin chalcogenide NCs of low size dispersion have been reported,2 they
have not yet been successfully integrated in solar cells. Mössbauer spectroscopy is a very accurate tool to
identify the oxidation state of tin. By using this technique (Fig. 1), we found that SnS NCs exhibit strong
surface oxidation upon exposure to air. A very similar behaviour was observed using six different synthesis
methods. In addition 119Sn-NMR, HRTEM, EDS and XRD analyses were used to investigate the oxidation
mechanism. Thanks to its high sensitivity, Mössbauer spectroscopy reveals that already after some minutes
exposure to air the NCs surface is oxidized through an amorphization process, yielding a ternary phase
composed of Sn, S and O (Fig. 1h). As expected, SnSe and SnTe exhibit an even higher tendency for oxidation.
We conclude that the passivation of tin chalcogenide NCs by appropriate shell materials is needed to avoid
their surface oxidation, which is likely impeding their application in optoelectronics.

1
Tang et al., Nat. Mat., 10 (2011) 765-771 ; Gao et al., Nano Lett., 11 (2011) 3 1002-8
2
Kovalenko et al., J. Am. Chem. Soc., 129 (2007) 37 11354-11355 ; Baumgardner et al., J. Am. Chem. Soc., 132 (2010) 28
9519-9521 ; Hickey et al., J. Am. Chem. Soc., 130 (2008) 14978-14980.
Figure 1: STEM and HRTEM images of
SnS nanocrystals prepared using a)
protocol A, b) protocol B, c) protocol
D, d) protocol E, e) protocol F. f)
Composition derived from EDS
measurements for all protocols. g)/h)
Tin-Mössbauer spectra measured at
10K for SnS NCs prepared using the six
different synthesis methods without
air exposure (g) and at different
oxidation steps for protocol A (h). i)
XRD diffractograms of SnS NCs using
protocol A before and after air
exposure.
 “Additional skills development in scientific projects (beyond the ITN)”

Frans Dekker
Managing Director / Consultant / Trainer / Coach
Idrealizer

[email protected]

Developing an idea for a new project, a new product, or for improvements in existing
ways of doing something is only a small part of the challenge we face. The real
challenge starts when we want to turn such an idea into reality. In any highly
competitive field with scarcity of resources, like experienced researchers, time,
money, equipment, and materials, many ideas don’t make it. Our success to turn our
idea into reality depends on many factors, many of them external. However, in
addition to the development of scientific knowledge, each of us has also the
possibility to increase his or her level of success, by working with the right attitude,
and by being able to use effective leadership, self-management, teamwork, and
interpersonal skills. Unfortunately, the development of these “additional” skills is often
not in scope in scientific projects, and completely depends on the personal
preferences, vision, and competencies of a scientific project coordinator and
supervisor(s) involved.

The initiators of the Dendreamers project wanted to take a different approach, and
clearly incorporated their vision on the development of additional skills into the
overall project plan. The objective of the additional skills development activities, was
to:
1. Increase the productivity and effectiveness of the research fellows while working
on their project;
2. Increase the possibilities for the research fellows to develop a successful career,
once they have finished their work on the Dendreamers project;
3. Accelerate the development of the field of research within Europe by means of
industrial collaboration, as well as by increasing the possibilities for future spin-off
research projects, or even start-ups.

With a combined approach of individual career development planning, summer

school skills training programs, and a series of web seminars on additional skills
development, we wanted to make sure that each of the Dendreamers fellows would
have the possibility to increase his or her effectiveness. In addition, we have worked
with a selected number of Dendreamers fellows, who applied and were granted
access to an Advanced Development Program (ADP). This ADP consisted of
individual 1:1 coaching, including personality type tests, identifying strengths and
weaknesses, as well as working on specific identified development objectives.
Overall, the results of the Dendreamers additional skills development program are
considered positive by many of the Dendreamers fellows.

We look forward to share our learning and insights on this project, and provide a
number of recommendations. We are confident, that these recommendations can
benefit anyone who is in charge of scientific projects, R&D projects, as well as to
anyone who is in charge of funding scientific projects.
 Electrochemical studies on semiconductor nanocrystals

L. de la Cueva1, C. Alonso2 and B. H. Juárez1

1
IMDEA Nanoscience, Cantoblanco, 28049, Madrid, Spain
2
Departamento de Química-Física Aplicada. Universidad Autónoma de Madrid, (UAM). Madrid, Spain

e-mail: [email protected]

Semiconductor nanocrystals (CdSe, CdS, CdTe, InP) deposited on electrodes have been extensively
1,2,3
studied by means of cyclic voltammetry. The oxidation peak in a cyclic voltammogram can be related
to the valence band of the nanoparticles (or the HOMO of the ligands) and the reduction peak can be
related to their conduction band. Thus, a correlation can be established between the optical and the
electrochemical gaps. The uncertainty in the measured values are related to parameters such as
concentrations, measuring conditions, etc…This work focuses on a revision of several parameters
affecting the peaks and potential shifts obtained in the voltammogram of CdSe nanoparticles including
the chemical environment (ligands, washing procedures), size, illumination conditions, etc. Others
parameters such us shape and orientation of the nanoparticles with respect to the electrodes, as well as
double layer effects will be also discussed.

1
Haram, S. K.; Quinn, B. M.; Bard, A. J. J. Am. Chem. Soc. 2001, 123, 8860.
2
Kucur, E.; Riegler, J.; Urban, G. A.; Nann, T. J. Chem. Phys. 2003, 119, 2333.
3
Voelker, J.; Zhou, X.; Ma,X.; Flessau, S.; Lin, H.; Schmittel, M.; Mews, A. Angew. Chem. Int. Ed. 2010, 49, 6865.
 TAILORING THE SYNTHESIS AND APPLICATIONS OF THIN-
FLAT GOLD NANOPRIMS
Pablo del Pino, Beatriz Pelaz, Jesús M. de la Fuente
Instituto de Nanociencia de Aragon (INA), Universidad de Zaragoza, 50018 Zaragoza, Spain

As the degree of control to fabricate noble metals with well-defined shapes evolves,
new applications based on these materials can be explored. The optical properties of
metallic NPs come mainly dictated by their plasmon band. The position of the plasmon
band can be tuned along the Vis-NIR by tailoring the shape and anisotropy (aspect ratio)
of the NPs. Among a variety of metallic NPs, gold NPs (GNPs) with a number of
shapes, such as pseudospheres, rods, cubes or triangular prisms, to name a few, have
found a great deal of interest in literature, especially in bioapplications of NPs. This
popularity can be attributed to the distinctive properties of GNPs including plasmon
band, biocompatibility and ease of surface modification by a wide list of thiolated
molecules. Importantly, the plasmon band of anisotropic GNPs can be set in the NIR
range by tailoring the anisotropy of the NPs. This is the case of Au triangular
nanoprisms where the major contribution to the UV-Vis-NIR spectrum corresponds to
the in-plane dipolar mode laying in the NIR range. Most of the methods to produce NIR
absorbing GNPs rely on challenging synthesis with several steps and/or seed-mediated
approaches with cetyltrimethylammonium bromide (CTAB) as a surfactant. To the best
of our knowledge, CTAB is the most widely used and convenient surfactant to
synthesize Au nanorods and nanoprisms although it is a well-known toxic cationic
surfactant. The development of straightforward and scalable synthesis methods of non-
cytotoxic Au anisotropic NPs is of the most importance.
Herein, we report a straightforward one-pot synthetic method produce single-crystalline
flat-thin triangular gold nanoprisms using “green” reagents (avoiding the use of CTAB).
In a typical synthesis, nanoprisms were prepared by reduction of chloroauric acid by
sodium thiosulfate in water at room temperature. While the thickness of nanoprisms
remained constant (9 nm), the edge can be tuned from 80 nm up to 200 nm by adjusting
the final concentration/molar ratio of gold salt and reducing agent (sodium thiosulfate).
This allows tuning the surface plasmon band of nanoprisms along the NIR range.
The resulting nanoprisms were derivatized with heterobifunctional polyethylene glycol
(PEG) and 4-aminophenyl ȕ-D-glucopyranoside (glucose) chains to improve their
stability and cellular uptake, respectively. The heating properties of colloidal solutions
of NPRs upon 1064 nm light illumination were evaluated. As a proof of concept, the
biocompatibility and suitability of functional NPRs as photothermal agents were studied
in cell cultures. Due to their biocompatibility (avoiding CTAB), ease of production,
ease of functionalization and remarkable heating features, the nanoprisms discussed
herein represent a significant advance in the biocompatibility of nanoparticles and serve
as an attractive alternative to those currently in use as plasmonic photothermal agents.1
Importantly, gold nanoprism are also capable of high resolution visualization of probes
under photoacoustic imaging and these can therefore simultaneously deliver anatomical,
functional and molecular information with both high resolution and penetration
capabilities.2

(1) Pelaz, B.; Grazu, V.; Ibarra, A.; Magen, C.; del Pino, P.; de La Fuente, J. M., Tailoring the Synthesis
and Heating Ability of Gold Nanoprisms for Bioapplications. Langmuir 2012.

(2) Bao, C.; Beziere, N.; del Pino, P.; Pelaz, B.; Gomez Estrada, G.; Tian, F.; Ntziachristos, V.; Cui, D.;
de la Fuente, J. M., Gold Nanoprisms as Photoacoustic Signal Nanoamplifiers for in Vivo Bioimaging of
Gastrointestinal Cancer. ACS Nano Submitted.
 Cellular Applications of Semiconductor Quantum Dots:
From Cytosolic Delivery to Multicolor Labeling

James B. Delehanty, Ph.D.

Center for Bio/Molecular Science and Engineering
US Naval Research Laboratory
Washington, DC

Semiconductor nanocrystals or quantum dots (QDs) are among an array of nanoparticle

materials currently being developed for use in cellular labeling and sensing applications. QDs
offer unique photophyisical properties that make them attractive for biological applications.
These include: 1-high quantum yield, 2-resistance to photo- and chemical degradation, 3-size-
tunable, symmetrical/narrow emissions, and 4-excitation of multiple QD populations at a single
wavelength far removed from their emission. Collectively, these attributes make QDs ideal
materials for use in multicolor labeling and multiplexed sensing applications. To realize their
full potential as intracellular imaging, labeling and sensing reagents, robust and efficient methods
for cellular QD delivery must be developed.
This talk will cover two current areas of active research within our laboratories: 1-the
bioconjugation of QDs to render them biocompatible and 2-the development of noninvasive
means of delivery to target the QDs to various subcellular compartments and structures. A
variety of methods for the intracellular delivery of QDs will be highlighted. Specifically, the use
of various peptidyl sequences for the endocytic uptake and the subsequent endosomal escape of
QDs to the cytosol will be demonstrated. Our results will be discussed within the context of
multicolor cellular labeling and imaging with regard given to the important issue of nanoparticle
cytotoxicity.
 Two-Color Antibunching from Band-Gap Engineered Colloidal
Semiconductor Nanocrystals
Zvicka Deutsch, Osip Schwartz, Ron Tenne, Ronit Popovitz-Biro, Dan Oron

Abstract
Quantum emitters of light usually tend to emit photons one by one, rather than in
bursts. This ‘photon antibunching’ is an inherently quantum phenomenon which is
reflected in a more even distribution of photons in time compared to that observed for
classical sources [1]. Antibunching is a ubiquitous phenomenon, already observed
from a variety of quantum emitters (atoms, dye molecules, quantum dots). However,
as light emission is usually observed only from the lowest excited state (‘Kasha’s
rule’), it is essentially a two-level, single-color phenomenon. This is a significant
limitation on the type of nonclassical light sources based on this principle. We devise
an engineered multicomponent quantum-dot fluorophore which, upon
photoexcitation, emits stochastically in either one of two distinct and independently
controlled colors, but exhibits strong antibunching between the two. We show that
exciton-exciton coupling within the quantum dot via the mechanism of Auger
recombination leads to nearly complete antibunching of the two emission colors, with
a suppression depth exceeding 80%. Effectively, in this system we transform a typical
quantum dot emitter from a two-level system to a three-level V system (at room
temperature), offering realization of optical control schemes. Our design is modular,
enabling its extension to new quantum light sources with significantly more complex
emission properties. As will be discussed in the presentation, a similar design can also
serve as a solid-state platform for nonlinear interactions, such as incoherent photon
upconversion with potential to boost photovoltaic cell efficiency beyond the
Shockley-Queisser limit.

In top right panel a single

quantum dot (QD) spectrum
is exhibited with green and
red arrows signifying the two
emissions. A schematic
energy diagram of the QD is
exhibited in the top left panel.
Bottom right and bottom left
panels exhibit antibunching
of the NIR emission and the
cross correlation of the VIS-
NIR emissions.

1. Lounis, B., Orrit, M. Single-Photon Sources. Rep. Prog. Phys. 68, 1129–1179
(2005).
 Design of liquid crystalline gold nanohybrids.

Cristina Domínguez, Zsuzsanna T. Nagy, Gareth L. Nealon, Dris Ihiawakrim, Benoît

Heinrich, Daniel Guillon, Jean-Louis Gallani and Bertrand Donnio*

Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504

(CNRS-ULP), 23 rue du Loess, BP 43, F-67034 Strasbourg Cedex 2 (France).
[email protected] & [email protected]

Liquid crystalline nanoparticles are currently of great scientific and

technological interest. The coating of gold nanoparticles with mesogenic ligands
enhances their processability and allows the investigation of novel and synergistic
properties, with potential applications in various fields ranging from of optics,
electronics, and catalysis to biomedical research. Furthermore, new properties can be
expected to develop from the spontaneous self-organization of the nanoelements due to
the collective interactions of the particles. Pro-mesogenics dendrons are versatile
candidates for the elaboration liquid crystalline applications due to their modular
arborescent architecture and the hierarchization of their functionalization. The type of
pro-mesogenic molecules in the metal coating has a profound influence on the self-
assembly of the nanohybrids. Nematic or lamellar phases are expected for linear pro-
mesogens attached to the metal particles and cubic phases for dendrimeric pro-
mesogens. In this work, gold nanohybrids were prepared by a solvent-mediated partial
exchange reaction of the protective layer of dodecylthiol by dendritic ligands, and their
liquid crystalline properties were investigated.

Nealon, G. L.; Greget, R.; Dominguez, C.; Nagy, Zs. T.; Guillon, D.; Gallani, J.-L.;
Donnio, B. Beilstein J. Org. Chem. 2012, 8, 349.
 Fullerene liquid-crystal dendrimers and core-shell nanohybrid liquid crystal dendrimers:
towards new applications

Kalman Toth, Zsuzsanna Nagy, Cristina Dominguez, Daniel Guillon, Jean-Louis Gallani, Delphine Felder-Flesch* and
Bertrand Donnio*
Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg (UMR7504), 23,
rue du Loess, BP 43, 67034 Strasbourg Cedex 2 (France)

e-mail: [email protected]

Nanostructured Materials provide one of the greatest potential for improving performance and extended
capabilities of products in a number of industrial sectors. Research in this area aims at promoting molecular
objects able to self-organize into periodic arrays, whose functions can be ultimately addressed by external
stimuli. Synergistic collective behaviors and emergence of new physical properties are also expected upon this
ordering in various ordered lattices. Since self-organization also takes place in systems that have some fluidity
during the process, liquid crystals appear as ideal candidates.
Our approach towards nanostructured materials consists in the covalent functionalization of non-
mesogenic cores (C60, clusters, metallic nanoparticles), endowed with electronic/magnetic/optical properties,
by structuring protodendritic ligands to induce LC mesophases formation. The induction of LC mesophases of
various nanomaterials based on C60 and Au NP respectively, whose supramolecular arrangements and physical
properties are controlled by their surface derivatization, are reported.
Anisotropic moieties grafted onto the perfectly isotropic fullerene surface can enforce ordered self-
assembly, thus fullerene-containing liquid crystals (LC) can be obtained. 1 A complete series of
methanofullerene-based photoactive liquid crystal dyads have been synthesized and characterized. The Bingel
type cyclo-propanation reaction with side-on connected (unsymmetrical or symmetric) malonates is a suitable
method for obtaining the designed topology and incorporating the desired properties (i.e. light induced charge-
transport, liquid crystallinity and amphiphilicity). The amphiphilic structure of the molecule allows producing
extremely thin films of the Langmuir or Langmuir-Blodgett type, with high degree of structural order;
furthermore the macroscopic alignment can be modified by the LC behavior. Optical (fluorescence) and LC
properties have been investigated and described.
Ordered assemblies of monodisperse nanoparticles (NPs) that provide 2D or 3D superlattices constitute an
attractive class of nanostructured functional materials for a wide range of applications from high density
recording media, single-electron microelectronic devices to nanoscale metamaterials. 2 The controlled solvent
evaporation of passivated NPs technique mostly leads to bcc, hcp or fcc compact arrays of spheres on
micrometers scale, since primarily governed by close-packing and geometrical criteria. Alternatively, self-
assembling NPs using mobile liquid crystalline (LC) phases seems very promising, since a higher modularity
in the organization is allowed due to the softening of interparticles boundaries. It was shown that the nature of
the mesogenic capping agents gives rise to specific organizations and orientations of hybrids into nematic, 3
smectic, 4 columnar, 5 cubic, 6 and more complex mesophases. 7 In this study, we report on the induction of LC
mesophases of various hybrids whose arrangements are governed by NPs surface derivatization with proto-
mesogenic dendritic ligands.

1
a) D. Felder-Flesch et al. J. Mater. Chem. 2006 16 304; b) H. Mamlouk et al. J. Mater. Chem. 2007 17 2199; c) H. Mamlouk- Chaouachi et al. J.
Mater. Chem. 2011 21 9121.
2
a) S. A. Claridge et al. ACS Nano 2009 3 244; b) E. V. Shevchenko et al. J. Am. Chem. Soc. 2006 128 3620; c) S. Sun Adv. Mater. 2006 18 393; d) E. V.
Shevchenko et al. Nature 2006 439 55; e) D. V. Talapin ACS Nano 2008 2 1097; f) Z. Chen et al. ACS Nano 2008 2 1219.
3
a) L. Cseh et al. J. Mater. Chem. 2007 17 311; b) A. Demortière et al. Small 2010 6 1341
4
a) M. Wojcik et al. Angew. Chem. Int. Ed. 2009 48 5167; b) M. Wojcik et al. Soft Matter 2010 6 5397; c) M. Draper et al. Adv. Funct. Mater. 2011 21
1260.
5
X. Zeng et al. Adv. Mater. 2009 21 1746.
6
a) B. Donnio et al. Adv. Mater. 2007 19 3534; b) K. Kanie et al. J. Am. Chem. Soc. 2012 134 808
7
G Nealon et al. Beilstein J. Org. Chem. 2012, in press.

1
 Measurement of the main refractive indices of a organosiloxane low-generation
liquid crystalline dendrimer with the Michelson interferometer
L. Dumitrascu1,2 , J. L. Figueirinhas1,2, C. Cruz1,2, D. A. Wilson4 , G. H. Mehl4
1
IST - Technical University of Lisbon, Dep. de Física, Av. Rovisco Pais, P-1049-001 Lisboa, Portugal
2
CFMC, Av. Prof. Gama Pinto, 2, P-1649-003 Lisboa, Portugal
3
CENIMAT / I3N, Departamento de Ciência dos Materiais, Faculdade de Ciências e Tecnologia, FCT,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
4
Department of Chemistry, University of Hull, Cottingham Road, Hull, HU6 7RX, United Kingdom

Low generation dendrimers may exhibit liquid crystalline properties [1], this characteristic can be used to
ease the formation of regular structures of these materials at the nano scale. Measurement of the main
refractive indices and of the optical linear birefringence has been one of the standard tools in the study of
anisotropic properties of materials for nearly two centuries [2, 3]. For this kind of measurement, a range of
experimental techniques using polarized light (interferometry, polarimetry, polarizing microscopy,
elipsometry, etc.) were optimised and applied in the study of the anisotropic materials such as solid crystals,
organic tissues, strained glasses, polymers, liquid crystals, etc [3]. Among these techniques the most sensitive
and accurate are those based on using interferometers [4]. In this work, a high-accuracy method based on a
modified Michelson interferometer used for determining the main refractive indices of a liquid crystal kept in
a rotating cell is presented; a similar technique has been successfully applied to study the solid transparent
samples [4]. For the liquid crystals kept in a rotating cell, the main difficulty arises from the multilayer
structure of the sample. The multiple internal reflections on the layers surfaces and the multi-beam
interference have important influences both on the amplitude of recorded signals and on the angular positions
of maxima and minima of interference found in the scanned interference patterns. To improve the accuracy,
the influence of the Airy-Fresnel transmittances [5] and of the Airy phase shift [5] are included in the
theoretical model used for processing of the recorded signals.
The improved technique presented is being used to determine the main refractive indices of an
organosiloxane low-generation liquid crystalline dendrimer which exhibits both the uniaxial (NU) the biaxial
(NB) nematic phases as detected by several other experimental techniques [6]. The results are discussed
considering the different types of NB phases proposed in the literature [7].

Acknowledgments: This work was partially supported by the Portuguese Science Foundation through project
PTDC/FIS/65037/2006 and by the European Commission under 7th Framework Programme through project
PEOPLE-2007-1-1-ITN-215884 (Dendreamers)
References
[1] V. Percec, W. D. Cho, and G. Ungar, J. Am. Chem. Soc. 122, 10273 (2000); J.-M. Rueff, J. Barbera, B. Donnio, D.
Guillon, M. Marcus, and J. L. Serrano, Macromolecules 36, 8368 (2003).
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A. M. Glazer, J. Microsc., 198, 1–9, (2000);
[3] W. Kaminsky, K. Claborn, and B. Kahr, Chem. Soc. Rev., 33, 514-525 (2004); A. Echalier, R. L. Glazer, V. Fülöp,
and M. A. Geday, Acta Cryst., D60, 696-702 (2004);
[4] G. D. Gillen and S. Guha, App. Optics, 43, No. 10, (2004); J. Zhang, J. Q. Xu, Ch. Y. Gao, Sh. Ch. Si, Optics and
Lasers in Engineering, 47, 1212–1215, (2009);
[5] W. N. Hansen, JOSA, 58, 380-390, (1968); M. Born, E. Wolf, “Principles of Optics,” Cambridge Univ. Press,
(1999);
[6] K. Merkel, A. Kocot, J.K. Vij, R. Korlacki, G.H. Mehl, and T. Meyer, Phys. Rev. Lett., 93, 237801 (2004); S. Diez,
D. Dunmur, M. R. De La Fuente, P. Karahaliou, G. H. Mehl, T. Meyer, M. A. Perèz Jubindo, and D. Photinos,
Liq.Cryst., 30, 1021 (2003); J.L. Figueirinhas, C. Cruz, D. Filip, G. Feio, A.C. Ribeiro, Y. Frère, T. Meyer, G. Mehl,
Phys. Rev. Lett. 94,107802, (2005); C. Cruz, J. L. Figueirinhas, D. Filip, G. Feio, A. C. Ribeiro, Y. Frère, T. Meyer, and
G. H. Mehl, Phys. Rev., E, 78, 051 702, (2008).
[7] P.K. Karahaliou, A.G. Vanakaras, D.J. Photinos, J. Chem. Phys. 131 124516 (2009);
S.D. Peroukidis, P.K. Karahaliou, A.G. Vanakaras, D.J. Photinos, Liq. Cryst. 36 727 ( 2009).
 Efficiency of Multi-exciton Generation in Quantum Confined Nano-
structures

Alexander L. Efros
Naval Research Laboratory, Washington DC

There are two models that explain the high efficiency of multiexciton
generation (MEG) observed in nanocrystals (NCs): the coherent superposition
model, based on the strong quasi-resonant coupling between exciton and multi-
exciton states in a NC [1,2] and non-coherent models that are based on the
important observation that the density of biexciton states is significantly larger
than the density of exciton states at the same energy [3]. We unify both
approaches and consider a single-photon excitation coherently coupled with many
multi-exciton-states in a NC within a full quantum-state evolution approach [4].
Our quantum simulations that include hundreds of thousands of exciton and
multi-exciton states show how the complex time-dependent dynamics of these
states in a closed electronic system yields a saturated MEG effect on a picosecond
timescale. The initial single-photon excitation becomes lost in the dense maze of
multi-exciton states of the NC and a single exciton does not appreciably revive.
Including phonon relaxation confirms that efficient MEG requires the exciton--
biexciton coupling time to be faster than exciton relaxation time.
Enhancement of the exciton-biexciton coupling is one way to increase the
efficiency of MEG. Such enhancement could be realized in thin nanorods (NRs)
and nanowires (NWs), because the carriers in such structures interact
predominantly through the surrounding media with a small dielectric constant.
Due to this enhancement the binding energy of excitons in PbSe NRs and NWs
could be as large as 400 meV [5]. Indeed, resent preliminary measurements of
PbSe NRs have shown the MEG efficiency, which is higher than the one
measured in spherical PbSe NC of the same size [6].

[1] R. J. Ellingson, et. al, Nano Lett. 5, 865 (2005).

[2] A. Shabaev, Al. L. Efros, and A. J. Nozik, Nano Lett. 6, 2856 (2006).
[3] R. D. Schaller, V. M. Agranovitch, and V. I. Klimov, Nature Physics 1, 189
(2005).
[4] W. M. Wayne, A. Shabaev, C. S. Hellberg, V. L. Jacobs, and Al. L. Efros,
Phys. Rev. Lett. 105, 137401 (2010).
[5] A. C. Bartnik, Al. L. Efros, W.-K. Koh, C. B. Murray, and F. W. Wise, Phys.
Rev. B 82, 195313 (2010).
[6] P. D. Cunningham, J. E. Boercker, E. E. Foos, M. P. Lumb, A. R. Smith, J. G.
Tischler, and J. S. Melinger, , Nano Lett. 11, 3476 (2011).
Synthesis and characterisation of Mn-doped ZnTe Magic Size Nanocrystals
Joren Eilers, Esther Groeneveld, Celso de Mello Donegá and Andries Meijerink
Condensed Matter and Interfaces – Debye Institute for Nanomaterials Science, Utrecht University

Semiconductor nanocrystals (NCs) are a class of materials that show exciting new properties. New
properties can be introduced by adding dopants, which leads to a range of new materials and possible
applications. For some of these applications, like spintronics, very low doping concentrations, down to
a single ion per NC, are required. One approach to achieve very low dopant concentration is doping
very small magic sized clusters (MSCs). The size can later be adjusted by growing an un-doped shell.
2+
We report successful doping of ZnTe MSCs with Mn via cation exchange. We have synthesized
colloidal ZnTe MSCs of different sizes using a hot-injection method. A discontinuous growth of the
2+
MSCs is observed with absorption peaks at 320 nm, 333 nm, 355 nm and 378 nm. Mn doped ZnTe
clusters have been prepared by a cation exchange method using Mn(II)cyclohexanebutyrate as a Mn
precursor. The doped nanoclusters show a strong, broad emission band around 620 nm which is
2+
characteristic for Mn in ZnTe. The absorption spectrum of the MSCs remains virtually unchanged
2+ 4 6
upon doping. Interestingly, the excitation spectrum of the Mn T1Æ A1 emission is characterized by
2+
the same MSC absorption peaks as in the absorption spectrum, showing that the Mn emission is
excited through the excitonic states of the ZnTe MSC host and that energy transfer occurs from the
2+ 4
host to the dopant.Time resolved luminescence measurements showa lifetime of the Mn T1 level of
2+
~45μs in these samples which is characteristic for emission from Mn inside a ZnTe lattice.

FIG1 (Left): Room temperature absorption spectra of ZnTe magic size nanocrystals a) before doping and b) after
4 6 2+
Mn doping FIG2 (Top Right): Room temperature excitation spectrum of the T1Æ A1 emission of Mn (emission
2+
wavelength: 615 nm)FIG3 (Bottom Right): Luminescence decay of the 620 nm emission of ZnTe: Mn under 355
nm excitation at 4 K.
Entropy and energy driven self-assembly of semiconductor nanocrystals.
W.H. Evers and D. Vanmaekelbergh

Self-assembly of colloidal nanocrystals (NCs) into (binary) superlattices is a promising

pathway towards novel materials with unique optoelectronic properties. While a host of
different crystal structures and material combinations have been reported, the driving forces
behind BNSL formation are not fully understood. This information, if available, would
provide avenues to novel classes of nanostructured materials.
I will present our findings with varies methods of crystallization of binary superlattices. The
nature (metallic Au or semiconducting PbSe or CdSe) and the size-ratio of the two
nanocrystals are varied systematically. With semiconductor nanocrystals, self-organization at
high temperature leads to superlattices in accordance with the phase diagrams for binary hard-
sphere mixtures; hence entropy increase is the dominant driving force. On the other hand, the
replacement of semiconductor by metallic nanocrystals leads to crystals structures that are
energetically stabilized.
The difference between semiconductor and metallic nanocrystals is in line with simulations of
the pair potential between these particles in a good solvent. It follows from this study that if
nanocrystal crystallization is driven by entropy, the resulting structures are determined by the
size-ratio of the nanocrystals, enabling the rational design of novel nanostructured materials.
In the region where the phase diagrams for hard sphere predicts no stable structure, also
several unknown crystal structures are observed. 1-4
While the binary self-assembly is mainly entropy driven, single component assembly can also
be achieved by ‘activation’ of crystal facets. In this way we have achieved oriented linear
attachment of PbSe NCs into large rods and 2-D attachment resulting into a monolayer thick
single crystalline sheet.5

1. Overgaag, K.; Evers, W.H; de Nijs, B.; Koole, R.; Meeldijk, J.; Vanmaekelbergh, D. Journal of the American
Chemical Society 2008, 130, (25), 7833-7835.
2. Evers, W.H..; Friedrich, H.; Filion, L.; Dijkstra, M.; Vanmaekelbergh, D. Angewandte Chemie International
Edition 2009, 48, (51), 9655-9657.
3. Evers, W. H.; Nijs, B. D.; Filion, L.; Castillo, S.; Dijkstra, M.; Vanmaekelbergh, D. Nano Letters 2010, null-null.
4. Friedrich, H.; Gommes, C. J.; Overgaag, K.; Meeldijk, J. D.; Evers, W. H.; Nijs, B. d.; Boneschanscher, M. P.; de
Jongh, P. E.; Verkleij, A. J.; de Jong, K. P.; van Blaaderen, A.; Vanmaekelbergh, D. Nano Letters 2009, 9, (7),
2719-2724.
5. Evers, W.H.; Bals, S; Vanmaekelbergh, D.; Dimensional control over oriented attachment; To be submitted.
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ZĞǀ͕ϮϬϭϭ͘ϲϯ;ϭϰͲϭϱͿ͗Ɖ͘ϭϮϮϴͲϰϲ͘
 Penetration of gold nanoparticles through rat skin
a b a*
Rute Fernandes , Neil Smyth , Antonios G. Kanaras
a
Physics and Astronomy, University of Southampton, Southampton, United Kingdom
b
Center for Biological Sciences, University of Southampton, Southampton, United Kingdom
*Corresponding author, [email protected]

Recent advances in nanotechnology result in increased exposure to nanoparticles. Along with

respiratory and gastrointestinal tracts, the skin is a major route for entry of these particles into the
1 2
body . Despite direct exposure to nanoparticles in cosmetics and topically applied drugs , their
penetration of the skin barrier, toxicity implications, biodistribution and potential elimination is poorly
studied.

Gold nanoparticles are particularly attractive for dermatological application due to their unique
physicochemical properties; they are readily modified in terms of size, topology and surface charge.
Their high surface area provides sites for drug loading and enhances solubility and stability of loaded
3,4
drugs . Further, the ability to functionalize gold nanoparticles with targeting molecules enhances
their therapeutic potency, decreases their side effects, and offers the possibility of multivalent
5
interactions with cell surface receptors or other biomolecules .

6
Skin is designed to prevent the absorption or penetration of substances . The stratum corneum is
strongly lipophilic, obstructing the permeation of hydrophilic molecules and retaining lipophilic drugs.
Topically applied nanoparticles must penetrate this layer to have a local effect and be absorbed
across further layers of the skin to result in distribution throughout the body.

To test the uptake and distribution of nanoparticles through the skin, gold nanoparticles were coated
with polyethylene glycol-based ligands with a carboxy or amino termini to impart a negative or positive
charge, respectively. First, we tested the toxicity of these nanoparticles in epithelial cells using an
assay for mitochondrial and hence cellular activity. Then we evaluated whether these nanoparticles
induced apoptosis in the basal layer and dermis in an organ culture system using perinatal rat skin.
Finally, using the same system we evaluated the penetration of gold nanoparticles into the rat
epidermis. Transmission electron microscopy and energy-dispersive X-ray spectroscopy were used to
assess the nanoparticles penetration qualitatively, while inductively coupled plasma optical emission
spectrometry was used to give a quantitative characterisation.

Our results allowed a better understanding of the penetration of charged gold nanoparticles through
skin, i.e. whether these particles were being taken up and transferred through the epidermal cells or
using paracellular transport systems.

References:

1 Elder, A., Vidyasagar, S. & DeLouise, L. Physicochemical factors that affect metal and metal oxide nanoparticle
passage across epithelial barriers. Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology 1, 434-
450 (2009).
2 Kemppainen, B. W. & Reifenrath, W. G. Methods for skin absorption. (CRC Press, 1990).
3 Alkilany, A. M., Thompson, L. B., Boulos, S. P., Sisco, P. N. & Murphy, C. J. Gold nanorods: Their potential for
photothermal therapeutics and drug delivery, tempered by the complexity of their biological interactions. Advanced
Drug Delivery Reviews, in press, (2011).
4 Ghosh, P., Han, G., De, M., Kim, C. K. & Rotello, V. M. Gold nanoparticles in delivery applications. Advanced Drug
Delivery Reviews 60, 1307-1315 (2008).
5 Dreaden, E. C., Alkilany, A. M., Huang, X., Murphy, C. J. & El-Sayed, M. A. The golden age: gold nanoparticles for
biomedicine. Chemical Society Reviews, in press, (2012).
6 Nohynek, G. J., Dufour, E. K. & Roberts, M. S. Nanotechnology, cosmetics and the skin: is there a health risk? Skin
Pharmacol Physiol 21, 136-149 (2008).
 The design and investigation of photo-active liquid-crystalline silsesquioxane based
nanocomposites

A. J. Ferreira, G.H. Mehl

Department of Chemistry, University of Hull, Hull, HU6 7RX, UK
[email protected]

The use of silsesquioxanes (POSS) as molecular scaffolding for liquid-crystalline systems

is largely due to their discrete molecular structure, in contrast to polymeric systems,
silsesquioxanes derivatives are monodisperse and of define three dimensional structure.
Photochromic polymers are widely studied due to their response to light. However
functionalization of POSS with azobenzene or cinnamate mesogens has not yet been
explored to any extent.
In this contribution we report on our efforts to investigate a number of octasilssesquioxane
compounds functionalized with azobenzenes and cinnamate derivatives showing mesogenic
behaviour. The synthesis and the chemical analysis of these materials will be reported and
the results of the investigation of the properties in the self-assembled state using OPM,
DSC and XRD will be presented and will be compared to structurally related materials.
Chemical inhomogeneity during the growth of MnFe2O4 nanocrystals

Anna M. Ferretti#, Sara Mondini#, and Alessandro Ponti#

#
Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via G.
Fantoli 16/15, 20138 Milano, Italy

The synthesis of MnFe2O4 nanocrystals (NCs) was investigated to understand how the reactants
stoichiometric ratio affects the resulting NC composition and morphology. We followed a solvothermal
synthesis protocol comprising the decomposition of Fe(CO)5 and Mn(oleate)2 1 in refluxing dioctyl ether
with oleic acid (OlAc) as a surfactant. In all cases, electron diffraction and HRTEM showed that the NCs are
monocrystalline with the cubic ferrite structure. The NCs are highly monodispersed in size, with diameters
ranging between 8 and 20 nm in different reaction conditions.
The initial Mn:Fe:OlAc molar ratio was varied from 1:2:4, to 1:2:6 and 1:3:9 in order to understand the role
of the reactants molar ratio. The NC chemical composition was determined with nanometer resolution by
the complementary techniques of STEM-EDX and EELS/ESI.
When using Mn:Fe:OlAc = 1:2:4, the resulting NCs (d = ϵŶŵ͕ʍсϳйͿhave a Mn:Fe ratio of about 1:1,
probably because Mn(oleate)2 totally decomposes faster than the iron oleate formed by reaction of
Fe(CO)5 and OlAc. Indeed, in the other two cases [Mn:Fe:OlAc = 1:2:6 (d сϮϬŶŵ͕ʍсϵйͿ or 1:3:9 (d = 9 nm,
ʍсϰйͿ΁ the reactant stoichiometry is conserved in the product.
To shed some light on this peculiar behavior, we studied the Mn:Fe:OlAc = 1:2:6 synthetic outcome as a
function of the NC growth time. After 15 min growth, the NCs have lozenge shape (Figure, left). The overall
chemical composition is Mn:Fe 1:2, but the distribution of the metal ions is not homogenous inside the
individual NCs. Mn is confined to the outer shell of the NCs, and the Fe:Mn ratio grows from about 0 at the
NC surface to about 3 at the NC center. Afterwards, the NC become more rounded, till a circular shape is
achieved for growth time ш 60 min. After 90 min growth (Figure, right), the NCs have circular shape. Mn has
diffused throughout the NCs and the Mn:Fe ratio is about 1:2 as expected for homogeneous MnFe2O4 NCs.
We also studied the magnetic properties of these MnFe2O4 NCs, which are strongly affected by the NC size
and shape but not significantly influenced by inhomogeneous composition.
1
A. Puglisi, S. Mondini, S. Cenedese, A.M. Ferretti, N.Santo, A.Ponti, Chem. Mater., 2010, 22 (9), pp 2804–2813.

Comparison of Mn (green), Fe (red) and Fe:Mn atomic

ratio line profiles of MnxFeyO4 NCs (reactant Mn:Fe:OlAc
molar ratio is 1:2:6 ) after 15 (left) and 90 min (right)
growth, obtained by STEM-EDX (bottom: STEM images).
 Reduction of gold(III) and gold(I) assisted by semiconductor
nanoparticles: a thermal vs. photochemical process

Raquel E. Galian,a,b Pilar Díaz,b Antonio Rivera,b Miguel de la Guardia a and Julia Pérez
Prietob
a
Dpto. Química Analítica,Universidad de Valencia, Valencia, España Ciudad; bInstituto
de Ciencia Molecular , Universidad de Valencia, Valencia, España

E-mail: [email protected]
The efficiency of a semiconductor nanoparticle (QD) as a photocatalyst depends on the
ability of the system to generate a charge separation induced by light [1]. In order to
increase this charge separation several authors have grown metal nanoparticles on
semiconductor surfaces [2].

The addition of gold salts to CdSe/ZnS core-shell quantum dots (CS QDs) produces a
fluorescence quenching of the nanoparticle; gold(III) was a better quencher than gold(I).
Luminescence recovery showed an interesting dependence on the size of the nanoparticle
and evidenced the reduction of the gold salt to gold(0).

The effect of visible-light (O > 420 nm) irradiation on the process was also studied.
Different techniques, such as high resolution transmission electron microscopy
(HRTEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray
spectroscopy (EDAX) were used to gain insight into the process. The role of the QD shell
in the thermal and photochemical process will be discussed.

References
[1] Galian, R. E.; Pérez Prieto, J.; Energy Environ. Sci., 2010, 3, 1488. Carbone, L.; Kudera, S.;
Giannini, C.; Ciccarella, G.; Cingolani, R.; Cozzoli, P.D.; Manna, L., J. Mat. Chem., 2006, 16,
3952.
[2] Saunders, A.E.; Popov, I.; Banin, U.; J. Phys. Chem. B. 2006, 1140, 25421.
Design and Applications of a Universal, Multi-Modality Fluorescence Reader

D. Gakamsky, R.B.Dennis and S.D.Smith

Edinburgh Instruments Ltd, 2 Bain Square, Kirkton Campus, Livingston, UK

A multi-modality, dual channel, luminescence plate reader has been developed to

measure, for the first time, a combination of intensity, fluorescence lifetime and time
resolved intensity and polarisation, with single photon counting sensitivity. Temporal
measurements span a broad range from picoseconds to microseconds using both time
correlated single photon counting (TCSPC) and multichannel scaling (MCS) techniques.
The optical design, with easily interchangeable excitation sources and wavelength
selection filters, coupled with cooled, gated photomultipliers, fast data acquisition
electronics and state of the art software allow a high flexibility for assay development and
perfectly meets requirements from partners within the EU Nanognostics project to
measure markers, for example for Alzheimer’s disease. All these measurements can be
made with the new reader, at a fraction of the cost of comparable commercial plate
readers, opening this market to greater acceptance and use.

Fluorescence lifetime is an attractive measurement modality for a growing body of

applications in biotechnological and medical diagnostics as it is an intrinsic property
which is independent of sample concentration and volume, and is unaffected by light
scattering and inner filter effects. Advanced lifetime analysis allows background
compound interference to be minimised to protect from false hits in drug screening
applications.

The application of quantum dots (QDs) has the potential to increase sensitivity and
provide a multiplexed readout of assay parameters to simultaneously detect several
antigens. The fluorescence time response of QDs has been measured over the entire
temporal range from picoseconds to milliseconds revealing, for the first time, a range of
lifetime components stretching from nanoseconds to hundreds of microseconds. The
microsecond emission of QDs needs to be taken into account in assay design.

Examples of applications of the reader will be given including:-

1) Fluorescence lifetime based (nanosecond range) assays for the identification and
profiling of protein kinase, protease and phosphatase inhibitors;

2) Antibody based, time resolved FRET (Förster Resonant Energy Transfer)

lanthanide complex assays (micro- and milli-second range) based on the time
course of donor emission only, showing a sensitivity of marker antigen
concentration down to <10pg/ml. Such FRET measurements require only one
detection channel and need less donor labelled antibody (typically 8-fold less)
opening the possibility of a budget price Point of Care (POC) instrument with
significantly reduced reagent cost without compromising assay accuracy and
sensitivity.
 Photogeneration, diffusion and annihilation
of charge carriers in quantum-dot solids
Yunan Gao1,2, Michiel Aerts1, Lucas T. Kunneman1, Juleon M. Schins1, Herre S. J. van der Zant2, Arjan J.
Houtepen1 and Laurens D. A. Siebbeles1
1
Optoelectronic Materials Section, Department of Chemical Engineering, 2Kavli Institute of Nanoscience,
Delft University of Technology, Delft, The Netherlands. Email: [email protected]

Films of colloidal semiconductor nanocrystals, so-called quantum-dot solids, were prepared

using the layer-by-layer dip-coating method. The mechanism and dynamics of charge
carrier photogeneration, diffusion and annihilation were studied by a combination of ultrafast
time-resolved terahertz spectroscopy (THz), transient optical absorption spectroscopy (TA), the
time-resolved microwave conductivity technique (TRMC), as well as Monte Carlo simulations
(MCS).
We demonstrate that in PbSe QD solids the charge carrier mobility is as high as 3 cm2/Vs
(TRMC) and that all photogenerated excitons dissociate into mobile charge carriers (THz and TA)
[1]. The high carrier mobility and the unit yield of mobile carriers make this material very
interesting for applications in solar cells and photo-detectors.
Due to the high mobility, the carriers can undergo hundreds of hopping steps in several
picoseconds. With the high hopping rate, the carriers execute a fast thermalization process within
3 ps [2], which is revealed by wavelength resolved TA.
We characterize two main annihilation paths for the carriers (TA and MCS). Diffusion
mediated Auger recombination occurs in ~100 ps, while trapping occurs on a nanosecond time
scale. Auger recombination occurs via a 3-particle reaction ( eeh o e or ehh o h ). Interestingly,
adding a CdSe shell around the PbSe QD core slows down charge trapping.
With this knowledge we present a complete picture of the “life and fate” of optical excitations
in this material, which is very useful for the design of QD based devices.

[1] Talgorn, E.; Gao, Y.; Aerts, M.; Kunneman, L. T.; Schins, J. M.; Savenije, T. J.; van HuisMarijn, A.;
van der ZantHerre, S. J.; Houtepen, A. J.; Siebbeles, L., D. A. Nat Nano 6, (11), 733-739.
[2] Gao, Y.; Talgorn, E.; Aerts, M.; Trinh, M. T.; Schins, J. M.; Houtepen, A. J.; Siebbeles, L. D. A. Nano
Letters 2011, 11, (12), 5471-5476.
 Functional Surface Assembly by Single-Molecule Cut-and-Paste
Hermann E. Gaub

Chair for Applied Physics & Center for Nanoscience Ludwig Maximilians University
Munich

Bottom up assembly of functional molecular ensembles with novel properties emerging from
composition and arrangement of its constituents is a prime goal of nanotechnology. With the
development of Single-Molecule Cut-and-Paste (SMC&P) we provided a platform technology
for the assembly of biomolecules at surfaces. It combines the Å-positioning precision of the
AFM with the selectivity of DNA hybridization to pick individual molecules from a depot
chip and allows to arrange them on a construction site one by one. An overview on different
applications of this technology will be given in this talk. One recent example demonstrates the
functional of receptors for small molecules. By SMC&P we assembled binding sites for
malachite green in a molecule-by-molecule assembly process from the two halves of a split
aptamer. We show that only a perfectly joined binding site immobilizes the fluorophore and
enhances the fluorescence quantum yield by several orders of magnitude. To corroborate the
robustness of this approach we produced a micron-sized structure consisting of more than 500
reconstituted binding sites. To the best of our knowledge this is the first demonstration of a
one by one bottom up functional bio-molecular assembly.

S. Kufer, Puchner E. M.,Gumpp H., Liedel T. & H. E. Gaub Science (2008), Vol 319, p 594-
S. Kufer, Strackharn, M., Stahl S.W., Gumpp H., Puchner E. M. & H. E. Gaub
Nature Nanotechnology (2009), Vol 4, p 45-
M. Erdmann, R. David. A.N. Fornof, and H. E. Gaub, Nature Chemistry (2010), Vol 2, p 755-
M. Strackharn, S. Stahl, E. Puchner & H.E. Gaub, Nanoletters (2012) in press
 Highly sensitive FRET-immunoassays for multiparameter detection

André Geßner, Fraunhofer Institute for Applied Polymer Research, Potsdam, Germany;
Daniel Geißler, University of Potsdam, Germany;
Stefan Stufler, Fraunhofer Institute for Applied Polymer Research, Germany;
Hans-GerdLöhmannsröben, University of Potsdam, Germany;
Niko Hildebrandt, Université Paris-Sud, Orsay, France

An early diagnosis often is vital for the effective treatment of a disease. Unfortunately, the
identification of some diseases, such as Alzheimer’s disease or lung cancer is complicated
and thus the condition of an early diagnosis in the course of a standard medical checkup
often can’t be met. In this talk we present, how a quick, selective and sensitive early
diagnosis can be achieved via the simultaneous detection of a set of serum-based
biomarkers in one sample (multiplexing).
An optically multiplexed homogeneous immunoassay is exemplarily demonstrated for
tumor-specific early stage lung cancer diagnostics using the tumor markers CEA, NSE,
Cyfra21.1, CA15.3 and SCC in 50 μL human serum samples. Using a single luminescent
terbium-complex as FRET donor for five different organic dye acceptors allows color
multiplexing with a single excitation source. The FRET donor as well as the FRET acceptors
where covalently coupled to different antibodies, which form sandwich-complexes with the
corresponding tumor markers. Time gated detection of FRET sensitized dye fluorescence
yields virtually background free signals which are directly proportional to the respective
tumor marker concentrations. Due to the spectral overlap of the broad dye emission bands
and the resulting cross talk, up to now FRET multiplexing with organic dyes as FRET
acceptors was rather limited. However, we developed an analysis method which allows for
an efficient correction of this cross talk. Thus, a very sensitive detection of five tumor
markers with detection limits in the low ng/mL range in a single assay is achieved.
The multiplexed homogeneous time-resolved FRET immunoassay was performed with
commercially available antibodies on a modified clinical plate reader system. With the low
detection limits and the general applicability also for other biomarkers this method has a
large potential for facile integration into clinically established in vitro diagnostics.
 Hybrid Organic/Inorganic Colloidal Quantum Dots for
Improved Photoconductivity
Carlo Giansante,1* Luigi Carbone,2 Cinzia Giannini,3 Zoobia Ameer,1 Giuseppe
Maruccio,1,2,4 Giuseppe Gigli1,2,4
1
CBN@UNILE, IIT Istituto Italiano di Tecnologia, via Barsanti, 73010 Arnesano (LE), Italy
2
NNL CNR-Istituto Nanoscienze, via per Arnesano, 73100 Lecce, Italy
3
Istituto di Cristallografia (IC-CNR), via Amendola 122/O, 70126 Bari, Italy
4
Departimento di Matematica e Fisica ‘E. De Giorgi’, University of Salento, via per Arnesano, 73100 Lecce, Italy

* [email protected]

As a consequence of their
nanometer scale dimensions,
semiconducting nanocrystals (NCs)
lye in the quantum confinement
regime that allows for band gap
tuning, but also show large surface-
to-volume ratios. Resulting
optoelectronic properties are thus
strongly dependent on NCs surface
ligands; moreover, such ligands
also markedly influence NCs
interactions with the surroundings, affecting their packing in ordered suprastructures.
Here we present a novel solution ligand exchange strategy to efficiently replace native oleate
ligands on lead sulfide NCs with short conjugated thiol molecules. The replacing ligands confer
good colloidal stability to PbS NCs and significantly reduce the optical band gap. Such reduction
has been attributed to further delocalization of the exciton on the replacing ligand shell, due to a
ligand-to-NC charge transfer. Moreover, surface modification induces a transition in self-
assembled PbS NC superlattices symmetry from hexagonal-packed to square-packed
suprastructures characterized by increased inter-NC electronic coupling. The coordination of
short conjugated thiol molecules onto PbS NCs surface induces intra- and inter-NC exciton
delocalization in thin-films, ultimately leading to enhanced photoconductivity thus showing
important implications for NC-based solar energy conversion.
Plasmonic Effects of Gold Nanoparticles on the Methylene Blue Triplet
Excited State
Maria Gonzalez-Bejar, Natalia L. Pacioni, Emilio Alarcón, Katherine L. McGilvray and
Juan C. Scaiano
Department of Chemistry, Centre for Catalysis Research and Innovation, University of
Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada, K1N 6N5

E-mail: [email protected]

The excitation of metallic nanoparticles with light at their Surface Plasmon Band
generates a strongly enhanced and highly localized electromagnetic field (as a near-field
effect) in their near vicinity. These Plasmonic effects play a key role in most of the
physical and chemical phenomena that are studied with nanomateriales. In particular,
photophysical properties of a molecule in the proximity of a metal nanoparticle surface
can be modified to some extent by Surface Plasmon interactions undergoing
transmitter/antenna effects. [1,2]
Generally, these interactions have been explored in the ground and singlet excited state,
where either quenching or enhancement of fluorescence has been observed.[3] The
plasmonic effects of aqueous gold nanoparticles a15 nm (AuNP) on methylene blue
triplet excited states (3MB*) upon 650 nm laser excitation have been previously
studied.[4]
In this contribution, we will discuss the transmitter/antenna effects by varying the
nanoparticles size and shape.

References
[1] Anger, P.; Bharadwaj, P.; Novotny, L., Phys Rev. Lett. 2006, 96, 4.
[2] Bharadwaj, P.; Novotny, L., Opt. Express 2007, 15, 14266.
[3] Lakowicz, J. R., Principles of Fluorescence Spectroscopy, 3rd Ed. Springer, 2006.
[4] Pacioni, N.L.; González-Béjar, M.; Alarcón, E.; McGilvray, K.L.; Scaiano, J.C., J.
Am. Chem. Soc. 2010, 132, 6298.
 Correlation effects in core-shell semiconductor
nanocrystal

T. H. Nguyen,1 J. Habinshuti,1 Y. Justo,2 R. Gomes,2 S. Godey,1 J. P.

Nys,1 Z. Hens,2 B. Grandidier 1
1
Institut d’Electronique, de Microélectronique et de Nanotechnologie, IEMN, (CNRS, UMR 8520)
Département ISEN, 41 bd Vauban, 59046 Lille Cedex, France
2
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent,
Belgium

Semiconductor colloidal nanocrystals are quite attractive, because of their physical

properties, such as discrete energy levels, which can be easily tailored from the variation of
their size and chemical composition, and also because of their compatibility with the
fabrication of low-cost electronic devices. However, devices prepared from semiconductor
nanocrystals are still facing limitations due to a high environmental sensitivity of their organic
shell. In order to increase their optical properties, core-shell nanocrystals have thus been
synthesized, where a new degree of freedom is offered by the presence of a junction
between two types of semiconductor material.
Scanning tunneling microscopy is the appropriate tool to image and probe the electronic
properties of individual nanostructures and, in particular, of heterostructure nanocrystals.
This system can be compared to a double barrier tunnel junction, where the transport
properties are governed by the probability transmission across both potential barriers. In
principle, the synthesis of an homogenenous shell around the core should thus favor
charging phenomena. Semiconductor PbSe/CdSe core-shell nanocrystals in a double barrier
tunnel junction have thus been investigated by means of scanning tunneling spectroscopy at
low temperature. From the analysis of the differential conductance peak position as a
function of the potential distribution in both potential barriers, we demonstrate a unipolar
transport regime for a large amount of nanocrystals. The same charge carriers are injected
on both sides of the zero-conductance gap and the peaks observed at higher energy arise
from the charging of the NCs.
Characterization of the PbSe/CdSe core-shell nanocrystals by X-ray photoemission
spectroscopy was also performed. It revealed the formation of unprotected PbSe facets that
have different orientations in the junction. Such variability in the geometry of the nanocrystal
allows to account for the different transport regime that are encountered in tunneling
spectroscopy of PbSe/CdSe core-shell nanocrystals.
 Monosaccharides versus PEG functionalized NPs: influence in the
cellular uptake.
María Moros1, Bruno Hernáez2, Elina Garet3, Jorge T. Dias1, Berta Sáez1,4, Valeria
Grazú1, África González-Fernández5, Covadonga Alonso2, and Jesús M. de la Fuente1
1
Biofunctionalization of nanoparticles and surfaces (BioNanoSurf), Instituto de
Nanociencia de Aragón, Universidad de Zaragoza. Mariano Esquillor, s/n, 50018,
Zaragoza (Spain); 2 Departamento de Biotecnología, Instituto Nacional de Investigación
y Tecnología Agraria y Alimentaria, INIA, Autovía A6 km 7,5, 28040, Madrid (Spain); 3
NanoImmunoTech SL, Pza. Fernando Conde, Montero Ríos 9, 36201, Vigo (Spain); 4
Instituto Aragonés de Ciencias de la Salud, Avda. Gomez Laguna 25, 50009, Zaragoza
(Spain); 5 Inmunology, Biomedical Research Center (CINBIO),University of Vigo,
Campus Lagoas Marcosende s/n, 36310, Vigo, Pontevedra (Spain)

Magnetic nanoparticles (NPs) hold great promise for biomedical applications. The core
composition and small size of these particles produce superparamagnetic behavior,
thus facilitating their use in magnetic resonance imaging and magnetically induced
therapeutic hyperthermia. However, the development and control of safe in vivo
applications for NPs call for the study of cell-NPs interactions and cell viability.
Furthermore, as for most biotechnological applications, it is desirable to prevent
unspecific cell internalization of these particles. It is also crucial to understand how the
surface composition of the NPs affects their internalization capacity. Here, through
accurate control over unspecific protein adsorption, size distribution, grafting density
and an extensive physicochemical characterization, we correlated the cytotoxicity and
cellular uptake mechanism of 6 nm magnetic NPs coated with several types and
various densities of biomolecules, such as glucose, galactose and poly(ethylene glycol).
We found that the density of the grafted molecule was crucial to prevent unspecific
uptake of NPs by Vero cells. Surprisingly, the glucose coated NPs described here
showed cellular uptake as a result of lipid raft instead of clathrin-mediated cellular
internalization. Moreover, these glucose-functionalized NPs could be one of the first
examples of NPs being endocytosed by caveolae that finally end up in the lysosomes.
These results reinforce the use of simple carbohydrates as an alternative to PEG
molecules for NPs functionalization when cellular uptake is required.
 Functional electroactivedendrimers for (opto)electronic and
applications
Juozas V. Grazulevicius

Department of Organic Technology, Kaunas University of Technology, Radvilenǐ pl. 19, LT-
50254, Kaunas, Lithuania, Email: [email protected]

Research from both academia and industry has been increasing steadfastly in the area of organic
electronics during the past decades because of the great hunt for cost-effective (opto)electronic
devices such as organic light-emitting diodes, field-effect transistors, photovoltaic cells.
Symmetrical star-shaped compounds including dendrimershave been explored extensively as
organic luminescent and charge-transporting materials for these applications. Dendritic organic
materials demonstrate a wide range of interesting physical properties, including effective charge-
transport and electroluminescence. Some derivatives are capable to form glasses with good
morphological stability whereas the compounds containing rigid core and flexible alkyl
substituents form organic liquid crystals. Various core-arm combinations in dendritic materials
represent an interesting methodology for the tunability of photophysical and photoelectrical
properties of these materials.
We have synthesised a series of multichromophores with dendritic architecture based on pyrene,
triphenylamine and triazine cores and various electron-donor substituents. Electron-donors like
carbazolyl groups with different linking topology, phenothiazinyl, fluorenyl, trialkoxy phenyl etc
were used for the studies. We also evaluated the thermal, optical, photophysical and
photoelectrical properties of these derivatives.
Triphenylamine-core centred organic materials containing different alkyl chains were
synthesised by Wittig reaction of tris(4-formylphenyl)amine; obtained by the Vilsmeier-Hack
reaction of triphenylamine, with the Wittig reagent synthesized from methyl-3,4,5-
trihydroxybenzoate. The triphenylamine derivative with longer alkyl substituents exhibit
monotropic liquid crystalline characteristics. These compounds also exhibit excellent thermal
stability and interesting photophysical properties.
Pyrene-cored derivatives exhibit promising fluorescence quantum yields. The ionization
potential values of thin layers of these derivatives measured by photoelectron spectroscopy range
from 5.2eV to 5.5 eV.
New star-shaped carbazole substituted triazine derivatives were synthesised by a combination of
classical and modern synthetic methodologies. The compounds possess good thermal stability
and high glass transition temperatures. The HOMO values estimated by cyclic voltametry in
solutions are in the range from -5.60 eV to -5.38 eV while ionization potentials of the solid
samples established in air range from 5.5 eV to 5.97 eV.
 Thermally-induced Atomic Reconstruction of PbSe/CdSe Core/Shell
Quantum Dots into PbSe/CdSe bi-hemisphere hetero-nanocrystals

'*URG]LĔVNDF. Pietra, W. Evers, M. A. van Huis, C. de Mello Donegá and D.

Vanmaekelbergh

Condensed Matter and Interfaces, Debye Institute, Utrecht University, Netherlands.

[email protected]

PbSe/CdSe heteronanocrystals are of considerable interest for novel optoelectronic materials

operating in the near IR. The atomic structure of the PbSe/CdSe heteronanocrystals
determines the energy level spectrum and optical properties, and is thus crucial.[1-5] On the
other hand, the presence of extended organically capped surfaces and a PbSe/CdSe interface
in each nanocolloid raises questions on the (thermal) stability of such systems. We have
investigated the structural and morphological evolution of PbSe/CdSe core/shell QDs upon
annealing under vacuum. Before annealing the PbSe core has an octahedral morphology with
several {111} facets, and the CdSe shell has zincblende crystal structure. Thermal annealing
under vacuum at temperatures between 150°C and 200°C induces a structural and
morphological reconstruction in which the PbSe core and the CdSe shell are reorganized into
two hemispheres joined by a common {111} Se plane. Thermal annealing in solution is
observed to lead to considerable changes in the absorption and pholuminescence properties of
the suspensions. These results open up the exciting possibility of using controlled thermal
annealing in solution to produce colloidal PbSe/CdSe heterohemisphere nanocrystals on a
large scale. The energy level spectrum of the bi-hemisphere hetero-nanocrystals and that of
the core/shell systems is currently investigated by UHV cryogenic tunneling microscopy and
spectroscopy.

1. Bals, S., M. Casavola, M.A. van Huis, S. Van Aert, K.J. Batenburg, G. Van Tendeloo,
and D.l. Vanmaekelbergh, Nano Letters, 2011. 11(8): p. 3420-3424.
2. Gao, J., J.M. Luther, O.E. Semonin, R.J. Ellingson, A.J. Nozik, and M.C. Beard,.
Nano Letters, 2011. 11(3): p. 1002-1008.
3. *URG]LĔVND':+(YHUV5'RUODQG-YDQ5LMVVHO0$YDQ+XLV$0HLMHULQN
C. de Mello Donegá, and D. Vanmaekelbergh, Small, 2011:
doi.org/10.1002/smll.201101819
4. Grodzinska, D., F. Pietra, M.A. van Huis, D. Vanmaekelbergh, and C. de Mello
Donega, Journal of Materials Chemistry, 2011. 21(31): p. 11556-11565.
5. Konstantatos, G., I. Howard, A. Fischer, S. Hoogland, J. Clifford, E. Klem, L. Levina,
and E.H. Sargent, Nature, 2006. 442(7099): p. 180-183.
 Highly Luminescent (Zn,Cd)Te-CdSe Colloidal Heteronanowires with
Tunable ElectronоHole Overlap
E. Groeneveld*, S. van Berkum, M. M. van Schooneveld, A. Gloter, J. D. Meeldijk,
D. J. van den Heuvel, H. C. Gerritsen and C. de Mello Donegá

* Condensed Matter and Interfaces, Debye Institute for Nanomaterials Science, Utrecht University,
3508 TA Utrecht, Netherlands

Semiconductor nanocrystals comprising two (or more) different materials joined together by
heterointerfaces, i.e., heteronanocrystals (HNCs), offer exciting possibilities regarding property
control.1 The localization regime of photoexcited charge carriers in HNCs (viz., type-I, type-I1/2, and
type-II) is determined by the offsets between the energy levels of the materials that are combined at
the heterointerface.1 ZnTe-CdSe is an attractive semiconductor combination for type-II HNCs, since
the energy offsets between the bulk valence and conduction bands are large (viz., 0.9 and 1.5 eV,
respectively) and the lattice mismatch between the two materials is very small (<1%). In our work we
have synthesized highly luminescent (Zn,Cd)Te-CdSe colloidal heteronanowires by using a multistage
approach in which ZnTe magic size clusters (MSCs) are used as seeds.2 The wire formation starts with
a partial Zn for Cd cation exchange, followed by self-organization into segmented heteronanowires.
Further growth occurs by inclusion of CdSe. The heteronanowires are very narrow (~2 nm in
diameter) and can be up to ~50 nm long (Fig. 1). The exciton photoluminescence (PL) ranges from
~530 to 760 nm with high quantum yields. The exciton radiative lifetime is long and the absorption
cross section at emission wavelengths is rather small. The results show that by increasing the CdSe
volume fraction of the heteronanowires the electron-hole overlap is reduced, leading to longer
exciton lifetimes and smaller spectral overlaps between PL and absorption, and shifting all exciton
transitions to lower energies. Semiconductor nanowires hold great promise for applications in
photovoltaics, solid-state lighting, solar energy conversion and photonics.3-4

Figure 1. (a) Absorption (Abs) and photoluminescence (PL, excitation at 400 nm) spectra of (Zn,Cd)Te-CdSe
colloidal heteronanowires obtained by using ZnTe magic size clusters (MSCs) as seeds. The absorption
spectrum of the ZnTe MSC seeds is also shown. (b) Representative TEM image of the (Zn,Cd)Te-CdSe
heteronanowire sample used to obtain the spectra shown in (a).

1. Donega, C. d. M.; Chem. Soc. Rev. 2011, 40, 1512-1546.

2. E. Groeneveld, S. van Berkum, M. M. van Schooneveld, A. Gloter, J. D. Meeldijk, D. J. van den Heuvel, H.
C. Gerritsen and C. de Mello Donega, Nano Letters, 2012, DOI: 10.1021/nl203695m
3. Tian, B.; Kempa, T. J.; Lieber, C. M.; Chem. Soc. Rev. 2009, 38, 16-24.
4. Hochbaun, A. I.; Yang, P.; Chem. Rev. 2010, 110, 527-546.
 Photoluminescence of Individual Au/CdSe Nanocrystal
Complexes with Variable Interparticle Distances

Xuedan Ma, Tobias Kipp, Marcin Grzelczak, Katharyn Fletcher, Zhe Wang, Alf Mews, Andres
Guerrero Martinez, I. Pastoriza-Santos, J. Pérez-Juste, and Luis M. Liz-Marzan

1) Institute of Physical Chemistry, University of Hamburg, Grindelallee 117, 20146 Hamburg,

Germany
2) Departamento de Quimica Fisica, Universidade de Vigo, 36310 Vigo, Spain

E-mail: [email protected]

Due to their unique spectral properties, photostability, and chemical versatility, colloidal semiconductor
nanocrystals (NCs) are interesting for fundamental research and have become promising candidates
for a wide range of electronic and optical applications, such as light emitting diodes (LEDs),
photovoltaics and biological labeling. However, there are still several issues limiting their applications,
in particular the universally observed fluorescence intermittency, also called blinking, which can be
[1]
observed at the single nanocrystal level. The optical properties of nanocrystals are changed by the
interaction with nearby metal nanoparticles. By time-resolved photoluminescence spectroscopy, we
investigate CdSe multishell nanocrystals coupled to Au nanoparticles. The distance between emitter
and metal is controlled by silica shells. These NCs showed increased fluorescence intensity, a
decreased fluorescence lifetime, strong blinking suppression. These observations can be explained by
[1]
the metal particle induced change of excitation and recombination rates. On the other hand, both
the radiative and nonradiative decay rates of fluorophores can be modified by the fluorophore-metal
interactions. The interaction can lead to a strong fluorescence enhancement but also to suppression of
[1]
blinking behaviour.

REFERENCES:
1. Xuedan Ma, Hua Tan, Tobias Kipp and Alf Mews, Nano Lett. 2010, 10, 4166–4174
2. Xuedan Ma, Katharyn Fletcher, Tobias Kipp, Marcin P. Grzelczak, Zhe Wang, Andres Guerrero-Martínez,
Isabel Pastoriza-Santos, Andreas Kornowski, Luis M. Liz-Marzan and Alf Mews* J. Phys. Chem. Lett. 2011, 2,
2466–2471
 COLLECTIVE CHIRALITY IN METAL NANOPARTICLES

a, a,
Andrés Guerrero-Martínez *, Luis M. Liz-Marzán *

a
Colloid Chemistry Group, Departamento de Química Física and Unidad Asociada CSIC-Universidade de Vigo,
36310 Vigo, Spain

Noble-metal nanoparticles with localised surface-plasmon resonances have been recently used to
1
prepare new materials with improved optical circular dichroism. This interest stems from a wide range
2
of applications in biology and physics, including the structural determination of proteins and DNA, and
3
the pursuit of negative refraction. Surface-plasmon mediated circular dichroism (SP-CD) in solution
has been so far explored using small spherical metal particles, invariably resulting in moderate signals
4
over a narrow spectral range. In contrast, we present herein a novel class of metamaterial consisting
of gold nanorods organised in three-dimensional (3D) chiral structures and yielding a record circular
dichroism anisotropy factor for metal nanoparticles, across visible and near-infrared wavelengths
5
(600–900 nm). The fabrication process can easily be upscaled, since it involves the self-assembly of
gold nanorods on a fibre backbone with chiral morphology. Our measurements are fully supported by
theoretical modeling based on coupled dipoles, unravelling the key role of gold nanorods in the
6
chiroptical response.

References

(1) D. B. Amabilino, Chirality at the nanoscale, Wiley-VCH, 2009.

(2) R. Quidant, M. Kreuzer, Nat. Nanotechnol. 2010, 5, 762–763.
(3) J. B. Pendry, Science 2004, 306, 1353–1355.
(4) J. George, K. G. Thomas, J. Am. Chem. Soc. 2010, 132, 2502–2503.
(5) A. Guerrero-Martínez, B. Auguié, J. L. Alonso-*yPH]='åROLü6*yPH]-Graña, M. Žiniü00&LG/0/L]-
Marzán, Angew. Chem. Int. Ed. 2011, DOI: 10.1002/anie.201007536.
(6) B. Auguié, J. L. Alonso-Gomez, A. Guerrero-Martínez, L. M. Liz-Marzán, J. Phys. Chem. Lett. 2011, 2, 846-851.
 The Effect of Nanoparticle Dimensionality on Fluorescence Resonance Energy
Transfer in Nanoparticle-Dye Conjugated Systems

Shira Halivni, Amit Sitt, Ido Hadar, and Uri Banin*.

Institute of Chemistry and the Center for Nanoscience and Nanotechnology,

The Hebrew University, Jerusalem 91904, Israel

Abstract

Fluorescence resonance energy transfer (FRET) involving a semiconductor nanoparticle (NP)

acting as a donor, attached to multiple acceptors, is becoming a common tool for sensing,
bio-labeling and energy transfer applications. Such nano-systems, whose dimensions are in
the range of FRET interactions, exhibit unique characteristics which are related to the shape
and dimensionality of the particles, and to the distribution of the acceptors in the vicinity of
the particle. Understanding the effect of these parameters is of high importance for
describing the FRET process in such systems and for utilizing them for different applications.

In order to demonstrate these dimensionality effects, the FRET between CdSe/CdS core/shell
NPs with different geometries and dimensionalities to Atto 590 dye molecules acting as
multiple acceptors covalently linked to the NP surface is examined. Steady state emission and
temporal decay measurement were performed on the NPs, ranging from spherical to rod-like
shapes systems, as function of acceptor concentration. Changes in the NP geometry, and
consequently in the distributions of acceptors, have led to distinctively different FRET
behaviors. The results are analyzed using a modified restricted geometries model, which
captures the dimensionality of the acceptor distribution, and allows extracting the
concentration of dye molecules on the surface of the NP for both spherical and elongated NPs.
The results obtained from the model are in high agreement with experimental results. The
approach may be useful for following the spatial dynamics of self-assembly, and for a wide
variety of sensing applications.
 Multitask Mix-and-Measure Luminescence Nanoparticle Methods for Sensitive
Quantification and Aggregation of Biomaterial and Polymers

Harri Härmä, Sari Pihlasalo, Pekka Hänninen

Laboratory of Biophysics, University of Turku, Tykistökatu 6A, FI-20520 Turku, Finland

A sensitive mix-and-measure luminescence method to quantify proteins, cells, polymers

and detergents have been developed. Size-dependent adsorption of the method also
provides a means to investigate aggregation processes and quality-control stability of
protein solutions. The method is based on the adsorption of sample and fluorescently
labeled protein to nanoparticles. The adsorption of sample to the particle is detected as
a decreased luminescence resonance energy transfer signal between the donor Eu(III)
labelled particle and the acceptor labelled protein.

The advantage of the developed method relates to high sensitivity, simplicity, tolerance
against common contaminants, and low protein-to-protein variability compared to the
commercially available methods. The assay sensitivity of low and sub micrograms per
liter of protein or nearly single eukaryotic cells is detected. The detection limits of 0.1-1
ng protein sample are 10-100 times more sensitive than the most sensitive
commercially available protein measurement methods. Moreover, the protein
concentration can be measured from cell lysates without any need for centrifugal
separation of non-soluble cell parts. Polymers are monitored at pico molar concentration
level, surfactants at nanomolar concentrations and protein aggregation can be followed
at nanomolar concentrations. A nanoparticle aggregation assay for beta-amyloids of the
Alzheimer’s disease is discussed.
The developed versatile mix-and-measure concept is evidentially highly suitable to
various targets. The assay is user-friendly, and no heating steps or toxic compounds
are required to gain extremely high sensitivity. As nanoparticles are key components of
the assay, properties such as particle surface charge can be potentially measured using
the same assay principle. Novel assay variants of the LRET nanoparticle concept are
presented and discussed.
 Short-Chained Alcohols Quench the Luminescence of PbSe and CdSe QDs
1 1 2 1
A. Hassinen , I. Moreels , J. C. Martins and Z. Hens
1
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium
2
NMR and Structure Analysis Unit, Ghent University, Krijgslaan 281-S4, 9000 Ghent, Belgium

A typical step in the processing of colloidal quantum dots (QDs) dispersed in apolar solvents
is their precipitation by addition of an non-solvent like methanol. Intriguingly, the exposure of
CdSe QDs to methanol and other non-solvents leads to a decrease of the
photoluminescence quantum yield (PL QY) of the QDs.[1] This has been attributed to the
progressive loss of datively bound (weak) ligands and the absorption of methanol molecules
to the surface of the QDs during purification. Herein, we present the results of the effects of
short-chained alcohols on purified PbSe and CdSe QDs stabilized by strongly binding oleate
(OA-) ligands. We also look into the effect of purification steps on freshly synthesized CdSe
QDs.

We have used nuclear magnetic resonance spectroscopy (NMR), which has been shown to
hold considerable potential for the in situ characterization of sterically stabilized colloidal
QDs,[2] to probe the effect of alcohols on the OA- ligands. We find that the repeated
exposure of the QDs to alcohols increases the loss of OA ligands and that the chain length of
the alcohols affects the intensity of the release. These NMR results are supported by PL
measurement, where the decreasing chain length of the alcohols increases the observed PL
quenching. In contrast, acetonitrile did not induce a measurable release of OA- ligands and
the PL did not quench upon addition. We speculate that the difference in between alcohols
and acetonitrile is related to the presence or absence of protons that can be exchanged with
the original OA- ligands. The organic ligands have shown to strongly affect the physical and
chemical properties of colloidal QDs.[3] As alcohols are used commonly as non-solvents in
the purification steps of colloidal QDs, it is important to realize that this purification affects the
ligands and this way the PL of the QDs, and that this effect is depended on the chosen non-
solvent.

1. Morris-Cohen, A. J.; Donakowski, M. D.; Knowles, K. E.; Weiss, E. A. J. Phys. Chem. C 2010, 114 (2), 897-906
2. Hassinen, A.; Moreels, I.; Donega, C. D.; Martins, J. C.; Hens, Z. J. Phys. Chem. Lett. 2010, 1, 2577-2581
3. Moreels, I.; Fritzinger, B.; Martins, J. C.; Hens, Z. J. Am. Chem. Soc. 2008, 130, 15081-15086
 Binding of Phosphonic Acids to CdSe Quantum Dots, a Solution NMR Study
1 1 2 1
A. Hassinen , R. Gomes , J. C. Martins and Z. Hens
1
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, 9000 Ghent, Belgium
2
NMR and Structure Analysis Unit, Ghent University, Krijgslaan 281-S4, 9000 Ghent, Belgium

In a hot injection synthesis, colloidal nanoparticles are made in a reaction mixture containing
precursor species, solvent and surfactants. These surfactants act as reagents during the
reaction and they stabilize the colloid by forming a molecular monolayer of ligands at the
nanoparticle surface.[1] Among the commonly used surfactants: thiols, amines, phosphine
oxides or carboxylic acids, phosphonic acids (-RPO(OH)2) stand out. Being used in the
synthesis of a variety of nanoparticles, they are typically considered as the strongest ligands,
for instance in the case of cadmium chalcogenide semiconductor nanoparticles or quantum
dots (QDs).[2] Moreover, phosphonic acids are essential to the formation of quantum rods
(QRs)[3], interesting nanostructures with anisotropic shape and therefore unique electrical
and optical properties. [4]

Here, solution nuclear magnetic resonance (NMR) spectroscopy is used to analyze the
binding of phosphonic acid to colloidal QDs. Especially in the case that free/bound exchange
is slow with respect to the NMR time scale, solution NMR is a suitable technique for this
purpose.[5,6] Resonances of bound ligands appear broadened and shifted with respect to
free ligand resonances, which enables to identify and quantify the ligands. Moreover,
additional information can be obtained using diffusion ordered spectroscopy (DOSY), where
the resonances of the free and surface-bound ligands are separated along the diffusion
dimension, or using nuclear Overhauser effect spectroscopy (NOESY), where efficient cross
relaxation is indicative of ligand/QD interaction.[5]

NMR experiments were carried out with wz-CdSe QDs that are used as seeds in the growth
of highly luminescent CdSe/CdS QRs. They are synthesized following the procedure
previously published by Manna et al [7] and the solvent/surfactant mixture is composed of tri-
octylphosphine oxide (TOPO), octadecylphosphonic acid (ODPA) and Se is delivered by hot
injection of TOP-Se (tri-octylphosphine selenide). We show that the ligand shell of CdSe QDs
synthesized in the presence of ODPA, TOP and TOPO is constituted by 45 % of the
octadecylphosphonic anhydride and 55 % of ODPA. The binding strength of the CdSe-ODPA
bond strongly exceeds that of the CdSe-OA bond. In particular, OA is readily and
quantitatively replaced by ODPA on QD-CdSe surfaces, while the reverse process is only
partially possible at elevated temperature. ODPA binds preferentially as a monodentate
hydrogen phosphonate ligand (ODPA-), as indicated by the stoichiometry of the ligand
exchange reaction and the charge balance between the Cd excess and the bound ligands.

1. Yin, Y. and Alivisatos, A. P. Nature 2005, 437, 664-670

2. Yu, W. W., Wang, Y. A. and Peng, X. Chem. Mater. 2003, 15, 4300-4308
3. Wolcott, A., Fitzmorris, R. C., Muzaffery, O. and Zhang, J. Z. Chem. Mater. 2010, 22, 2814-2821
4. Talapin, D. V., Koeppe, R., Götzinger, S., Kornowski, A., Lupton, J. M., Rogach, A. L., Benson, O., Feldmann, J. and Weller,
H. Nano Lett. 2003, 3, 1677-1681
5. a) Fritzinger, B., Capek, R. K., Lambert, K., Martins, J. C. and Hens, Z. J. Am. Chem. Soc. 2010, 132, 10195-10201. b)
Fritzinger, B., Moreels, I., Lommens, P., Koole, R., Hens, Z. and Martins, J. C. J. Am. Chem. Soc. 2009, 131, 3024-3032
6. Moreels, I., Fritzinger, B., Martins, J. C. And Hens, Z. J. Am. Chem. Soc. 2008, 130, 15081-15086
7. Carbone, L., Nobile, C., De Giorgi, M., Sala, F. D., Morello, G., Pompa, P., Hytch, M., Snoeck, E., Fiore, A., Franchini, I. R.,
Nadasan, M., Silvestre, A. F., Chiodo, L., Kudera, S., Cingolani, R., Krahne, R. and Manna, L. Nano Lett. 2007, 7, 2942-
2950
 From a high precision synthesis of monodisperse Indium, Tin, and Indium-Tin
colloidal nanocrystals to transparent Indium-Tin-Oxide nanoelectrodes
Maksym Yarema,1 Stefan Pichler,1 Dominik Kriegner,1 Julian Stangl,1 Olesya Yarema,1
Raimund Kirchschlager,1 Sajjad Tollabimazraehno,2 Markus Humer,1 Gang Chen,1 Wolfgang
Heiss1

1) Institute of Semiconductor and Solid State Physics, University Linz, Linz, Austria
2) Center for Surface and Nanoanalytics, University Linz, Linz, Austria

Optically transparent indium-tin-oxide (ITO) electrodes are major components of

optoelectronic devices, including solution processed solar cells and nanocrystal based
photodetectors. Whereas industrial ITO films are predominantly prepared by deposition from
vapour phase, the world wide shortcoming of In resources triggered a search for novel,
material-effective methods for preparation of patterned ITO electrodes, including also
deposition from nanoparticle solutions. Since electrodes from ITO nanoparticles usually
suffer from low conductivity, improvements are required, which are suggested to be
obtainable by optimizing particle size distributions and composition homogeneities. While
such efforts are reported for ITO nanoparticle inks, in this work we show up an alternative
procedure towards a material effective fabrication of nano-patterned ITO electrodes, based
on: (i) the synthesis of monodisperse indium and indium-tin (In1-xSnx) colloidal nanocrystals
(NCs) with desired size and composition, (ii) the preparation of nanosized patterns from In1-
xSnx NCs on structured substrates, and (iii), oxidation of the NC patterns to convert the In1-
xSnx NCs to compact, conductive, and transparent ITO electrodes.
The In1-xSnx NCs with concentrations x up to 10 atomic % are synthesized via hot-
injection of their silylamide salts into amine. Small amounts of super-hydride are added to
initiate the nuclei formation. The size of the NCs, synthesized at a growth temperature above
the NCs melting temperature, is accurately tuned between 8 and 19 nm. The tin content is
adjusted solely by the ratio between the injected Indium and Tin precursors. The NCs exhibit
almost perfect spherical shapes and extremely narrow size distributions, down to 2.2%. The
unique monodispersity of the NCs is proven by the formation of highly-ordered 2D and 3D
self-assemblies, with outstanding long range ordering, deduced from an analysis of the
autocorrelation function from SEM and TEM images.1
Uniform NC films are produced by a sequence of spin casting and cross linking steps.
These films are treated by ozone plasma to convert the indium NCs into In2O3 and the In1-xSnx
NCs into ITO. After oxidation the films are optically transparent and electrically conductive,
due to the conversion of the materials and the removal of the surface ligand shell. A
subsequent annealing step in air improves the sheet resistance by two orders of magnitude,
and the obtained conductivity values are competitive to the best reported values for films from
ITO nanoparticle inks. Electrodes from In1-xSnx NCs are also fabricated by the Damescene
process2 on patterned substrates to get nanosized electrodes with lateral dimensions as small
as 25 nm, which can be achieved only due to the small size dispersion of the used NCs.

/1/ S Pichler, M. I. Bodnarchuk, M. V. Kovalenko, M. Yarema, D. V. Talapin, W. Heiss, Evaluation of ordering

in single-component and binary nanocrystal superstructures by analysis of their autocorrelation functions.
ACS Nano 5, 1703 (2011)
/2/ G. Chen, M. I. Bodnarchuk, M. V. Kovalenko, G. Springholz, W. Heiss, W. Jantsch, E. Platzgummer, H.
Loeschner, J. Schotter, Damascene process for controlled positioning of magnetic colloidal nanocrystals,
Adv. Mat. 22, 1364 (2010)
Seeded growth of large and luminescent CdSe/CdS nanoparticles

Marco Cirillo1, Raquel Gomes1, Zeger Hens1

1
Physics and chemistry of nanostructures, Ghent University, Belgium.

CdSe quantum dots (QDs) have been widely studied in the last two decades for their
size dependent opto-electronic properties. This has lead to highly controlled synthesis
routes that yield QDs well defined in terms of size and shape. The main disadvantage of
CdSe QDs is their low photoluminescence quantum yield (PLQY) after sample
purification. This problem is typically addressed by the growth of an inorganic shell
around a starting core QD to passivate the QD surface. In the case of CdSe QDs, CdS
or ZnS shells are often grown by the stepwise addition of the shell precursors, forming
the additional shell in a layer by layer fashion (SILAR). These process, although
successful, are time consuming, especially for the synthesis of thick shells. Here, we
report on a fast (3 minutes) and easily reproducible shell growth method to obtain large
core shell NCs through seeded growth. This new synthetic route is applicable to different
kinds of core QDs, such as wurtzite and zinc blende CdSe and ZnSe. The method is
based on the injection of the CdSe (ZnSe) cores together with the sulfur precursor in
the reaction mixture containing the Cd precursor for the shell growth. This contribution
focuses on controlling the shell growth by adapting the composition of the reaction
mixture. We found that both the amount of oleic acid and Cd precursor are of
importance. The first acts on the solubility of the precursors and reaction intermediates.
When it is present in a constant excess, 4.4 mmol, the synthesis results in
monodispersed nanoparticles (10%) and secondary nucleation of CdS nanocrystals is
suppressed. The amount of Cd on the other hand is important to tune the final size of
the nanoparticles while operating in presence of excess of sulfur, having as end result
particles ranging from 6 to 18 nm with about 23 layer of CdS. This result can be
compared to a SILAR reaction of several hours. The resulting core/shell QDs are
spherical and show a strongly improved PLQY (up to 50%).
 Absorption enhancement in colloidal quantum dot monolayers through coherent dipolar coupling
Pieter Geiregat1,2,3, Yolanda Justo1,3, Zeger Hens1,3
1
Physics and Chemistry of Nanostructures, Ghent University, Belgium
2
Photonics Research Group, Ghent University, Belgium
3
NB Photonics – Center for Nano and Biophotonics, Ghent University, Belgium
Nanocrystals are thought to be viable candidates for the fabrication of solar cells, light emitting diodes,
photodetectors, .... In such a device context, nanocrystals will always be deposited in thin layers. However,
colloidal nanocrystal properties (e.g. absorption cross sections, exciton lifetime, ...) are typically evaluated
in solution using effective medium approaches such as the Maxwell-Garnett (MG) model1.These models
assume that the nanocrystals behave as uncoupled dipoles embedded in a host medium with given
permittivity. However, it is clear that this assumption no longer holds for a close packed film of
nanocrystals where those dipoles tend to couple through electromagnetic multipolar interactions. Using
properties measured in solution to evaluate the performance and physics of thin film devices is therefore
incorrect, or at least a serious simplification.
The basic idea is that the internal field of a particle in close proximity to other dipoles will be a
superposition of the influence of the external field and the induced dipolar fields of the neighbouring
particles. We expect that this type of electromagnetic coupling will increase the absorption cross section
relative to that of the particles in solution. We therefore define an 'enhancement factor‘E’, being the ratio
between the absorption cross section in film to the cross section in solution.
To access the enhancement E experimentally, we measure the absorption spectrum of single and multiple
close packed monolayers of nanocrystals on glass substrates using a standard UV-VIS-NIR
spectrophotometer. The layers are deposited using Langmuir-Blodgett deposition2and are well defined (i.e.
particle density and lattice symmetry are uniform over large areas). The enhancement predicted by our
intuitive reasoning is substantial, leading to a size-dependent value of E up to 5 for PbS monolayers. The
effect is smaller in CdSe because of the smaller dielectric screening in these materials. The latter probably
decreases the influence of a dipole on its neighbours.
Starting from our intuitive coupling idea, we can calculate E from theory as a function of particle size. To
achieve this, we use the coupled dipole model (CD model) which was developed to understand the localised
plasmonic response of coupled arrays of metallic nanoparticles3. We are able to predict the size-dependence
of the measured enhancement, both for CdSe and PbS using a limited number of free fitting parameters.
We use monolayers since they are 2D structures that are easy to model in a scalar approach. In a device
context (e.g. a solar cell) nanocrystals will be stacked in multiple layers to achieve a certain thickness (e.g.
to absorb sunlight). Our model can be extended to predict the behaviour in these technologically very
relevant multilayers. It turns out the enhancement is also present in these stacked systems.
We also expect the coupling in these nanocrystal solids to affect the emission properties. Research is
ongoing to investigate collective properties such as sub- and superradiance. This will provide us with a
complete picture on the very exciting optical behaviour of quantum dot solids, extending their applicability
to new fields as quantum optics.
We believe our results have paved the way to a more general understanding of nanocrystal solids, the latter
being very relevant for real-life applications of nanocrystals such as thin-film solar cells. We show that in
close packed layers, properties such as absorption cross section are not intrinsic to the nanocrystal but are
determined by their interactions with other particles. These interactions can be tuned through ligand length
and particle size, both of which are easily accessible during the colloidal synthesis or through post-
deposition processing (e.g. ligand exchange).
References
(1) Moreels, I. Lambert, K. Smeets, D. Muynck, D. De; Nollet, T. Martins, J. C. Vanhaecke, F. Vantomme, A.
Delerue, C. Allan, G.; Hens, Z. ACS Nano2009, 3, 3023-30.
(2) Justo, Y. Moreels, I. Lambert, K.; Hens, Z. Nanotechnology2010, 21, 295606.
(3) Zhao, L. Kelly, K. L.; Schatz, G. C. The Extinction Spectra of Silver Nanoparticle Arrays: Influence of Array
Structure on Plasmon Resonance Wavelength and Width. The Journal of Physical Chemistry B2003, 107,
7343-7350.
Broadband and Ultrafast Intraband Absorption in Lead based Colloidal QuantumDots
1,3,4 1,3,4 2 2
Bram De Geyter , Pieter Geiregat , Yunan Gao , Sybren ten Cate , Arjan J.
2 2 3,4 2
Houtepen ,Juleon M. Schins , Dries Van Thourhout , Laurens D.A. Siebbeles , Zeger
1,4
Hens
1
Physics and Chemistry of Nanostructures, Ghent University, Belgium
2
Department of Chemistry, Delft University of Technology, The Netherlands
3
Photonics Research Group, Ghent Univeristy, Belgium
4
NB Photonics – Center for Nano and Biophotonics, Ghent University, Belgium

Colloidal nanocrystal quantum dots and dot-in-dots are highly tunable optical materials due to
strong quantum confinement of the carriers. The quantum confinement not only raises the
bandgap energy, it also relaxes intraband selection rules, making multicarrier Auger
recombination ultrafast and optical dipole transitions between intraband states allowed.

We present a transient absorption study combined with tight binding calculations, which
shows that photoinduced absorption below the bandgap in lead-chalcogenide core- and
core/shell colloidal quantum dots ( PbS, PbSe and PbSe/CdSe) can be attributed to intraband
absorption.

The power dependence of the photoinduced absorption (PA) agrees with a state-filling model
of the bandgapexcitonic states. Also, the dynamics of the PA decay correspond to the
bandgapexciton lifetime, dominated by picosecond Auger recombination for multi-exciton
states. This indicates that the initial state of the PA process is a band-edge state.

The strength of the intraband transition is wavelength-independent up to (at least) 2000 nm

and amounts to about 10% of the bandgap oscillator strength. This allows us to partially
exclude the role of surface defects for the final state. Also, the energy of the probe photons is
too ‘high’ to induce discrete state transitions (such as 1S to 1P) as measured previously using
mid-IR probes. We therefore attribute the observed effect to intraband absorption from a
discrete, quantum confined level to a continuum of states.

We further confirm the intrinsic nature (i.e. non-defect related) of the process by tight binding
simulations. In the calculations, no defect –or phonon-related mechanisms are taken into
account. The simulations confirm the experimental data both quantitatively (up to factor of 2)
and qualitatively (broadband). They also justify the picture of a phonon-less, photo-induced
transition from a confined band-edge state to a continuum.

Apart from the fundamental scientific interest, a phenomenon as intraband absorption can
have consequences for photonic applications of infared colloidal nanocrystals. The presence
of ultrafast PA might limit the performance of lead-chalcogenides as optical gain media.
Other applications, however, might benefit from this mechanism: the broadband nature, the
ultrafast dynamics and the high cross section make this process ideal for all-optical high-
speed signal processing , e.g. on the silicon photonics platform in both the near and the mid-
infrared wavelength range.
 Structural aspects and application perspectives of highly porous
metallic aerogels produced by template-free 3D self assembly

Anne-Kristin Herrmann, Nikolai Gaponik, Alexander Eychmüller

Physical Chemistry and Electrochemistry, TU Dresden, Bergstr. 66b,
01069 Dresden, Germany; contact: [email protected]

In addition to the control of size, shape and functionalization also the assembly and
arrangement of metal nanoparticles come into the focus of materials scientists. This
is due to the creation of a variety of properties by the interaction and linkage of a
large number of nanoobjects. For building up of complex structures and usable
devices several techniques such as the employment of templates and lithography as
well as the directed self assembly of nanoparticles are available.
Here we show a new method for the preparation of networked structures which is
based on the controlled destabilization of noble metal nanoparticles in order to create
macroscopic, spongelike, extremely light and highly porous materials which show
structuring on the nanometer scale.[1,2] The fusion of the initial nanoparticles leads to
a complex and self-supporting network which forms a monolith with several
millimeters in diameter. These materials are formed in liquid media and supercritical
drying is used to transform them into aerogels. Several methods such as optical and
electron microscopy (SEM, TEM), XPS, nitrogen adsorption etc. were used to unravel
important characteristics of the materials created. The related list of promising
application fields is wide-ranging: heterogeneous- and electrocatalysis, optical
sensors, SERS substrates, broad band optical limiters, and conducting transparent
substrates. Hence, future work focuses on the characterization and modulation of
these materials in order to realize efficient applications and devices.[3]

[1] Bigall, Herrmann, Vogel, Rose, Simon, Carrillo- Cabrera, Dorfs, Kaskel, Gaponik,
Eychmüller, Angew. Chem. Int. Ed. 2009, 48, 9731.
[2] Herrmann, Bigall, Lu, Eychmüller, in Complex-Shaped Metal Nanoparticles, ed.
Rogach, Wiley-VCH, 2011, in press.
[3] Gaponik, Herrmann, Eychmüller, J.Phys.Chem. Lett. 2012, 3, 8.
Thermo-responsive Platforms with Quantum Dots and Au Nanoparticles Trapped
by Optical Tweezers; Synthesis and Optical Studies

Silvia Hormeño, Neus G. Bastús, Andrea Pietsch, Horst Weller, Ricardo Arias González, and Beatriz H. Juárez

We have studied the hydrodynamic size and optical response of systems composed of both
colloidal quantum dots (QDs) and Au nanoparticles immobilized on individual thermoresponsive
microspheres (pNIPAM)1 by optical tweezers.2 The herein used optical tweezers system consists of two
equal counterpropagating laser beams (two 835-nm diode lasers) brought to the same focus.3 This design
offers improved trapping efficiency for metallic particles since the opposite absorption and scattering
forces, which point along the propagating direction of the beams, provide axial stability to the particle,
thus leading to a net 3D gradient-force trap. In addition to the optics, the set-up includes an automated
hydrodynamic flow system consisting of computer-controlled solenoid valves, glass micro-dispensers and
pressure sensors. From the trapping experiments we observed that while moderate shrinkage is observed
for bare pNIPAM beads, severe shrinkage is observed for pNIPAM/Au ones due to the extra heating
induced by the presence of a surface ensemble of Au NPs. The presence of QDs on the pNIPAM beads
reduces the local heating of water in the polymeric network leading to higher sizes. While a constant
emission (minute range) from the pNIPAM/QDs beads is recorded, emission and subsequent quenching
due to energy transfer from the QDs to the metallic NPs take place in the optical trap for
pNIPAM/Au/QDs microspheres. This effect is the consequence of plasmon-exciton interactions as QDs
and Au NPs get closer upon pNIPAM shrinkage. These systems combine the ability for thermal sensing
(due to the properties of pNIPAM systems and Au NPs), and labeling (due to the QDs), representing very
interesting platforms for the design of thermal sensors in biological studies. The ability to trap and
manipulate specimens along with the possibility to immobilize cells or organelles in fixed positions open
the way to carry out imaging studies between interacting pNIPAM beads and cells. These studies may
contribute to shed more light on the required forces for internalization processes. In addition, the use of
thermoresponsive elements as the ones presented here may also be an effective way to measure and
calibrate the temperature in optical trapping set-ups.

Upper image: sketch of a thermo-responsive pNIPAM bead trapped by optical tweezers. Lower image: TEM image
of a pNIPAM bead decorated with Au nanoparticles (dark spots) and colloidal quantum dots (grey spots).

1) A. Salcher, M. Nikolic, S. Casado, M. Velez, H. Weller and B. H. Juarez, “CdSe/CdS nanoparticles immobilized on
pNIPAM-based microspheres” Journal of Materials Chemistry 20, 1367–1374, (2010)
2) S. Hormeño, N. G. Bastús, A. Pietsch, H. Weller, R. Arias-Gonzalez, B. H. Juarez, “Plasmon-Exciton interactions
demonstrated by Optical Tweezers”, Nano Letters, DOI: 10.1021/nl202560j (2011)
3) S. B. Smith, Y. Cui, C. Bustamante, “Optical-trap force transducer that operates by direct measurement of light
momentum“ Methods in Enzymology 361, 134-62, (2003)
Programmed Assembly of Gold Nanoparticles using DNA click-chemistry
AmelieHeuer-Jungemann,a,b RobertKirkwood,a TomBrownb and Antonios G.Kanarasa*
a
Physics and Astronomy, bChemistry, University of Southampton, Southampton, UK,
SO171BJ
Corresponding author: [email protected]

Abstract
Controllingnanoparticle self-assembly in a very effective and easy way can have many
applications in several scientific fields such as nanophotonics and metamaterials,
nanoelectronics and nanodiagnostics.1 In particular the employment of DNA as a scaffoldfor
the organization of nanoparticles is exceptionally attractive and has been utilized to arrange
nanoparticles into dimers,trimers or more complex structures. This is due to the uniquebase
pairing nature of DNA that offers versatility and specificity. On the other hand, restriction
enzymes and ligases have been further used to manipulate DNA-nanoparticle conjugates with
great success.
In this poster we present a new approach to control the self-assembly of DNA coated
nanoparticles using ‘click-chemistry’.4ssDNA gold nanoparticles
monoconjugatesfunctionalised with an azide and an alkyne group respectively can be brought
together via a partially complementary DNA template strand, and ‘clicked’. The reaction can
take place without the use of CuI as a catalyst, simplifying the preparation steps. The template
strand can then be removed using a template complement. Dimers, trimers and higher ordered
assemblies can thus easily be formed, connected to each other via ssDNA, excluding the
reversible base-pairing approach.Some of the advantages of the newly form organized
structures are the higher degree of flexibility and the opportunity to decrease particle distance
through the addition of pre-defined lengths of a complementary DNA strand.

This strategy can be easily extended to different types of gold nanoparticlesespecially

anisotropic particles such as rods and prisms, and form plasmonic ‘artificial molecules’,
whose physical properties will be of great interest.

References:
[1] (a) Talapin, D. V.; Lee, J. S.; Kovalenko, M. V.; Svechenko, E. V. Chem. Rev. 2010, 110, 389–458. (b)
Claridge, S. A.; Castleman, A. W., Jr; Khanna, S. N.; Murray, C. B.; Sen, A.; Weiss, P. S. ACS Nano2009, 3,
244–255.
[2] a) Park, S. Y., Lytton-Jean, A. K. R. ; Lee, B. ; Weigand, S.; Schatz, G. C.; Mirkin, C. A. Nature2008, 451,
553-556; b) Mastroianni, A. J.; Claridge, S.A. and Alivisatos, A. P. J. Am. Chem. Soc., 2009, 131, 8455 – 8459;
c) Coomber, D.; Bartczak, D.; Gerrard, S.R.; Tyas,S.; Kanaras, A.G; Stulz, E. Langmuir2010, 26, 13760–13762.
[3] a) Claridge, S.A.; Mastrioanni, A. J. ; Au, Y .B. ; Liang, H. W.; Micheel, C.M.;Fréchet J.M.J. and Alivisatos,
A. P.J. Am. Chem. Soc., 2008, 130, 9598 – 9605;, b) Kanaras A. G.; Wang Z.; Bates A. D.; Cosstick R.; Brust M.
Angew. Chem. Int. Ed., 2003, 42, 191-194.
[4] Shelbourne, M.;Chen, X.; Brown,T.;and El-Sagheer, A.H. Chem. Commun., 2011, 47, 6257 – 6259.
 Photoluminescenceenhancementbylocalizedsurfaceplasmon
resonanceofAunanoparticles
EsmaeilHeydari,ToninoGreco,JoachimStumpe

FraunhoferInstituteforAppliedPolymerResearch,Geiselbergstraße69,14476Potsdam,Germany

Email:[email protected]

Recently photoluminescence (PL) enhancement based on the localized surface plasmon resonance
(LSPR) of metal nanoparticles has attracted extensive attention for biosensors, optoelectronic
devices and nanolasers. It is demonstrated that LSPR enhance the PL by changing the excitation
and/oremissionratesofluminophore.

PL enhancement of Rose bengal in close vicinity of gold nanoparticles (AuͲNPs) was
investigated herein. AuͲNPs were immobilized on glass substrates with the soͲcalled silanization
method(FIG.1.a).AspacerlayerofPMMAwasappliedontopoftheAuͲNPstoavoidquenching.In
ordertogetaninsightonthecontributionoftheexcitationandemissionrateonPLenhancement,
measurements were performed for different excitation wavelengths. It was observed that PL
enhancementfactorincreasedwhentheexcitationwavelengthgotclosetotheresonancepeakof
AuͲNPs. PL lifetime was recorded in the presence of AuͲNPs and it showed the minor changes. PL
measurementswerecarriedoutfor20,40,60,80,and100nmAuͲNPs.Itrevealedthatthelargest
enhancementwasbelongedto100nmAuͲNPs(FIG.1.b).WebelievethatPLenhancementofRose
bengalispredominantlysupportedbytheexcitationrateenhancementduetopresenceofAuͲNPs.

20

15
Y[μm]

10

0
0 5 10 15 20

X[μm]

FIG.1(a)Left,Distributionof100nmAuͲNPs(b)Right,PLenhancementbaseon100nmAuͲNPs

Acknowledgment

This work has been supported by the Marie Curie Actions, Seventh Framework Programme,“Dendreamers”
project.
 Terbium to quantum dot FRET in homogeneous sandwich immunoassays.
Toward multiplexed early diagnostics of Alzheimer’s disease.

K. David Wegner, Zongwen Jin, Stina E. Lindén and Niko Hildebrandt*

Université Paris-Sud, Orsay, France

[email protected]

Although a preventative or curative treatment for Alzheimer's disease (AD) is not available today
the existing drug treatment is most effective in the early stages and thus an early diagnosis of AD
is of paramount importance. Today’s combination of psychological testing, brain-imaging and
exclusion of other neurological disorders makes the diagnosis of AD complicated and time
consuming. A rapid, sensitive and specific immunoassay for protein markers in whole blood or
plasma would therefore largely improve early diagnosis as well as therapy and disease
progression monitoring for the benefit of clinicians and patients. Homogeneous assays based on
FRET (Förster or Fluorescence Resonance Energy Transfer) from one fluorophore labeled
specific primary antibody (AB1) to another (AB2) within an “AB1-biomarker-AB2” immune
complex are an ideal basis to meet these challenging requirements of in vitro diagnostics. The
combination of Tb complexes and semiconductor quantum dots (QDs) in FRET-based bioassays
has many advantages concerning multiplexing and ultra high sensitivity. So far only proof-of-
principle studies with biotin-streptavidin model systems have been performed and the
transformation to real-life clinical diagnostic systems using antibody-based immunoassays has
not yet been demonstrated. In this contribution we show homogeneous sandwich immunoassays
for L-selectin, in which AB1 and AB2 (against L-selectin) were labeled with Tb-complexes and
red emitting QDs, respectively. Although the immunocomplexes of two full IgG antibodies (ca.
150 kDa, with lengths of ca. 9 nm for each Fab and 8 nm for the Fc), the L-selectin biomarker
(ca. 80 kDa) as well as the PEG and lipid functionalized QDs (ca. 15-20 nm in diameter) are
quite large, we were able to demonstrate specific FRET from Tb-AB1 to QD-AB2 once the L-
selectin biomarkers were added in nanomolar concentrations to the antibody solutions. We will
provide a detailed description of the biomolecular design as well as the FRET immunoassays for
L-selectin detection using these Tb-to-QD FRET immunoassays.
Photogeneration, fissusion and decay of charge carriers in quantum-dot solids
Arjan.J. Houtepen

Abstract:
Films of colloidal semiconductor nanocrystals, so-called Quantum-Dot solids, are
heavily investigated as candidates for photodetectors and solar cells. The
operation of such devices requires efficient charge-carrier photogeneration, high
charge-carrier mobilities and long charge carrier lifetimes. For photovoltaic
application Quantum Dots are of particular interest since it has been
demonstrated in recent years that absorption of a single high energy photon can
result in the generation of multiple excitons (multiple exciton generation, MEG).
If these excitons can be converted into mobile charge carriers this process will
lead to an increased photocurrent and, hence, an increased power conversion
efficiency in solar cells.
We have prepared QD solids composed of PbSe nanocrystals with very short
interparticle distances that fulfill all these requirements.The processes of
(multiple) carrier photogeneration1, 2, diffusion and decay3 have been studied by
a combination of terahertz spectroscopy, transient absorption spectroscopy and
temperature-dependent time-resolved microwave conductivity. Using these
techniques we demonstrate that the charge carrier mobilities are as high as 3
cm2/Vs and that all photogeneratedexcitons dissociate into mobile charge
carriers. The exciton dissociation rate is sufficiently high to allow even multiple
excitons, created efficiently via MEG, to dissociate into mobile charge carriers2.
As a result, multiple carriers per absorbed photon, generated efficiently via MEG,
are directly available, without the aid of an electric field or interfaces that
provide an additional driving force for exciton dissociation.
Our results demonstrate that Quantum-Dot solids are very promising candidates
for simple and cheap optoelectronic devices.

1. Talgorn, E.; Gao, Y.; Aerts, M.; Kunneman, L. T.; Schins, J. M.; Savenije, T. J.;
van Huis, M. A.; van der Zant, H. S. J.; Houtepen, A. J.; Siebbeles, L. D. A. Nat.
Nanotechnol. 2011, 6, (11), 733-739.
2. Aerts, M.; Suchand Sandeep, C. S.; Gao, Y.; Savenije, T. J.; Schins, J. M.;
Houtepen, A. J.; Kinge, S.; Siebbeles, L. D. A. Nano Lett. 2011, 11, (10), 4485-4489.
3. Gao, Y.; Talgorn, E.; Aerts, M.; Trinh, T.; Schins, J. M.; Houtepen, A. J.;
Siebbeles, L. D. A. Nano Lett. 2011, 11, (12), 5471-5476
Evaluation of Biomarkers for Alzheimer’s Disease by a FRET-based Detection
System
T. Hug*, A. Lüschow#, F. Geissler#, J. Dernedde*, Charité - Universitätsmedizin Berlin, *Institut für Laboratoriums-
medizin, Klinische Chemie und Pathobiochemie, #Klinik und Hochschulambulanz für Neurologie und Klinische
Neurophysiologie

Background/aim: The aim of the collaborative EU project „Nanognostics“ is to develop

quantum dot-based highly sensitive immunoassays for multiplexed diagnostics of
Alzheimer`s disease (AD). Charité’s tasks are: 1) Recruitment of patients with mild cognitive
impairment (MCI) and non-demented healthy controls (NDC). 2) Validation of antibodies
and/or aptamers applicable for the FRET-based multiplexed detection of AD marker proteins
from patient blood samples.
Methods: Potential AD markers: epidermal growth factor (EGF), vascular epidermal growth
factor (VEGF) and L-selectin are analyzed by using optimized ELISA technology to disclose
detection limits. The affinities of the different matched pairs of antibodies are calculated by
applying surface plasmon resonance measurements (Biacore). Patients recruited from the
memory clinic, as well as healthy controls, are examined and scored for mild cognitive
impairment (MCI) by applying Mini Mental Status Exam (MMSE) and a test battery of the
consortium to establish a Registry for Alzheimer`s Disease (CERADplus). From each study
participant a blood sample (5 ml, plasma (EDTA)) is drawn.
Results: By applying optimized ELISA technology we can detect in plasma (EDTA) EGF at a
concentration of less than 1 pg/ml, VEGF at a concentration of less than 25 pg/ml and L-
selectin at a concentration of less than 100 pg/ml. The calculated affinities of matched pairs
of antibodies are: EGF: MAB636, KD: 166 nM; AF236, KD: 68.4 nM; VEGF: MAB293, KD: 32.6
nM; BAF293, KD: 11.7 nM. A total of 46 probands have been enclosed. The 32 patients of the
Alzheimer`s disease group have an average age of 73.09r8.95 years, enclose 34% female
and have an average MMSE score of 21.06r3.29 (out of 30). The 14 probands of the healthy
control group have an average age of 66.43r5.92 years, enclose 64% female and have an
average MMSE score of 29.17r0.83 (out of 30).
Conclusion: At this intermediate time point of the collaborative project we are able to detect
the set of potential AD markers (EGF, VEGF, L-selectin) at physiological concentrations in
plasma (EDTA) by using optimized ELISA technology. The affinities of the matched pairs of
antibodies that we are providing to our partners are in the nanomolar range. At the moment
we have enclosed a total of 46 well documented probands (32 patients in the Alzheimer`s
disease group and 14 probands in the healthy control group). We are continuing to enclose
probands so that in future the newly developed quantum dot-based immunoassays can be
tested with a broad number of sample materials.
 Photo-stimulated gold nanoheaters in polymer and biological media:
Characterization of mechanical destruction and boiling

D. Hühn1, A. Govorov2, P. Rivera Gil1, W. J. Parak1

1
Fachbereich Physik and WZMW, Philipps-Universität Marburg, Marburg, Germany
2
Department of Physics and Astronomy, Ohio University, Athens, Ohio 45701, USA
Contact: [email protected]

Gold nanoparticle (Au NP) assisted remote- Laser beam

A B Medium

controlled release of immobilized molecules

out of layer by layer (LBL) deposited Polymer
Au cluster films
polyelectrolyte interfaces [1] might be a
promising application for drug delivery Hot region glass

approaches. For that the recently thoroughly

C D
investigated characteristics of the
light to heat conversion of gold
nanoparticles/clusters upon their
surface plasmon resonance (SPR) and the
heat transfer to the surrounding medium
might play the essential role [2,3].
Agglomerated Au NP clusters embedded in LBL assembled polyelectrolyte films (A) were optically
excited (B), which resulted in local ablation of material from the polyelectrolyte films (D) and in some
cases led to the formation of a gas bubble (C). Evidence is given that this process is mediated by
superheating of the medium around the excited Au NP clusters. This process is highly dependent on the
used medium. Besides the boiling point also salt and proteins in the medium affect the formation of gas
bubbles. These data demonstrate that the type of medium has to be considered for describing light-
mediated heating of Au NP clusters, which are fixed in a matrix surrounded by medium.

[1] G. Decher, Science 277, 1232 (1997).

[2] A. O. Govorov, H. H. Richardson, Nano Today 2, 30 (Feb, 2007).
[3] C. Hrelescu et al., Journal Of Physical Chemistry C 114, 7401 (Apr 29).
Surface study of CdSe nanocrystals attached to sp2 carbon surfaces by XPS and
solid NMR

Fabiola Iacono,1 Leonor de la Cueva,2 Cristina Palencia,2 Jonathan Rodriguez-Fernández,1 J. M.

Gallego,2,3 Roberto Otero,1,2 and Beatriz H. Juarez.2

1 Departamento de Física de la materia condensada, Universidad Autónoma de Madrid, Madrid, Spain.

2 IMDEA Nanoscience, Madrid, Spain
3 Instituto de Ciencia de Materiales de Madrid, ICMM, (CSIC) Spain

[email protected]

Rod-like nanocrystals ripen in the presence of chlorine compounds to yield dihexagonal pyramidal
nanocrystals that interact with sp2 carbon such us the surface of carbon nanotubes or highly oriented
pyrolytic graphite (HOPG) substrates (see figure). This interaction has been explored in detail studying
the nanoparticle surface and ligand shell composition by means of X-ray Photoelectron Spectroscopy
(XPS) and solid Nuclear Magnetic Resonance (NMR) analysis. XPS characterization of pyramidal
nanocrystals show a clear contribution of Cl, not present in the case of rod-like, probing the active role of
chlorine in the nanoparticle ripening. XPS analysis and Scanning Electron Microscopy (SEM) inspections
show higher coverage of the carbon surface at increasing Cl concentrations what indicates an interaction
mediated by chlorine. Furthermore, XPS characterization of both rod-like and dihexagonal pyramids
show energy shifts in the phosphorous signal as well as differences in the sp3 carbon and oxygen
contributions. Solid 31P NMR studies confirm different organic ligand shell of both systems and suggest
breaking of octadecylphosphonic anhydrides form at longer reaction times by Cl. Complementary 113Cd
solid NMR and Thermogravimetry Thermal Analysis TGA experiments indicate a less phosphorous
passivated surface of dihexagonal pyramidal nanocrystals compared to rod-like. These results point to a
modification of the ligand shell composition as well as a displacement of original phosphorous ligands by
chlorine.

(a,b) TEM images of CdSe nanoparticle grown on HOPG flakes at different magnifications. The base of
the pyramidal-shaped nanoparticles corresponding to the (001) CdSe wurtzite facet is in contact with the
sp2 carbon surface. (c) SEM image of CdSe nanoparticles grown on HOPG
 New chiral liquid crystalline superstructures

Ionut C. Ichim, Georg H. Mehl

Department of Chemistry, University of Hull, HU67RX, UK – [email protected]

The combination of silsesquioxane cores, which are known to promote microphase

separation in liquid crystal materials, and cholesterol groups containing mesogens, has not yet
been explored to any great extent.
In order to investigate this issue, two cholesterol groups containing mesogens were
designed and synthesized. To promote exclusively chiral nematic phase behaviour in these
mesogens, as well as low melting points and low transition temperatures, the cholesterol
groups were designed to be attached “laterally” to the silsesquioxane cores by
hydrosilylation, resulting in materials with liquid crystal phase at room temperature.
We report on the design, synthesis of these materials and the structural
characterization of the final products, based on optical measurements (POM, polarimeter,
VCD), DSC and XRD studies.
Structurally related to silsesquioxanes are small nanoparticles. We report on our effort
to connect laterally linked cholesteryl based mesogens to small nanoparticles.
We report on the design, synthesis of these materials and the analysis of these
heterogenic structures by optical means (POM, VCD), DSC, XRD and TEM.
The properties of these two classes of materials will be discussed and compared.

References

[1] B. Donnio, D. Guillon, Adv. Polym. Sci., 201, 45. (2006)

[2] H. Leube, H. Finkelmann, Polym. Bull., 20, 53. (1988)
[3] P.K. Karahaliou, P.H.J. Kouwer, T. Meyer, G.H. Mehl, D.J. Photinos, Soft Matter, 3, 857.
(2007)
[4] L. Cseh, G.H. Mehl, J. Am. Chem. Soc., 128, 13376. (2006)
 2D Assembly of Gold-Poly-N-isopropylacrylamide Core-Shell Nanoparticles

Sarah Jaber, Matthias Karg, & Paul Mulvaney

Nanoscience Laboratory, School of Chemistry & Bio21 Institute

[email protected]

1
One of the main challenges in nanoscience is the ordered assembly of nanocrystals. Such ordering
requires control of interparticle spacing which has previously been done using block copolymers or
silica shells as coatings for the particles. Microgels as nanoparticle coatings are of particular interest
due to their soft-sphere character and thermoresponsive nature. Furthermore, interparticle spacing
can be tuned by controlling the shell thickness during the synthesis by varying the monomer
concentration. The responsive behaviour of the system can also be controlled by varying the cross-
linker density.

We report the assembly of Gold-poly-N-isopropylacrylamide (Au-PNIPAM) particles prepared via a

generic and facile synthetic route resulting in particles having a single nanoparticle core, as
2
determined by transmission electron microscopy (TEM). Using atomic force microscopy (AFM), we
investigate the 2D assembly of these particles with different shell thicknesses, and exploit
electrostatic interactions to determine the best ordered arrangement of the particles. Furthermore,
annealing the particles removes the PNIPAM shell leading to a monolayer of uncoated well-spaced
gold nanoparticles.

References:

[1] Jaber, S., Karg, M., Morfa, A., and Mulvaney, P. 2D Assembly of Gold-PNIPAM Core-Shell Nanocrystals,
PCCP, 2011, 13, 5576 – 5578.

[2] Karg, M., Jaber, S., Hellweg, T., and Mulvaney, P. Surface Plasmon Spectroscopy of Gold-Poly-N-
isopropylacrylamide Core-Shell Particles. Langmuir 2011, 27, 820-827.
 Modification of nano-and microparticles with ion-specific ligands

Dorleta Jimenez de Aberasturi1,2, Idoia Ruiz de Larramendi1,Ricardo Pinedo1,Teófilo

Rojo1, Jose Maria Montenegro Martos2, Wolfgang J. Parak2

1
Department of Inorganic Chemistry (UPV/EHU), Apdo 644, 48080, Bilbao (Spain)
2
Fachbereich Physik, Philipps Universität Marburg, Marburg, Germany

Nanomaterials have shown to possess distinctive mechanical, magnetic, optical,

electronic, catalytic and chemical properties that contribute to promising applications
[1-2] .Their small size gives them a high surface area-to-volume ratio and facilitates the
interaction with several kinds of chemical species.

Due to a specific functionalization of the nanomaterials we could provide new

properties to them. By modifying the surface of nanoparticles with ion-specific ligands
we could use these novel compounds for different fields such as applications in the
direction of sensing [3], imaging [4], and separation [5].

For some applications, such as imaging, where small size is required, the use of
colloidal nanoparticles is a promising approach. Colloidal stability is a key requirement
to keep the maximal binding capacity, as agglomeration would reduce the effective
surface area. The use of amphiphilic polymers to disperse originally hydrophobic
nanoparticles in aqueous solution is a suitable approach in this direction [6]. Moreover
ion specific ligands could be directly integrated in the polymer shell around the
particles, as it has been already demonstrated for chelators for In and Gd ions [4].

Alternatively, polyelectrolyte capsules as carrier for ion-specific ligands can be

used, and in this way the quantity of ligand incorporated can be increased, putting
them into the capsule cavities and walls. Moreover the walls of the capsules could be
modified assembling different nanoparticles which give them additional properties.
For separation, multilayer capsules containing magnetic nanoparticles in the wall
[7] and ion-specific ligands in the cavity have been synthesized. By linking several
magnetic particles to one matrix the effective magnetic moment is increased, which
facilitates magnetic separation. By applying an external magnetic field their separation
from the aqueous phase is fast and easy and has also already been demonstrated [8].

We demonstrate that attaching ion-specific ligands to particles we could improve

their properties and use them for different applications such as sensing, imaging and
separation.
[1] J. Manuel Perez. Nature Nanotechnology2, 535 - 536 (2007)

[2] R. Pinedo, I. Ruiz de Larramendi, D. Jimenez de Aberasturi, I. Gil de Muro, J.I. Ruiz
de Larramendi, M.I. Arriortua, T. Rojo. J.Power Sources, 196 4174–4180 (2011)

[3] D. Jimenez de Aberasturi, J.M Montenegro, I. Ruiz de Larramendi, T. Rojo, T.A. Klar,
R.Alvarez-Puebla, L. M. Liz-Marzán, W.J. Parak. Chem Mater. (2012) Accepted

[4] Z. Ali, A. Z. Abbasi, F. Zhang, P. Arosio, A. Lascialfari, M. F. Casula, A. Wenk, W.

Kreyling, R. Plapper, M. Seidel, R. Niessner, J. Knöll, A. Seubert, W. J. Parak, Analytical
Chemistry 83, 2877-2822. (2011).

[5] A. Uheida, M. Iglesias, J. Colloid and interface Science 301, 402–408 (2006)

[6] Cheng-An J. Lin, Ralph A. Sperling, Jimmy K. Li,Ting-Ya Yang, Pei-Yun Li, Marco
Zanella, Walter H. Chang, and Wolfgang J. Parak, Small, 4, No. 3, 334 – 341 (2008).

[7] A. Z. Abbasi, L. Gutiérrez, L. L. del Mercato, F. Herranz, et al. Journal of Material

Chemistry C, (2011)

[8] B. Zebli, A. S. Susha, G. B. Sukhorukov, A. L. Rogach, W. J. Parak, Langmuir 21, 4262-

4265 (2005)
 MR and magnetic particles: imaging viscosity, reactive antibodies,
and the ongoing PCR reaction
Lee Josephson

Massachusetts General Hospital, Harvard Medical School, Martinos Center for Biomedical
Imaging

When placed in a magnetic field, magnetic particles (but not nanoparticles) aggregate in a time
dependent fashion with increases in solution T2. This increase in T2 with aggregation is
opposed by viscosity and therefore can be used to design relaxometry-based viscometers. T2
based viscometers can determine viscosity in enclosed samples, avoiding potential
contamination, with small volumes (~50 uL). Application and removal of magnetic fields can be
used to enhance reactions between magnetic particles and target molecular analytes in a
technique termed magnetically assisted chemical aggregation (MACA). The reactions of anti-
influenza antibodies with magnetic particles bearing influenza peptides have been amplified with
MACA, providing extremely fast, sensitive protocols for the detection of anti-influenza
antibodies. Finally, we have developed methods of surface functionalizing magnetic
nanoparticles with DNA binding fluorochromes and used these nanoparticles to obtain MR
images of PCR generated DNA from within ongoing PCR reaction tubes. When used in
conjunction with small relaxometers, magnetic nanoparticles or particles form a valuable and
practical approach to the design of novel reagent/instrument systems that can provide
information on a variety of analytes and in a wide variety of settings.
Multiple dot-in-rod PbS/CdS heterostructures with high photoluminescence
quantum yield in the near infrared.

1,2 3 1,2 1,2,4 3 1,2*

Yolanda Justo , Bart Goris , John Sundar Kamal , Pieter Geiregat , Sara Bals and Zeger Hens
1
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Gent, Belgium
2
Center for Nano and Biophotonics, Ghent University, Belgium
3
EMAT, University of Antwerp, Groenenborgerlaan 171, 2020 Antwerp, Belgium
4
Photonics Research Group, University of Ghent, Belgium

Due to their shape anisotropy, colloidal quantum rods (QRs) are an attractive class of colloidal
nanocrystals. Especially in the case of visibly emitting CdSe/CdS dot-in-rods, extensive research has
demonstrated properties like polarized emission, exciton storage based on the quantum-confined Stark
effect, amplified emission and lack of blinking.[1]. At present, similar QRs emitting in the near IR are
missing. In the case of lead chalcogenides (PbX), a few examples of the synthesis of rod or wire-like
structures have been reported, typically based on the oriented attachment of spherical quantum dots, with
limited control over the size and shape of the resulting structure [2].
Here, we present cationic exchange as an alternative approach for synthesizing PbS QRs [3]. Starting
from wurtzite CdS, we obtain PbS by a two-step process in which Cd is first exchanged for Cu, followed
by the exchange of Cu for Pb. Although the cationic exchange process does not maintain the single
crystalline nature of the original CdS QRs, the overall shape is preserved and PbS QRs are obtained. On
the other hand, the photoluminescence of the PbS QRs thus formed is strongly quenched. We show that
the subsequent growth of a CdS shell by a final cationic exchange step dramatically increases the PL
quantum yield (QY). By carefully setting the time and the temperature of the exchange process, PbS/CdS
QRs with a QY of 45-55% can be obtained. Using STEM-HAADF, we show that this leads to the
formation of unique multiple dot-in-rod PbS/CdS heteronanostructures. We argue that the formation of
multiple dot-in-rods is related to the initial polycrystallinity of the PbS quantum rods, where each PbS
crystallite transforms in a separate PbS/CdS dot-in-dot. Effective mass modeling indicates that electronic
coupling between the different PbS conduction band states is feasible for the multiple dot-in-rod
geometries obtained, while the hole states remain largely uncoupled.
Clearly, this new material opens the way to transfer the large body of research results obtained with
visibly emitting QRs to the near IR.

1 Nano Lett. 2007, 7, 2942

2 JACS, 2010, 132, 3909
3 JACS, 2009, 131, 16851
Band-Like Transport in Semiconductor Nanocrystal Arrays: The Role of Surface Ligands and Doping

Cherie R. Kagan, University of Pennsylvania, Department of Electrical and Systems Engineering,

Department of Materials Science and Engineering, Department of Chemistry

The long, insulating ligands commonly used in the synthesis of colloidal semiconductor nanocrystals
(NCs) inhibit strong interparticle coupling and charge transport once NCs are assembled in the solid
state into NC arrays. We introduce ammonium thiocyanate (NH4SCN) to exchange the long, insulating
ligands commonly used in the synthesis of colloidal semiconductor NCs. NCs may be exchanged with the
new ligand in solution to form dispersions from which NC arrays are deposited or NC arrays with the
long, insulating ligands may be exchanged in the solid state with the new ligands. The new compact
ligands enhance interparticle coupling in thin film, NC arrays as seen by red-shifts in the optical
absorption and concomitant increases in carrier mobilities, consistent with carrier delocalization and
band transport. Doping of the QD thin films by thermal diffusion of a low temperature, high diffusivity
metal shifts the Fermi energy, fills traps, and provides access to the bands. Thiocyanate-capped CdSe
thin film, NC arrays form sensitive photodetectors and n-type field-effect transistors with electron
mobilities as high as 27 cm2/Vs and current modulation of >106, while preserving NC quantum
confinement. Temperature-dependent transport measurements reveal band-like transport in NC arrays,
overcoming carrier hopping that has typified transport in NC arrays until recently. The non-corrosive,
chemically benign nature of the ammonium thiocyanate treatment enables the fabrication of NC thin
film devices and circuits on flexible plastics.
 Advanced colloidal nanoparticles control cellular functions.
Dorota Bartczaka, Otto L. Muskensa, Tilman Sanchez-Elsnerb, Timothy M. Millarb,
Antonios G. Kanarasa*,
a
Physics and Astronomy, Faculty of Engineering and Applied Sciences, The University
of Southampton, Southampton, UK, b Faculty of Medicine, General Hospital,
Southampton, UK
*Corresponding author: Antonios G. Kanaras, Fax +442380593910, e-mail:
[email protected]
Abstract:
An important step to manipulate biological processes is to understand how the
engineering, in terms of size, shape and functionality, of advanced colloidal nanoparticles
can be employed to our benefit in order to control cellular functions.
In this presentation we show the interactions of functional nanoparticles with endothelial
cells-the building units of angiogenesis.1-4 We found that angiogenic genes are over-
expressed in the case of pro-angiogenic-coated gold nanospheres and down-regulated in
the case of anti-angiogenic-coated gold nanoparticles. The striking observation is that
when the anti-angiogenic or pro-angiogenic molecules are attached to the gold
nanospheres, the particles are 500 times more reactive in up-regulating or down-
regulating the expression of angiogenic genes than the unbound angiogenic molecules.
Furthermore, we employ a low intensity laser-induced technique to manipulate the
damage and repair of endothelial cells.5 We will show that the degree of damage and
repair of the cells is influenced by laser illumination in the presence of gold nanoparticles
of various morphologies, which target the cellular membrane. Thus, we illustrate that
plasmon-mediated mild laser hyperthermia, combined with specific targeting of cellular
membranes, can enable new routes for controlling cell permeability and gene regulation
in endothelial cells.

References:
1. Bartczak D.; Sanchez-Elsner T.; Louafi F., Millar T.; Kanaras, A. G. Small 2011, 7,
388–394.
2. Bartczak D.; Kanaras A. G. Langmuir 2011, 27 (16), 10119–10123
3. Bartczak, D.; Muskens, O. L.; Nitti, S.; Millar, T. M.; Sanchez-Elsner, T. Kanaras, A.
G. Small 2011, ASAP.
4. Kanaras, A. G.; Bartczak, D.; Millar, T. M.; Sanchez-Elsner, T.; Muskens, O. L. Proc.
of SPIE 2011, Vol. 7909 79090J-1 doi: 10.1117/12.871602.
5. Bartczak, D.; Muskens, O. L.; Millar, T. M.; Sanchez-Elsner, T. Kanaras, A. G.
NanoLett. 2011, 11, 1358–1363.
 Controlling the surface exchange on gold nanorods

Calum Kinnear

The plasmonic properties of gold nanorods have been exploitedfor over a decade now with numerous
applications from nanomedicine to biosensors. However there is a continued effort to control their
surface chemistry, being more complex than spherical nanoparticles due to their anisotropic shape and
crystal faces. We have investigated the surface exchange of a surfactant with polyethylene glycol
(PEG) and its impact on colloidal stability of the nanorods, with an insight into how to best complete
this reaction.

By far the most common route to synthesise gold nanorods is through a seed mediated method
utilising the surfactant cetyltrimethylammonium bromide (CTAB). This cationic molecule forms a
stable bilayer on the surface of the rods, controlling their growth and imparting stability. However,
CTAB is cytotoxic and due to the bilayer structure can be difficult to entirely remove. A number of
routes have been proposed such as exchange in ionic resin1; round trip-phase transfer ligand exchange2
orpolyelectrolyte coatings3. In our lab these routes were found to be either ineffective, too complex,
low yield or did not overcome the problem of complete CTAB removal.

Through studying the effect of concentrations of reagents in the surface exchange, we were able to
completely remove the CTAB and find the limits of stability controlled by three key variables:
concentration of CTAB, thiolated PEG and ethanol. The stability and extent of exchange was followed
by UV-Vis spectroscopy, 3D-DLS and Zeta-potential. PEG was chosen due to its well documented
stealth properties, biocompatibility and ubiquitous use in nanomedicine.

Initially we found that simply mixing the thiolated PEG with the nanorods resulted in little surface
exchange as the rods still displayed a high zeta potential and low stability (upon addition of ethanol).
Therefore, the concentration of CTAB in solution was minimised while maintaining colloidal stability.
This was simple due to the dynamic equilibrium between the surface attached CTAB and those in
solution, either in micellar or monomer form. We discovered that CTAB was still attached to the
particles even when the bulk concentration was far below the cmc, although time dependence was
observed.

Through addition of ethanol, the CTAB was solubilised in solution and the rods lost colloidal stability.
This was balanced by addition of thiolated PEG at various concentrations. The minimum
concentrations of PEG needed for stability over different time intervals was found, which allowed a
method to be built for complete removal of CTAB and replacing it with PEG.

Quite unexpectedly however, we found that even at high concentrations of PEG (100 PEGnm-2) and
with the addition of ethanol, the nanorods maintained a positive zeta potential. A dual step
replacement procedure was proposed; with two consecutive PEGylation steps balancing the
destabilising effect of ethanol with the stabilising effect of PEG. We propose this as a simple, cost
effective and efficient method to detoxify gold nanorods for use in future biological studies.

(1). Dai, Q.; Coutts, J.; Zou, J.; Huo, Q. Surface exchange of gold nanorods through a place exchange reaction inside an
ionic exchange resin. Chem. Commun. 2008, 25, 2858-2860.
(2). Wijaya, A.; Hamad-Schifferli, K. Ligand Customization and DNA Functionalization of Gold Nanorods via Round-Trip
Phase Transfer Ligand Exchange. Langmuir2008, 24, 9966-9969.
(3). Leonov, A. P.;Zheng, J.;Clogston, J. D.; Stern, S. T.; Patri, A. K.; Wei, A. Detoxification of Gold Nanorods by
Treatment with Polystyrenesulfonate. ACS Nano2008, 2 (12), 2481-2488.
 Optical Spectroscopy of Single Semiconductor Nanocrystals
Close to Gold Nanoparticles

T. Kipp, X. Ma, K. Fletcher, M. P. Grzelczak, Z. Wang, A. Guerrero-Martínez, I. Pastoriza-Santos, A.

Kornowski, L. M. Liz-Marzán, A. Mews
Institute of Physical Chemistry, University of Hamburg, Germany
Departamento de Química Física, Universidade de Vigo, 36310 Vigo, Spain

Here we show that the optical properties of individual (NCs) are drastically changed by the interaction
with adjacent metal nanoparticles. We have synthesized CdSe multishell NCs coated with silica shells
and coupled them to gold nanoparticles prepared on glass cover slides. The NCs showed an average
increase of the on-time fluorescence intensity by a factor of up to 3 and a decreased fluorescence
lifetime by about 1 order of magnitude. In addition we observed fluorescence from gray states and a
strong blinking suppression with an increase of the on-state fraction from 60% to more than 90%.
These observations are explained within a comprehensive physical picture. With the help of finite-
difference time-domain simulations the PL enhancement can be predominantly attributed to a gold-
nanoparticle induced local increase of the electric field of the excitation laser at the position of the NC.
The lifetime reduction has its origin in the coupling of the excited NC to the metal-nanoparticle
plasmon. This coupling increases both the radiative and non-radiative recombination rates of the
hybrid NC-metal emitter as compared to the NC alone. Within the so-called fluctuating barrier model
and with the help of Monte-Carlo simulations, we show that the blinking suppression has its physical
reason in the increased recombination rates. The emission from gray-state is explained also by the
increased radiative recombination rate that, in our system, becomes competitive to the fast and thus
typically dominant non-radiative rate of the off-state.

[1] X. Ma, H. Tan, T. Kipp, A. Mews, Fluorescence Enhancement, Blinking Supression, and Gray
States of Individual Semiconductor Nanocrystals Close to Gold Nanoparticles, Nano Letters, 10, 4166-
4174 (2010).

[2] X. Ma, K. Fletcher, T. Kipp, M. P. Grzelczak, Z. Wang, A. Guerrero-Martínez, I. Pastoriza-Santos,

A. Kornowski, L. M. Liz-Marzán, and A. Mews, Photoluminescence of Individual Au/CdSe Nanocrystal
Complexes with Variable Interparticle Distances, Journal of Physical Chemistry Letters, 2, 2466
(2011).
 Truly two-dimensional colloidal nanocrystals
Christian Klinke, University of Hamburg, 20146 Hamburg

Controlled assembly leading to anisotropic nanostructures poses a conceptual challenge in

materials research. Oriented attachment of nanocrystal, a self-assembly of particles into larger
single crystalline objects, is one of the most promising approaches in nanotechnology to
synthesize anisotropic materials. One-dimensional assemblies of oriented attachment have been
reported, and in most cases the anisotropy during self-assembly is caused by crystal planes with
preferred reactivity and dipole moments in the crystallites. Systems with cubic crystal symmetry,
however, like PbS and PbSe, where beautiful one-dimensional oriented attachment occurs, are
somewhat more difficult to explain. In a new approach we synthesized truly two-dimensional
nanocrystals by oriented attachment with lateral dimensions on the micrometer scale. We show
that the formation of ordered and densely packed ligand surface layers of oleic acid on {100} PbS
surfaces can drive the normally isotropic crystal growth into a two-dimensional oriented
attachment of nanocrystals. Hereby the presence of chlorine containing co-solvents during the
initial nucleation and growth process of the nanocrystals plays a prominent role. In the talk the
synthesis and the formation mechanism will be discuss and detailed characterizations will be
introduced. The obtained two-dimensional structures can be readily integrated in a photo-detector
device without further treatment.

Literature
Schliehe et al., Science 329 (2010) 550.
Shape control of colloidal copper (I) sulfide nanorods.
M. Kruszynska, H. Borchert, J. Parisi, and J. Kolny-Olesiak
University of Oldenburg, Department of Physics, Energy and Semiconductor Research
Laboratory, Carl-von-Ossietzky Str. 9-11, Oldenburg, 26129,

Inorganic nanocrystals have exhibited many interesting, novel size- and shape-dependent
properties. Especially elongated nanostructures draw scientific attention, due to their unique
chemical and physical properties, caused by their dimensional anisotropy. They are e.g.
promising absorber materials for photovoltaic applications, because they not only have
tunable absorption properties, due to the size quantization effect, but also a better
conductivity, compared to 0D, spherical nanoparticles.
However, many of the most intensively studied materials, which can be synthesized in a
variety of shapes and sizes, have serious drawback, namely, they contain highly toxic
components, e.g., heavy metals, such as Cd or Pb. Here, copper sulfide nanocrystals
composed of less toxic elements, shape out as an interesting alternative. Many synthetic
methods have been developed for the synthesis of Cu2S nanocrystals during the last decade.
Their success has been, for the most part, limited to zero- or two-dimensional Cu2S
nanostructures; many reports exist on the synthesis of copper sulfide nanodots or polyhedra,
as well as hexagonal or trigonal Cu2S nanoplates.
Here we are going to present our work on the colloidal synthesis of Cu2S nanorods.1 We
obtained one-dimensional growth of copper sulfide nanocrystals by using reaction conditions
of high chemical potential. Adjustment of the nucleation temperature made it possible to tailor
uniform nanorods with lengths from 10 nm to 80 nm. The nanorods are single crystalline and
grow along the a-axis of djurleite. The shape, the size, the morphology and the growth
process of the nanorods was investigated through UV-Vis absorption spectroscopy,
transmission electron microscopy and powder x-ray diffraction measurements.

(1) Kruszynska, M.; Borchert, H.; Bachmatiuk, A.; Rümmeli, M. H.; Büchner, B.;
Parisi, J.; Kolny-Olesiak, J. J Am. Chem. Soc. submitted
Novel Strategies for Combining Nanocrystals, Molecules and Clusters,
into Functional Inorganic Solids

Maksym V. Kovalenko1,2

1. ETH Zurich, Department of Chemistry and Applied Biosciences, CH-8093, Zurich,

Switzerland
2. EMPA-Swiss Federal Laboratories for Materials Science and Technology, CH-8600
Dübendorf, Switzerland

Chemically synthesized inorganic nanocrystals are considered to be promising building

blocks for a broad spectrum of applications including electronic, thermoelectric, and
photovoltaic devices. To achieve high degree of electronic coupling, the nanocrystal surface
chemistry and surrounding medium need to be properly designed.
This talk will provide an overview of the most recent developments towards functional
inorganic materials built from nanoscale building blocks. Special attention will be paid to
rational combinations of inorganic molecules, clusters and nanocrystals – from synthesis
strategies to device applications. As examples, we will discuss all-inorganic design of infrared
active materials, solution-processed thermoelectrics and high-mobility electronic devices.
 Charge Transport in nanoscale “all-inorganic” networks of CdSenanorods linked by Au
domains

RomainLavieville, YangZhang, Alessandro Genovese, Alberto Casu, Liberato Manna, EnzoDi

Fabrizio and RomanKrahne
Istituto Italiano di Tecnologia, Via Morego, 30, Genova, 16163, Italy

E-mail:[email protected]

Charge transport across metal-semiconductor interfaces at the nanoscale is a crucial issue in

nanoelectronics, and semiconductor nanorod chains linked by Au particles are an ideal model
system in this respect. We investigated the electrical properties of networks in which
CdSenanorods were connected (“nanowelded”) by Au nanoparticles with well-defined metal-
semiconductor interfaces[1]. As deposited networks frequently manifested small Au domains at
the lateral facets of the nanorods. Thermal annealing removed these lateral Au domains and
resulted in larger Au particles within the nanorod junctions, which also increased the cross section
of the Au-CdSe interface. The networks were positioned on interdigitated electrodes by
dielectrophoresis, and the conduction of the devices was investigated at room and cryogenic
temperatures. We will report on the impact of the annealing on the current-voltage curves and
discuss our room temperature data in terms of the Schottky-Richardson model that describes
thermionic emission over a metal-semiconductor interface. The network devices showed an
increased conductivity at low temperature after annealing, and the current voltage curves could be
described by charge tunneling.

Figure 1.Transmission electron microscopy (TEM) images showing the different stages of a
typical network synthesis of (a) CdSenanorods, (b) nanorods with gold domains at their tips, and
(c) nanorod networks linked by gold domains. (d) High Angle Annular Dark Field (HAADF)
scanning transmission electron microscopy image displaying the nanorods and the higher contrast
Au domains acting as junctions. (e) Current-voltage curves of dumbbells and networks
demonstrate the increase in conductivity due to the network formation.

References

1. Figuerola, A., et al., Advanced Materials, 2009. 21: p. 550-554.

 Electron and hole dynamics in semiconductor quantum dots: A new access to blinking
statistics

Cornelius Krasselt, Robert Schmidt, and Christian von Borczyskowski

Institute of Physics and nanoMA (Center for nanostructured Materials and Analytics),
Chemnitz University of Technology, 09107 Chemnitz, Germany.

Single semiconductor quantum dots (QD) typically exhibit intermittence in their

photoluminescence, so called blinking, which manifests in bright on-, dimmed intermediate-
and dark off-events. Commonly, this effect is attributed to photoinduced charge separation.
Probability distributions of both on- and off-durations show power law dependency for short
and (more pronounced for on-times) exponential dynamics for long times.1 Furthermore, in
certain environments the on-times feature additional exponential dynamics which overlay the
truncated power law.2 So far, no comprehensive model accounts for all characteristics
accompanying QD blinking.

In this contribution we elaborate a microscopic approach to the mechanisms generating

blinking dynamics by trapping and detrapping of both electrons and holes. Using an extended
change point analysis3 we determine intermediate photoluminescence intensities (between
completely off- and on-states). This approach allows to identify states with different
photoluminescence life times and an analysis of the cross-over probabilities among these
states.

We take core/shell CdSe/ZnS QDs and their interfaces as well as the surrounding local
environment into account. In case of off-times we ascribe the power law part to detrapping of
electrons from broadly distributed traps in the environment or on the surface and show the
resulting influence on the polarity of the embedding medium.4

Via change point analysed intensity time traces we show evidence that the intermediate states5
are related to hole trapping. These states allow for power law dynamics also for on-times.
Moreover, the truncation for longer on-times can be related to the trapping of photoejected
electrons.6 Finally, assuming well defined (environment induced) single hole traps with high
trapping probability, additional exponential detrapping dynamics complement the on-time
statistics.2
1
F. Cichos, C. von Borczyskowski and M. Orrit, Curr. Opin. Colloid Interface Sci. 2007, 12, 272 - 284.
2
C. Krasselt, J. Schuster and C. von Borczyskowski, Phys. Chem. Chem. Phys. 2011, 13, 17084 - 17092.
3
L.P. Watkins and H. Yang, J. Phys. Chem. B 2005, 109, 617–628.
4
A. Issac and C. von Borczyskowski and F. Cichos, Phys. Rev. B 2005, 71, 161302(R).1 - 161302(R).4.
5
R. Schmidt, C. Krasselt and C. von Borczyskowski, in preparation
6
A. Issac, C. Krasselt, F. Cichos and C. von Borczyskowski, in preaparation
 Dendritic compounds having 2,4,6-triphenyl-1,3,5-triazine as a core

Nadzeya A. Kukhta1, J. Simokaitiene1, Juozas V. Grazulevicius1

1
Kaunas University of Technology, Department of Organic Technology,
Radvilơnǐ Plentas 19LT-50254, Kaunas, Lithuania

Organic semiconducting materials with high charge carrier mobilities have attracted much attention
during last decades due to their potential industrial applications as active media in organic light-
emitting diods, light-driven switches or components in electro-optic devices [1]. Molecules based on
starburst architecture are among the most desirable for these applications due to good charge
transporting properties and morphological stability of the materials. In contrast to the polymers and
oligomers, star-shaped molecules and dendrimers possess a well-defined and monodisperse
molecular structure as well as superior chemical purity. Their solutions are processable and
precisely designable in device fabrication being thus advantageous to polymers. 1,3,5-Triazines are
currently gathering considerable interest because they provide a core for liquid crystalline materials
and appear to be good building blocks for the materials applicable in electroluminiscent devices[2].
In current work we present the synthesis and properties of the dendritic materials having 2,4,6-
triphenyl-1,3,5-triazine as a core and fluorene derivatives as the peripheric groups linked via single,
double and triple bonds. The materials were obtained by Suzuki, Sonogashira couplings and Wittig
reaction at the main steps. The compounds obtained were characterized by various experimental
methods including NMR, IR, UV, mass, fluorescence, electron photoemission spectrometries,
differential scanning calorimetry, thermogravimetry, cyclic voltametry, time off flight technique.
Furthermore, DFT geometrical and HOMO-LUMO calculations have been done for the compounds
under consideration. It was shown, that the values of HOMO and LUMO energies for 2,4,6-tris[p-2-
(9,9-diethylhexylfluorenephenyl)-]1,3,5-triazine, obtained by Suzuki cross-coupling, are -5.71 eV
and -1.86 eV relatively, which is in good agreement with the requirements for the OLEDs.

[1] V. Lukeš et al., J. Phys. Chem. B 115 (2011), 3344 – 3353.

[2] T. Iijima et al., Optical Materials 29 (2007), 1782 – 1788.
 Understanding Liquid Crystal Dendrimers via Dimer Liquid Crystal modeling.

Anant Kumar, Alexandros G. Vanakaras and Demetri J. Photinos

Department of Materials Science, University of Patras, Patras 26504, GREECE

Liquid crystal dimmers, consisting of two mesogenic units linked by flexible spacers, can be
considered as an oversimplified, zero generation liquid crystal dendrimer. The positional and
orientational constrains of the mesogens belonging into a single dimer may have severe implications
on the molecular dynamics, the structure and phase sequence of a dimeric mesophase in comparison
with the corresponding properties of a system of the same, but not coupled, mesogens. Recently a
series of calamitic cyanobiphenyl dimers CB_Cn_CB (two CB mesogenic cores linked by
hydrocarbon spacers of length n) have been synthesized and their physicochemical properties are
being investigated. Several compounds of this series exhibit a nematic-nematic (N-N) transition. This
N-N phase transition is supported by a set of independent experimental (optical, colorimetric, ESR
and NMR) studies[1,2]. However, the nature of this transition is still debated. In this work we apply
a molecular theory[3] that takes explicitly into account the short range orientational correlations
imposed by the flexible spacer to the linked mesogens. Our results account well for the experimental
observations and give insights into the molecular organization and molecular dynamics of the two
nematic phases. We show how the same model can be extended for the description of the I-N phase
transition of liquid crystal polymers of various architectures including polypodes (star-like
architectures) and dendrimers.

Acknowledgment: This research has been funded through the EU 7th Framework Programme
(FP7/2007-2013), Marie Curie Actions, People-ITN, under the project “Functional LC Dendrimers:
Synthesis of New Materials, Resource for New Applications” (DENDREAMERS, proj. #215884).

References

[1] M.-G. Tamba, A. Kohlmeier, R. A. Lewis and G. H. Mehl, Book of Abstracts, ILCC 2010

[2] M. Cestari,et al , Phys. Rev. E, 84, 031704 (2011).

[3] P. K. Karahaliou, A. G. Vanakaras, and D. J. Photinos, Liquid Crystals, 32, 1397-1407 (2005);
A.G. Vanakaras and D.J. Photinos, J. Mater. Chem. 15, 2002-2012 (2005).
THz spectroscopy investigates electron-hole dynamics in CdSe-
core CdS-shell nanorods
L. T. Kunneman†, M. Zanella*, J. M. Schins†, L. Manna*, L. D. A.
Siebbeles†
†
Optoelectronic Materials Section, Department of Chemical Engineering, Delft University of
Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
*
NanoPhysics and NanoChemistry Division, IstitutoItaliano di Tecnologia, 16136 Genova, Italy

Photo-excited CdSe-core CdS-shell nanorods capture the hole in the CdSe core, due
to the type I1/2 band alignment in the heteronanocrystal1,2. How the electron behaves
in the electric potential of the localized hole is not immediately obvious, and presents
both an experimental and a theoretical challenge. Two limiting cases are electrons
fully bound to the hole, and electrons which are free to move on the rod, regardless of
length. We employ time resolved THz spectroscopy to obtain the complex
conductivity, and elucidate the behavior of the electron in photo-excited CdSe-core
CdS-shell nanorods of 33 x 2.5 nm and 75 x 3.0 nm. We find a strong real component
of conductivity, indicative of mobile charge. This rules out the case of a tightly bound
electron-hole pair. But neither can the complex conductivity of the nanorods be
consistently fit as unbound, free charge on a domain. To model the conductivity of the
electron, we take into account both the confinement of the nanocrystal and the
attractive potential formed by the hole. This shows that although the electron has a
high probability to reside near the hole, it is indeed free to probe the length of the
CdS rod. Analysis of the complex conductivity yields the potential of the hole felt by
the electron.
1. C. M. Donega, Synthesis and properties of colloidal heteronanocrystals. Chemical Society
Reviews 40, 1512 (2011).
2. M. G. Lupo et al., Ultrafast Electron-Hole Dynamics in Core/Shell CdSe/CdS Dot/Rod
Nanocrystals. Nano Letters 8, 4582 (2008).
 Dual-emitting MnxZn1-xSe/ZnSe:Mn2+ nanocrystals with tunable relative
emission, wavelength and lifetime
Sébastien A. Lamarrea,b, Vincent Veilleuxa, Anna M. Ritceya,b and Claudine Nì. Allena
a
Centre d'optique, photonique et laser (COPL), département de physique, de génie physique et d'optique, 2375
rue de la Terrasse, Université Laval, Canada
b
Centre de recherche sur les matériaux avancés (CERMA), département de chimie, 1045 avenue de la Médecine,
Université Laval, Canada

Nanocrystals with an alloyed core of MnxZn1-xSe and a shell of ZnSe doped with Mn2+ have been
synthesized by ion diffusion using a modified synthesis from Pradhan et al. [1]. The synthesized
nanocrystals have a size of 3.9 nm and tend to grow four small branches as illustrated in Figure 1 (a).
Spectroscopic measurements reveal that the nanocrystals exhibit dual emission from the dopant (4T1ĺ
6
A1 transition of Mn2+) and from the ZnSe shell (radiative exciton recombination). Figure 1 (b) shows
the emission spectra of some samples. Furthermore, the relative intensity of the two emissions can be
tuned by changing the composition of the alloyed core. Since the ratio of the two emissions is also
temperature-dependent, a model based on thermoactivated transfer from the dopant states to
nanocrystal excitons is proposed [2,3]. Tunability is also observed for the wavelength of maximum

200 Ps with increasing zinc fraction. We tentatively attribute the observed changes in emission
dopant emission from ~583 to ~557 nm, and for the dopant photoluminescence lifetime from 30 to

wavelength and lifetime to strain in the local environment of the dopant. In the case of the latter
parameter, the difference between the lattice parameter of the core and the shell causes an anisotropic
tension that could make the d-d transition less forbidden, thus increasing the photoluminescence
lifetime when zinc is added to the core. Cryogenic photoluminescence studies reveal that the emission
at 580 nm is characteristic of the emission of Mn2+ in a ZnSe matrix, but the temperature dependence
of the ~557 nm emission does not fit with a Debye model for phonon coupling. These nanocrystals
have also been successfully dispersed in water after functionalization with mercaptopropionic acid [4].
However, the excitonic emission is totally quenched whereas the dopant emission is enhanced

compared to the original chloroform dispersion (Figure 1 (c) and (d)).

Figure 1. (a) MnSe/ZnSe nanocrystals TEM micrography, (b) Photoluminescence spectra of MnxZn1-xSe/ZnSe:Mn2+
nanocrystals and chloroform (bottom) and water (top) dispersions of (c) MnSe/ZnSe and (d) Mn0.51Zn0.49Se/ZnSe
nanocristals

[1] Pradhan, N. and Peng, X. J. Am. Chem. Soc. 2007, 129, 3339-3347.
[2] Vlaskin, V. A.; Jansan, N.; Rijssel, J.; Beaulac, R.; Gamelin D. R. Nano Lett. 2010, 10, 3670-3674.
[3] Yu, X.-F.; Peng, X.-N.; Chen, Z.-Q.; Lian, C.; Su, X.-R.; Li, M.; Liu, B.-L., Wang, Q.-Q. Appl. Phys. Lett. 2010, 96,
123104-123107.
[4] Pradhan, N.; Battaglia, D. M.; Liu ,Y.;Peng, X. Nano Lett. 2007, 7, 312-317.
Norman Tschirner,Holger Lange,Andrei Schliwa,Amelie Biermann,Christian
Thomsen,Karel Lambert,Raquel Gomes,andZegerHens
Institut für Festkörperphysik, Technische Universität Berlin, Germany,
and Center for Nano- andBiophotonics(NB-Photonics), Ghent University, Belgium

Interfaces in CdSe/CdSheteronanocrystals
Weinvestigatetheinterfacebetweencoreandshell in zinc blende CdSe-basedCdSe/CdSdot-in-
dotheteronanocrystals. Using x-
raydiffractionandtransmissionelectronmicroscopy,weshowthat a
CdSshellgrowscoherentlyaroundtheCdSecore. A detailedanalysisoftheCdSe/CdS
Ramanspectrarevealstheappearanceof additional features upon shellgrowth. A
comparisonwithpure CdSeSalloyednanocrystalsrelatesthesefeaturestoalloyvirbrations.
Weshowthattheseobservationspointtowardsthepresenceof a mixedCd(Se,S)
layerattheCdSe/CdSinterface (Figure 1).

Figure 1: Sketch oftheinterfaceand comparisonof (a) CdSecoreand (b) CdSe-CdS

coreshell Raman spektra.

The reductionoftheAugerrecombination rate in CdZnSe/ZnSequantumdotshasbeenlinkedto a

graded,ratherthan abrupt transitionbetweencoreandshell.
However, theassignmentoftheCdSe-CdSmixedmode in thePLspectrato an alloylayeris not
unambiguous,
since2ndorderprocessesinvolvingphononsofeithermaterialswouldyieldsimilarenergieswithoutt
henecessityof an alloylayer.
Weusethe Raman spectrumofCdSe/CdSheteronanocrystalstoaddresstheissueof a
mixedCd(Se,S) interfaciallayer. Westartfromzinc blende CdSecoresandgrow a CdSshellusing
asuccessiveionlayeradditionandreactionapproach.This
approachyieldsCdSe/nCdScore/shellheterenanocrystalswith an adjustablenumber n
ofCdSlayers. Combiningtransmissionelectronmicroscopy, x-raydiffractionand Raman
spectroscopy, weshowthattheCdSshellgrowscoherently on theCdSecore.
Specific Raman modesasidetheCdSeandCdS LO appear after shellgrowth. Basedon
theevolutionoftheirfrequencyandintensitywithincreasingshellthickness, thesecanbeattributedto
a Cd(Se,S) alloylayeratthecore/shellinterface.
These resultsshowthatthestructureoftheinterface in heteronanocrystals,
whichiscloselyrelatedtotherelaxationbehaviorof multipleexcitons, canbeanalyzed in
detailstartingfromits Raman spectrum.
 Near-infrared Ag2Se nanoheterostructures

Marc-Antoine Langevina,b, Anna M. Ritceya,b , Claudine Nì.Allena

aCentred’Optique,Photonique et Laser (COPL), Université Laval, département de physique, de génie physique et d’optique, G1V 0A6,
Québec, Canada
bCentre de recherchesur les matériauxavancés (CERMA), Université Laval, Département de chimie, G1V 0A6, Québec, Canada

Inorganic semiconductors nanocrystals, also known as colloidal quantum dots

(cQDs), are attracting much scientific interest, especially because they are more stable and
robust than organic fluorescent dyes. They are easily synthesized and their
photoluminescence emission bands are characteristically narrow. The near-infrared
spectral window is interesting forapplications in biological imaging (800-1100 nm) and
solar cells (300-2000 nm)[1]. However, most of the NIR emitting cQDs contain toxic heavy
metals such as lead, cadmium or mercury. Recently, Ag2Se cQDs were shown to emit in the
1000nm to 1300nm spectral range, although the quantum yield was quite low (~1.7%)[2].
Here, we are developingheterostructures based on Ag2Se cores. Following the work of
Yaremaet al. on type-I Ag2Se/ZnSe core-shell[2],our group focuses on the synthesis of
different heterostructures such as type-I and type-II core-shells and heterodimers. For
example, Ag2Se/Ag2S core-shellsnanocrystals were easily grown. The Ag2Se cores were
synthesized [2], purified and dispersed in oleylamine at 70°C. The Ag2S shell was
grownusingthioacetamide and silver trifluoroacetate as S and Ag precursor respectively.
TEM micrographies and emission spectra of Ag2Se cores left in the same conditions without
S and Ag precursors show negligible Ostwald rippening. Phosphine sulfides cannot be used
as S precursor because the P=S link is too strong for the low temperature synthesis (403
kJ/mol for TBP=S)[3].The decrease in emission intensity of a factor 15 accompanied by a
redshift of 120 nm may be caused by either non-radiativerecombinaison centers induced by
extra crystalline defects or by the presence of a type-II heterostructure. We also use a
partial cation exchange method for the synthesis of heterostructuresbecause of the high
mobility of Ag+.

Fig.1. ~2nm Ag2Se cores Fig.2 ~6nm Ag2Se/Ag2S Core-shells Fig.3 PL spectra of a) ~2nm Ag2Se cores,
b) ~2nm Ag2Se coreswith TBP=S, c)
~2nm Ag2Se coreswith Ostwald
rippening and d) ~6nm Ag2Se/Ag2S core-
h ll
[1] K. Ramasamy, A. OlufunkeNejo, N.Ziqubu, Pullabhotla V. S. R. Rajasekhar, A. A. Nejo, N.Revaprasadu, P. O'Brien.,Eur. J. Inorg. Chem.
2011, 33, 5196-5201.
[2]M. Yarema, S. Pichler, M. Sytnyk, R. Seyrkammer, R. T. Lechner, G. Fritz-Popovski, D. Jarzab, K. Szendrei, R. Resel, O.Korovyanko, M.
Antonietta Loi, O. Paris, G. Hesser, W.Heiss., ACS Nano, 2011, 5 (5), 3758–3765.
[3] M.Saruyama,Y.-G. So,K.Kimoto,S.Taguchi,Y.Kanemitsu,T.Teranishi, J. Am. Chem. Soc., 2011, 133 (44), 17598–17601.
Peptides on gold as protease sensors and for supramolecular stamping.
A. Laromaine1,3,6*, L. Koh1, R. V. Ulijn2, O. Akbulut3,4, F. Stellacci3,5, M. M. Stevens1
1
Department of Materials and Institute of Biomedical Engineering Imperial College, London, UK,
2
WestCHEM, Department of Pure & Applied Chemistry, University of Strathclyde, Glasgow
3
Department of Materials and Engineering Science, MIT, 02139 Cambridge (MA), US
4
Currently: Sabanci University, Tuzla (Istanbul), TR
5
Currently: Supramolecular NanoMaterials and Interfaces Lab, EPFL, Lausanne, CH
6
Currently: Institut Ciència de Materials de Barcelona, Campus UAB, 08193 Bellaterra, ES
*
E-mail of presenting author. [email protected]

The optical and chemical properties of gold surfaces have been exploited recently in biosensing and drug
delivery applications amongst others.[1] Peptides are interesting tethers for assembly onto gold surfaces as
the huge availability of amino acids allow for sequences to be tailored to different physical properties and
offer the ability to control the dynamic assembly of nanostructures under physiological conditions. Two
examples are presented:

Protease sensor: Proteases are particularly suited to trigger the dis-assembly of peptide-gold nanoparticle
(Au NP) conjugates as they are (i) chemo, regio, and enantioselective; (ii) work under mild conditions;
and (iii) are involved in disease states such as HIV, Alzheimer’s disease, Hepatitis C, and pancreatitis.[2]
We proposed that the selective dis-assembly of peptide-AuNP conjugates by proteases would produce a
change in the state of assembly, producing a change in color of the peptide-AuNP solution. The protease,
thermolysin, known to be selective for hydrophobic residues for P2 and non-selective for residues in the
P1 position (P1-P2), is used to demonstrate this proof-of-concept.[3] Peptide, N-Fluorenyl-9-

attachment to AuNP via gold-thiolate bond[4] and SS interactions[5] between the Fmoc groups would
methoxycarbonyl (Fmoc)-peptide is designed to have this specificity; Cys amino acid facilitates

cause an aggregation of peptide-Au NP. The selective hydrolysis of the peptide bond would produce a
positive charge at the N-terminus, resulting in a dispersion of the system. We successfully designed a
high sensitivity protease sensor using peptide-functionalised AuNP assemblies, which enables rapid
protease detection.[6, 7] Our approach offers dynamic control over the assemblies under mild conditions,
which could prove useful for the development of a new class of biologically-controlled materials with
applications in drug delivery and in the monitoring of enzymes.

Replication of peptide-DNA motifs: Bio-medical industries are currently seeking rapid fabrication
techniques to obtain biodevices with small feature size and complex chemistry. The production of
microarrays with two different types of biomolecules is still a difficult endeavor. Here, we present the
application of Liquid Supramolecular Nanostamping (LiSuNS) to replicate mixed arrays protein and
DNA biomolecules in a single cycle for the first time.[8] We used a common folding motif in proteins in
which two alpha-helices are wrapped together like the strands of a rope to structure the coiled-coil motif
and the hybridization capabilities of DNA. Molecular recognition of these folding motifs and their design
principles are well- studied and they can be folded in a reversible fashion under specific conditions.
LiSuNS is a modification of SuNS which utilizes liquid PDMS pre-polymer after the hybridization step
as a secondary surface. Supramolecular Nanostamping (SuNS) achieves replication of a DNA master in
three steps.[9] In brief, a master (i.e. a DNA microarray made of DNA features immobilized onto a
surface) is hybridized with its complementary DNA (cDNA) molecules terminated with ‘sticky’ end
groups. A secondary surface is then placed onto the hybridized master to bond through the ‘sticky ends’
of the complementary DNA. Afterwards, the master and the secondary surface are separated using heat or
mechanical forces; effectively achieving a replica of the original DNA array.[10, 11]
[1]Chowdhury, M.H., C.J. Coates, and G.L. Coté, Journal of Biomedical Optics, 2004. 9(6): p. 1347.[2]Dustin J. Maly, L.H.J.A.E.,
ChemBioChem., 2002. 3(1): p. 16.[3]Doeze, R.H.P., B.A. Maltman, C.L. Egan, R.V. Ulijn, and S.L. Flitsch, Angew. Chem. Int.
Ed., 2004. 43(24): p. 3138.[4]Niemeyer, C.M., Angew.Chem.Int.Ed., 2001. 40: p. 4128.[5]Toledano, S., R.J. Williams, V.
Jayawarna, and R.V. Ulijn, J. Am. Chem. Soc., 2006. 128(4): p. 1070.[6]Laromaine, A., L.L. Koh, M. Murugesan, R.V. Ulijn, and
M.M. Stevens, J. Am. Chem. Soc., 2007. 129(14): p. 4156.[7]Maher, R.C., S.A. Maier, L.F. Cohen, L. Koh, A. Laromaine, J.A.G.
Dick, and M.M. Stevens, J. Phys. Chem. B, 2010. 114(16): p. 7231.[8]Laromaine, A., O. Akbulut, F. Stellacci, and M.M. Stevens, J.
Mater.Chem., 2010. 20(1): p. 68.[9]Akbulut, O., J.-M. Jung, R.D. Bennett, Y. Hu, H.-T. Jung, R.E. Cohen, . . . F. Stellacci, Nano
Lett., 2007. 7(11): p. 3493.[10]Yu, A.A., T. Savas, S. Cabrini, E. diFabrizio, H.I. Smith, and F. Stellacci, J. Am. Chem. Soc., 2005.
127(48): p. 16774.[11]Yu, A.A. and F. Stellacci, Adv. Mater., 2007. 19(24): p. 4338.
 Synthesis of Colloidal GaAs and other III-V Semiconductor
Nanocrystals by Using a Transmetallation Route
Jannika Lauth, Tim Strupeit, Andreas Kornowski and Horst Weller
University of Hamburg, Institute of Physical Chemistry, Grindelallee 117, D-20146
Hamburg, Germany
Colloidal III-V semiconductor nanocrystals (NCs) have attracted much attention in the
last decade because of their exceptional properties associated with the quantum
confinement. However, the utilization of the size dependent properties in these
materials so far has been strongly restricted owing to difficulties in applicable
synthesis routes for the compounds.
GaAs is one of the most important III-V semiconductors and a very promising
material for modern electronic applications like optoelectronic devices and solar cells
[1], [2]. Due to its direct band gap of 1.42 eV and the large exciton radius of 13 nm
(0 K) the quantum confinement in GaAs should be very distinct [3].
The possibility to synthesize III-V NCs, which are crystalline, monodispersed
and readily obtained by using wet chemical methods, is a main problem. The high
covalent character of the GaAs atomic lattice causes problems in effective
syntheses. The few existing ways to obtain GaAs nanostructures are mainly based
on variations of the dehalosylation reaction of a metal salt with (Me3Si)3As, but the
structures obtained are neither continuously crystalline nor monodispersed [4].
We present a novel simple synthetic route to colloidal GaAs NCs, with high
crystallinity and narrow size distribution by using a wet chemical approach and
reagents with low toxicity. Different gallium(III) halides are transmetallated with
n-butyllithium and subsequently reduced to elementary gallium, which reacts with
Mg3As2 to form well defined GaAs NCs.
The implementation of the transmetallation reaction can be used to obtain a variety of
the most conventional III-V NCs like GaAs, InAs, InP and GaP. The presented
synthesis route significantly broadens the scope of possible applications for GaAs
and other III-V semiconductor NCs.
[1] A. W. Bett, F. Dimroth, G. Stollwerck, O. V. Sulima, Appl. Phys. A, 1999, 69, 119.
[2] M. Bosi, C. Pelosi, Prog. Photovolt: Res. Appl., 2007, 15, 51.
[3] J. Nayak, R. Mythili, M. Vijayalakshmi, S.N. Sahu, Physica E, 2004, 24, 227.
[4] S. S. Kher, R. L. Wells, Chem. Mater., 1994, 6, 2056.
Structure-dependent charge transfer in hybrids of poly(2,7 carbazole)s and CuInS2 nanocrystals

Aurélie Lefrançois,a Lukas Brückner,a Chiara Ottone,a Jérôme Faure-Vincent,a Frédéric Chandezon,a
Mario Leclerc,b Adam Pron,a Saïd Sadki,a Peter Reissa
a INAC/UMR 5819 SPrAM (CEA-CNRS-UJF)/LEMOH, CEA Grenoble, 17 rue des Martyrs, Grenoble, France
b Département de Chimie, Université Laval, Québec, Canada
E-mail: [email protected]
Recently developed poly(2,7-carbazole)s such as PCDTBT have a high potential for use as
organic semiconductors in photovoltaic devices.[1] They combine low band gap, high hole mobility
and solution processibility on large, flexible substrates. When poly(carbazole)s are blended with
semiconductor NCs to form a organic/inorganic hybrid material, depending on the energy level
alignment charge or energy transfer can occur at the interface of both components. To make the
transfer more efficient, stabilizing ligands containing long alkyl chains, generally used during NCs’
synthesis, have to be exchanged by smaller ones.
We synthesized dodecanethiol-capped CuInS2 NCs with a mean size of 7.5 nm. 2-ethyl-
hexanethiol has been chosen for ligand exchange, because this molecule provides a compact organic
shell and maintains good colloidal stability. Successful ligand exchange was confirmed by NMR
spectroscopy thanks to the peak of the methine proton in the new ligand, absent in the initial ligand.
We probed the electronic energy levels of the CuInS2 NCs and of a series of novel carbazole based
copolymers by means of electrochemical measurements using differential pulse voltammetry and
cyclic voltammetry.[2] Photoluminescence spectroscopy using varying polymer:NCs ratios is an
appropriate tool to investigate charge or energy transfer processes in solution. All polymers exhibited
increasing photoluminescence quenching upon addition of increasing amounts of NCs. Also, in all
cases the effect was stronger when using shorter ethyl-hexanethiol ligands than original dodecanethiol
ligands. However, the quenching efficiency is strongly dependent on the chemical structure of the used
copolymer with a maximum value of 47% obtained for the compound shown in Fig. 1. For all studied
copolymers we observed a direct relationship between the PL quenching efficiency and the offset of
the electrochemically determined HOMO and LUMO levels between the electron donor (polymer) and
the electron acceptor (NCs).

Figure 1: a) Photoluminescence spectra of a 2,7-carbazole copolymer (cf. structure in the inset) in dichloroben-
zene upon addition of an increasing amount of CuInS2 NCs; b) TEM image of the 7.5-nm CuInS2.

[1] S.-H. Park, A. Roy, S. Beaupré, S. Cho, N. Coates, J. S. Moon, D. Moses, M. Leclerc, K. Lee, A. J. Heeger,
Nat. Photon. 3, 2009, 297-302.
[2] A. Lefrançois, E. Couderc, J. Faure-Vincent, S. Sadki, A. Pron, P. Reiss, J. Mater. Chem. 21, 2011, 11524-
11531.
 Photothermal microscopy as a new imaging tool for visualising
the cellular uptake of iron oxide nanoparticles

L. K. Bogart1, A. W. Taylor2, Y. Cesbron1, Steve R. Williams3,

Patricia Murray2 and R. Lévy1
1
Structural and Chemical Biology, Institute of Integrative Biology, University of Liverpool
2
Institute of Translational Medicine, University of Liverpool
3
School of Cancer and Enabling Sciences, University of Manchester

1. Introduction

The use of superparamagnetic iron oxide nanoparticles (SPION) for cell tracking requires an efficient
labelling of cells with the nanoparticles in order to render them visible via magnetic resonance imaging.
Good imaging techniques that allow the visualisation of SPION internalised within cells are therefore of
major importance in the development of new SPION or when devising new protocols for cell labelling.
Current methods for visualising SPION internalisation are either destructive (prussian blue staining,
electron microscopy) or rely on the use of agents that would not necessarily be of interest for its clinical
application (i.e. fluorescent tags for indirect visualisation via fluorescence microscopy). In this work, we
propose the use of photothermal microscopy as means to non-destructively image the magnetic
nanoparticles in live cells and compare this novel method with the standard imaging modalities in order to
show its suitability for studying the dynamics of SPION uptake.

2. Materials and Methods

A kidney-derived murine stem cell line was used as a model for imaging the uptake a commercially
available SPION consisting of an iron oxide core and a dextran shell functionalised with a fluorescent tag.
The cells were labelled with different amounts of SPION by exposure to culture medium containing
various concentrations of the nanoparticles for 24 h. The cells were then fixed and imaged by standard
methods (epifluorescence microscopy, transmission electron microscopy and prussian blue staining) as
well as by photothermal microscopy allowing a direct comparison of the different techniques. We have
additionally imaged the dynamics SPION uptake in live cells by photothermal imaging at several time
points after initial exposure to the nanoparticles.

3. Results and Discussion

The SPION taken up by cells could be imaged via photothermal microscopy and the localisation of the
particles correlated with that observed via epifluorescence microscopy and prussian blue staining. In all
cases the signal obtained was proportional to the concentration of nanoparticles to which the cells had
been exposed. The images obtained using the photothermal microscope were found to be sharper and of a
better resolution when compared to the other two methods. In all cases the signal obtained originated
from well defined spots within cells which were found to be a result of SPION compartmentalisation in
vesicles as observed via TEM. Live-cell imaging using the photothermal method was possible without
any major cytotoxic effects arising from the laser illumination which is required in this technique. Our
uptake studies revealed an initial build up of SPION on the cell membrane surface which was later
observed to accumulate in perinuclear vesicles.

4. Conclusions

We have shown the feasibility of using photothermal microscopy to directly visualise SPION within cells
in a non-destructively manner without the use of further aids such as fluorophores. Our preliminary live
cell imaging results evidence the potential of using this technique for investigating the dynamics of
SPION uptake. This method can be particularly useful for in vitro studies employing SPION designed for
clinical applications, which do not usually bear a fluorescent tag and are thus difficult to image in vitro.
 Semiconductor Quantum Dots in FRET-Immunoassays
a a b c a
Liermann, K. ; Geißler, D. ; Stufler, S. ; Wegner, D .; Löhmannsröben, H.-G.
a
Universität Potsdam , Physikalische Chemie, Potsdam-Golm (Germany)
b
Institute for Applied Polymer Research, NanoPolyPhotonics, Potsdam-Golm (Germany)
c
Université Paris-Sud, Institut d'Electronique Fondamentale, Nano Bio Photonics, Orsay (France)

Semiconductor nanocrystals (quantum dots - QDs) possess unique photophysical properties

making them highly interesting for many possible biochemical applications. In direct
consequence of their size-dependent absorption and emission features and their strong
absorption over a broad wavelength range, QDs offer several advantages for the use as
Fluorescence Resonance Energy Transfer (FRET) acceptors and donors. Therefore, QD-
based FRET pairs can be used efficiently as biological and chemical sensors for highly
sensitive multiplexed detection. [1; 2]
In this contribution we present the use of commercial biocompatible QDs (Qdot®
Nanocrystals – InvitrogenTM) as FRET donors in combination with commercial organic dyes
(Alexa Fluor® - InvitrogenTM) as FRET acceptors. We display an improvement of the
detection limits (LOD) to the low picomolar range and present potential perspectives for
these FRET-Systems in a homogeneous immunoassay.
We also present the comparison of homogeneous to heterogeneous FRET-immunoassays.
For this we used terbium complexes, labeled to antibodies as FRET donors and commercial
biocompatible QDs labeled to second antibodies as FRET acceptors. The use of Tb
complexes with long excited state lifetimes in the millisecond range allows for ultra-sensitive
time gated detection and for detailed analysis of the FRET process in the time domain. We
demonstrate the principle advantage of homogeneous over heterogeneous immunoassays in
sensitivity and economy of time. However, sensitive homogeneous FRET assays not only
rely on high binding efficiency of the antibody sandwich pair but also require sufficiently low
donor-acceptor distances. We present how these two potential limitations to the overall
FRET efficiency can clearly be distinguished by decay time analysis as well as comparisons
of heterogeneous and homogeneous assays. In practical assay development this knowledge
is vital for finding the best route to further refinements.

[1] a) D. Geißler et al., Angew. Chem. 2010, 122, 1438-1443; b) D. Geißler et al., Angew.
Chem. Int. Ed. 2010, 49, 1396-1401.
[2] W. Russ Algar et al., Anal. Chem. 2011, 83, 8836-8837.
 Fine structure of multiple exciton emission of a single CdTe/CdTexSe1-x colloidal
quantum dot
E. Lifshitz, G. Maikov, J. Tilchin, Schulich Faculty of Chemistry, Russell Berrie Nanotechnology Institute and
the Solid State Institute, Technion,Haifa 3200, Israel ([email protected])

The scientific and technological interest in colloidal quantum dots (CQDs) over two decades was
served around their special electronic properties, exhibiting atomic-like density of states manipulated by
variation of size and shape - those making them attractive for various opto-electronics and biological
applications. Nowadays a new profit is recognized, implementing the CQDs as efficient component in
quantum computing and spintronics device, anticipating generation of single or multiple excitons with
defined spin orientation with a relatively long coherent time. Hence, this emerging interest requires a
detailed investigation of excitons’ fine structures, including exploration of spectral split and polarization
properties of excitons’ recombination emission.

This work aimed to resolve the fine structure of neutral single and multiple excitons (bi-exciton,
triple-exciton, quantra-exciton) in the micro- -PL) spectrum of an isolated
CdTe/CdTexSe1-x core/shell CQD, with an extremely thin shell (~ monolayer). The CdTe/CdTexSe1-x CQDs
exhibit a quasi type-II electronic alignment, showed in the past a reduced Auger rate, a unique spectral
stability with a blinking free behavior, viz., they are the most suitable CQD for the current study. The
multiple excitons were generated by a sequential filling of the states with an increase of excitation power,
when recorded at 4.2 K. The fine structure was resolved by following the linear or circular polarization
components detected at various angles
with respect to a laboratory frame. 60
BX'
Representative spectra of a CQD with A X
40
diameter of 4 nm, recorded at various
Intensity

TX'
excitation powers, are shown in Figure 20 QX
TX

1. The exciton notations follow the Ex BX

cit 0
diagram given in Panel B of the figure. ati 5
on
Panel C approves the spectral stability, po 4
we 3
r(
while Panel D guarantees detection of a ar 2
b. 1.95 2 2.05 2.1
un 1 1.85 1.9
single CQD, using photon it s) Energy (eV)
autocorrelation measurement. The C 50
B
counts

observations revealed the following C 40

C
information: (a) determination of the 30
confinement geometry and its influence 0 200 400 600 800
sec
on a single and multiple excitons’ fine D
1
()

structure; (b) polarization nature D

(2)

0.5
(circular, linear or elliptical) of the
g

0
multiple exciton recombination 0 1000 2000
Time  (ns)
processes; (c) the direct and indirect
(exchange) Coulomb interactions in
1: (A) µ-PL spectra of a single CdTe/CdTe Se CQD recorded at various laser excitation
CdTe based CQDs; (c) theoretical Figure x 1-x
powers, varying from 0.1µW – 10 µW; (B) Schematic drawing of the electronic configuretion of a single
exciton X, bi-excitons BX and BX’, triple excitons TX and TX’and quatra-exciton. The most probable
evaluation of the excitons' binding electron-hole recombination routes are designateded by the black arrows. The appearance of the
various excitons in the µ-PL spectra are labeled in Panel (A). (C) Plot of the fluorescence intensity trace
energy and the Coulomb interaction vesus time, suggesting a non blinking behavior; (D) Plot of the cw second-order autocorrelation function
versus time, presenting an antibunching point at τ=0, designating the existence of a single CQD.
energies.
Trace-detection of PAHs pollutants in a multicomponent mixture by using
functionalized SERS-active devices

I. López-Tocón1, J.C. Otero1, J.F. Arenas1, J.V. Garcia-Ramos2, S. Sanchez-Cortes2

1
Department of Physical Chemistry, Faculty of Science, University of Málaga, E-29071 Málaga, Spain.
2
Instituto de Estructura de la Materia, CSIC, Serrano 121, E-28006 Madrid, Spain.

Polycyclic Aromatic Hidrocarbons (PAHs) are hydrophobic and dangerous pollutants

which are considered strong carcinogens. Therefore, it is of great importance to find a routine
control analysis for their trace detection in water. We have employed Surface-Enchanced
Raman Scattering (SERS)-active sensing devices in which the viologen lucigenin (LG)
adsorbed on hydroxylamine silver nanoparticles is used as a molecular tether to create
interparticle hot spot, capable to enhance the SERS signal as well as allocated analyte
molecules [1,2]. The detection ability of such substrates is tested in the analysis of a group of
six PAHs with different numbers of fused benzene rings, namely anthracene, pyrene,
triphenylene, benzo[c]phenantrene, chrysene and coronene.
The self-assembly of the LG viologen on metallic surface leads the formation of
intramolecular cavities where PAH can be hosted and has been checked by analyzing SERS
intensities of their bands at different LG concentrations. The adsorption of PAHs on LG-
functionalized Ag NPs fits to a Langmuir-like adsorption isotherm (Figure 1). The affinity of
the PAHs to bind LG depends on the respective sizes and molecular structures in order to fit
into the intermolecular LG cavities. The limit of detection at trace-level concentration is
confirmed by the presence of their characteristic fingerprint vibrational bands. The LG
surface coverage does not affect significantly the Raman signal of PAHs at concentrations
above 5·10-7 M. The LG concentration was kept fixed to 10-4 M in order to determine the
limit of detection (LOD) for each pollutant.

28
26 ANT 1380 cm-1
Coronene shows the lowest LOD,
24 PYR amounting 10-8 M (§ SSE ZKLOH
TP
22
BcP
1400 cm-1 the systems with four and three
20
18 CHR 590 cm-1 fused rings show higher LOD’s of
10-7 M and 10-6 M, respectively,
SERS Intensity

COR 1340 cm-1

16
14
698 cm-1 i.e., some 20 ppb. The direct
12 545 cm-1
10
detection of multicomponent
678 cm-1
8 691 cm-1-1 mixtures of all these pollutants was
1382 cm
6
567 cm-1
possible without any of the pre-
4
2
750 cm-1
680 cm-1
concentration treatments needed in
1351 cm-1
0 482 cm-1 other analytical techniques.
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3
[PAHs] / M

Figure 1. Variation of the SERS intensities of several marker

PAH bands when changing the pollutant concentration.

[1] P. Leyton, S. Sánchez-Cortes, J.V. Garcia-Ramos, C. Domingo, M. Campos-Vallette, C. Saitz,

R.E. Clavijo, J. Phys. Chem. B 108 (2004) 17484-17490.
[2] M. Moskovits, Rev. Mod. Phys. 57 (1985) 783-826.
 Colloidal Quantum Dots and Organics: Towards Hybrid Nanostructures

R. F. Mahrt

IBM Research GmbH, Säumerstrasse 4, 8803 Rüschlikon, Switzerland

Short distance optical interconnects and all-optical signal processing are gaining
interest due to the steady increase of bandwidth demand in telecommunication
and IT industries. The required level of opto-electronic integration demands small
form factor device structures and new materials with tailored optical properties.
Therefore, quantum dots and organic semiconductors have attracted
considerable interest during recent years. If successful, lasers, light-emitting
devices and switches based on quantum dots and/or hybrid organic-inorganic
nanocomposites could become important due to their integration potential on
arbitrary substrates.

In the present work, we use precisely engineered colloidal CdSe/CdS dot-in-rod

hetero-nanostructures to experimentally demonstrate the tunability of the exciton
fine-structure splitting by electron-hole wavefunction manipulation. We focused
our investigation on higher-lying energy states in addition to the more
characterized dark-bright splitting. Our results demonstrate that samples with
small core and/or thick-rod diameters exhibit a strongly reduced fine-structure
splitting resulting from a reduced electron-hole exchange interaction. Therefore,
our work expands on and extends previous work on the ability to tailor the band-
edge exciton-fine structure, showing a way to potentially control all electronic
energy levels.
On the other hand organic semiconductors are known to have extremely large
oscillator strengths and are therefore ideal candidates as optically active
materials in microcavities allowing studying the strong coupling regime at room
temperature. In view of novel device applications, the fundamental question
regarding hybridization of small Frenkel excitons and more extended Mott-
Wannier excitons will be addressed. We will indicate how such novel systems
could lead to devices with optimized functionalities.
Tunable Localized Surface Plasmon Resonances in Tungsten Oxide Nanocrystals

Karthish Manthiram†,§ and A. Paul Alivisatos*,‡,§

†Department of Chemical Engineering and ‡Department of Chemistry, University of California, Berkeley,
California 94720, United States
§Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United

States

Free charge carriers, which are dielectrically-confined to a nanoparticle, participate in

resonant, collective oscillations known as localized surface plasmon resonances (LSPRs).
The vast majority of investigations of LSPRs have been conducted on noble metals. LSPRs
in heavily-doped semiconductors have also been reported and are unique because the
LSPR energy may be tuned by adjusting the stoichiometry. Transition metal oxides (TMOs)
are interesting candidates for LSPR hosts as they exhibit fascinating properties arising from
the unique character of the outer-d valence electrons. We demonstrate that nanoscale
tungsten oxide supports a strong and tunable LSPR. As a result, free electrons are shown to
contribute significantly to the optical properties of the metallic phases of tungsten oxide.
The identification of an LSPR mode in tungsten oxide may enable applications in the areas
of bioimaging and photocatalysis.
 3D crystals of nanoparticles: from surface chemistry to self-assembling
M. Postic, T. Bizien, P. Even-Hernandez, C. Hamon, E. Henry, A. Dif, E. Mazari, C. Gosse,
F. Artzner, V. Marchi-Artzner
Université Rennes 1, Sciences Chimiques de Rennes, CNRS UMR 6226 ICMV, Campus de Beaulieu,
Rennes Cedex 35042, France
[email protected]

The inorganic nanoparticles possess a range of tunable optical fluorescence or absorption

properties depending on their chemical composition (semi-conductor (QD) and metallic gold) and
their shape (quasi spheres or rods) whereas the surface ligands can be optimized to tailor
interactions with the surroundings. They are also ideal building blocks in order to build up ordered
3D structures for optical materials and energy conversion.1
We describe here the surface chemistry and two methods for self-assembling the
nanoparticles into 3D crystals at a macroscale by using dynamical templates or a controlled slow
rate of water evaporation. Biological molecules and molecular self-assemblies are promising
templates to organize well-defined inorganic nanostructures. We demonstrate the ability of a self-
assembled 3D crystal template of helical actin protein filaments and lipids bilayer2, 3 to generate a
hierarchical self-assembly of quantum dots.2 Functionnalized tricystein peptidic Quantums Dots,4
QDs, are incorporated during the dynamical self-assembly of this actin /lipid template resulting in
the formation of crystalline fibers. The crystal parameters, 26.5u18.9u35.5 nm3 are imposed by the
membrane thickness, the diameter, and the pitch of the actin self-assembly as shown by SAXS. A
second approach concerns the formation of 3D smectic-like crystals of nanorods by using PDMS
mould and a controlled rate of water evaporation to build up patterned surface of 3D crystals of
nanorods at a macrorange as demonstrated by MEB and SAXS experiments.5 These processes
ensure the high quality of the crystal and result in original optical properties. These methods of
preparation offer opportunities to generate crystals with new symmetries and a large range of
distance parameters.

From right to left: lipid/actin QD 3D-crystal, smectic-like 3D-crystal of functionalized gold nanorods

References:
1. Jones, M. R.; Osberg, K. D.; Macfarlane, R. J.; Langille, M. R.; Mirkin, C. A., Templated techniques for the synthesis and
Assembly of plasmonic Nanostructures. Chem. Rev. 2011, 111, 3736-3827.
2. Henry, E.; Dif, A. l.; Schmutz, M.; Legoff, L.; Amblard, F. o.; Marchi-Artzner, V. r.; Artzner, F., Crystallization of Fluorescent
Quantum Dots within a Three-Dimensional Bio-Organic Template of Actin Filaments and Lipid Membranes. Nano Letters 2011.
3. Dif, A.; Henry, E.; Artzner, F.; Baudy-Floc'h, M.; Schmutz, M.; Dahan, M.; Marchi-Artzner, V., Interaction between water-
soluble peptidic CdSe/ZnS nanocrystals and membranes: Formation of hybrid vesicles and condensed lamellar phases. Journal of the
American Chemical Society 2008, 130, (26), 8289-8296.
4. Dif, A.; Boulmedais, F.; Pinot, M.; Roullier, V.; Baudy-Floc’h, M.; Coquelle, F. M.; Clarke, S.; Neveu, P.; Vignaux, F.;
Leborgne, R.; Dahan, M.; Gueroui, G.; Marchi-Artzner, V., Small and stable peptidic PEGylated Quantum dots to target polyhistidine-tagged
proteins with controlled stoichiometry. Journal of American Chemical Society 2009, 131, (41 ), 14738–14746.
5. Hamon, C.; Postic, M.; Mazari, E.; Bizien, T.; Dupuis, C.; Even-Hernandez, P.; Courbin, L.; Gosse, C.; Artzner, F.; Marchi-
Artzner, V., 3D smectic macroscale self-assemblies of chemically functionalized gold nanorods with defined geometry. To be submitted.
 NaNaX5

Dynamic Properties of CdSe QDs/Copolymer Films at the air-water interface

B. Martín-García, M.M. Velázquez

Departamento de Química Física, Universidad de Salamanca, Plaza de los Caídos s/n
Salamanca, 37008, Spain
[email protected]

From a technological point of view, the fabrication of Quantum Dots (QDs)/polymer

nanocomposites in thin film architectures comprising semiconductor nanoparticles and polymers
is important for the development of optical and electronic devices, such as solar cells or LEDs
and sensors [1]. The understanding of the nanocomposite mechanical properties, such as
elastic modulus and creep behavior, is essential to the processability, reliability and stability of
the QD/polymer devices. Little is known about the effect of QDs on the mechanical behavior of
nanocomposite devices due to the difficulties of measuring their mechanical properties without
the interference from the underlying substrate (substrate effect) [2]. The aim of this work is to
study the surface rheological properties in QDs and copolymer mixtures in order to improve the
understanding of the hybrid system response to mechanical stress. With this objective in mind,
we suggest the mixed Langmuir monolayers of QDs and copolymer as a platform to analyze the
rheological properties of this type of ultrathin films [3]. Characterization of the Langmuir films
was performed by surface pressure-area isotherms and Brewster Angle Microscopy (BAM). To
study the rheological properties of the films, dynamic studies were realized by sinusoidal
deformation of films [4].

The addition of QDs to polymer monolayers produces isotherms more expanded and
decreases the equilibrium elasticity. Two kind of interactions between the copolymer, poly
styrene co maleic anhydride partial 2-butoxy ethyl ester, and the QDs ligand are observed,
attractive and repulsive, depending on the mixed monolayer composition. The effect of these
interactions is highlighted in the different response of the mixed monolayers to compression-
expansion cycles: dilatational elasticity, reorganization and formation of aggregates. BAM
images allow us to observe the dynamic response of the monolayer to the shear deformation:
rearrangements, packing and formation of shear-oriented fractures. The relaxation experiments
suggest that the system rearrangement involves different time scales. Atomic Force Microscopy
(AFM) images of Langmuir-Blodgett (LB) films, deposited after shearing cycles, show the
existence of different aggregates depending on the monolayer composition and deformation
amplitude. Thus, from our results we conclude that the interactions between the copolymer and
the QDs ligand play an important role in the rheological properties of the QDs/copolymer films.
This fact must be taken into account to improve the technological application of QD/polymer
nanocomposite films.

References
[1] Tomczak, N; Janczewski, D.; Han, M.; Vancso, G.J. Progress in Polymer Science, 34,
(2009) 393.
[2] McCumiskey, E.J.; Chandrasekhar, N.; Taylor, C.R. Nanotechnology, 21, (2010), 225703.
[3] Zhang, D.; Langevin, D.; Binks, B.P.; Wei, B. Phys. Rev. E, 81, (2010), 011604.
[4] Hilles, H.; Monroy, F.; Bonales, L.J.; Ortega, F.; Rubio, R.G. Adv. Colloid Interface Sci.,
122, (2006), 67.

Acknowledgments
The authors thank financial support from ERDF and MEC (MAT 2010-19727). B.M.G.
wishes to thank European Social Fund and Junta de Castilla y León for the FPI grant. The
authors want to thank especially to Dr. J.A. Pérez-Hernández and C.L.P.U. (University of
Salamanca) for the AFM measurements and facility.
 Femtosecond phase-resolved microscopy of plasmon
dynamics in individual gold nanospheres

F. Masia1, W. Langbein1, and P. Borri1,2

1
School of Physics, Cardiff University, The Parade, Cardiff, CF24 3AA, United Kingdom
2
School of Biosciences, Cardiff University, Museum Avenue, Cardiff, CF10 3AX, United Kingdom
E-mail: [email protected]

Metallic nanoparticles (NPs) exhibit morphology-dependent electromagnetic resonances also called surface
plasmon resonances (SPR) which couple to propagating light. These resonances originate from a coherent
oscillation of electrons in the metal where the restoring force is due to the electric field created by the
corresponding charge displacement. Since this electric field depends on the morphology, the SPR frequency and
linewidth is a function of the shape and size of the NP and its dielectric environment. The resulting local optical
resonances can be exploited to image metallic NPs with high spatial resolution and to probe nanoscale regions in
the NP vicinity through the local electric field of the resonance. Especially gold NPs are ideal optical labels for
biological applications owing to their bio-compatibility and photostability, and much effort has been devoted
recently to develop techniques capable of detecting gold NPs in cells and tissues with high contrast and
sensitivity to the single particle level [1].
Ultrafast optical spectroscopy of metallic NPs is an intriguing area of research investigating the correlated
electronic and vibrational dynamics in nanosized metals. Due to limited detection sensitivity, only few reports
on ultrafast pump-probe spectroscopy on single small metallic NPs are available to date [2]. Importantly, these
experiments lacked the ability to extract the change in the NP dielectric function as a complex quantity
separating its real and imaginary part. This however is the key physical quantity of interest, being a function of
the electron and lattice temperatures transiently changing during the thermalization dynamics.
Here, we demonstrate a novel phase sensitive four-wave mixing microscopy in heterodyne detection to resolve
for the first time the ultrafast changes of real ('HR) and imaginary part ('HI) of the dielectric function of single
small (< 40 nm) spherical gold nanoparticles. The experimental
results (black lines in the figure) can be quantitatively reproduced
by considering the transient electron temperature and density in the
nanoparticle. Importantly, both intraband and interband (direct
excitation of electrons from d states to the conduction band)
transitions are included in the model (red lines). We find that the
effect of interband transitions in the excitation is important to
explain not only the magnitude of the measured FWM but also its
initial dynamics which is dominated by the formation of hot
electrons via Auger electron-hole recombination with ~50fs time
constant, much faster than the well characterized 500fs electron
thermalization dynamics for intraband excitation. The transient
change of H has been probed at different wavelengths (on and off
resonance with the SPR) providing information on the spectral
profile of the complex dielectric constant.
Beyond fundamental interest, our FWM technique offers
background-free detection of the full complex susceptibility change
even in a highly scattering environment and operates at power
levels corresponding to negligible average photothermal heating,
hence is compatible with live cell applications. Moreover it can be
readily applied to any metal nanostructure. The amplitude and
phase-resolved detection demonstrated here provides an intrinsic
ratiometric readout which has the potential to bring unprecedented
sensitivity in SPR-based applications, for example monitoring
nanoscale distance changes with plasmon rulers in cells and tissues.

References
[1] D. Boyer et al., Science, 297, 1160 (2002). K. Lindfors et al., Phys. Rev. Lett., 93, 037401 (2004). F. Masia
et al., Opt. Lett., 34, 1816 (2009).
[2] G. V. Hartland, Chem. Rev., 111, 3858 (2011). O. L. Muskens et al., Nano Lett., 6, 552 (2006). M. A. van
Dijk et al., Phys. Rev. Lett., 95, 267406 (2005).
Functional nanocrystals as tunable platforms for chemical reactions, sensing and
imaging

H Mattoussi ([email protected]), Florida State University)

Semiconductor quantum dots (QDs), metal nanoparticles and metallic clusters exhibit unique
optical and physical properties that are not shared by their bulk parent materials. These
nanoscale colloids have very large surface to volume ratios, and can provide flexible platforms
for arraying various functional molecules ranging from proteins and peptides to redox active
small molecules. The emission of luminescent of QDs can be highly sensitive to potential
interactions with proximal dyes and metal complexes. We have developed phase transfer
approaches, based on ligand exchange, along with covalent coupling and non-covalent self-
assembly to conjugate various biomolecules to CdSe-ZnS core-shell QDs and Au nanoparticles
(AuNPs). These nanocrystals were rendered water-soluble using polyethylene glycol (PEG)-
based modular multidentate and multifunctional ligands.
In this presentation, we will start with a description of the ligand design, characterization and a
new phase transfer strategy based on chemically-activated ligand exchange applied to
luminescent QDs and AuNPs. We then provide a few specific examples of hybrid bioconjugates,
and the use of those conjugates in sensor design based, for example, on charge transfer
interactions. We will also describe the effective use of these hydrophilic QDs for the in vivo
deep tissue imaging of blood capillaries based on two-photon fluorescence.
 – Colloidal chemical synthesis of indium antimonide quantum dots –
Axel MAURICEa,b, Bérangère HYOTa, and Peter REISSb
a
CEA GRENOBLE – DRT/LETI/DOPT/SIONA/LTN
b
CEA GRENOBLE – DSM/INAC/SPrAM (UMR 5819 CEA-CNRS-UJF)/LEMOH
17 rue des Martyrs, 38054 Grenoble cedex 9, France
[email protected]

Over the past two decades, extensive work has been carried out on II–VI and IV–VI
semiconductor quantum dots (QDs) triggered by the development of reproducible synthetic
procedures yielding high quality samples. III–V QDs like InP and InAs are also studied as alternative
candidates for a wide range of applications.1–4 The III–V semiconductor family exhibits large exciton
Bohr radii and narrow band gaps, theoretically allowing their optical features to be tuned from the UV
to the mid-IR. Besides, the constituting elements are more environmentally friendly and less
dangerous for human health than group IIb and IVb heavy metals such as Cd, Hg, and Pb.

Among all binary semiconductor compounds, indium antimonide (InSb) shows the narrowest
bandgap (0.176 eV) along with the largest exciton Bohr radius (65.48 nm) and a high static dielectric
constant value (17.88) therefore constituting an ideal candidate for obtaining strong quantum
confinement. According to theoretical predictions,5 one can expect to tune the band gap of InSb
nanocrystals (NCs) from the bulk value to more than 3 eV by varying the mean particle size, which
could lead to a wide range of applications such as LEDs, photodetectors and other optoelectronic
devices.

Literature on the chemical synthesis of InSb NCs is extremely sparse6 because appropriate
antimony-containing precursors, such as (TMS)3Sb, are not commercially available. Therefore, we
developed a synthetic scheme using a novel precursor and the hot-injection method yielding InSb QDs
of a mean size of 10 nm. Energy dispersive (EDS) measurements clearly indicate the presence of both
In and Sb in the samples, with In:Sb ratio being close to 1:1. Powder X-ray diffraction (Fig. 1a)
revealed a mixture of two cubic phases of InSb and high crystallinity of the nanoparticles. The size and
shape of the NCs was investigated by scanning transmission electron microscopy (Fig. 1b). Finally, the
photoluminescence (PL) spectrum of the NCs recorded with a 500 nm laser excitation source shows a
peak centred at 740 nm, clearly manifesting a strong blue-shift with respect to the bulk due to
quantum confinement.

Figure 1 – a) Powder X-ray diffractogram of InSb nanorystals deposited by drop casting on a disoriented silicon
substrate and recorded with a Co KD source. Bragg peaks of the bulk cubic zinc-blende structure In0.5Sb0.5 (red
dotted lines) and of the In0.4Sb0.6 cubic phase (green dashed lines) are given for comparison. b) STEM image of
the InSb NCs and HRTEM picture (inset) of a single crystal.
(1) D. Battaglia and X. Peng, Nano Lett. 2, 1027 (2002)
(2) L. Li, M. Protière, and P. Reiss, Chem. Mater. 20, 2621 (2008)
(3) L. Li, P. Reiss, J. Am. Chem. Soc. 130, 11588 (2008).
(4) J. Zhang and D. Zhang, Chem. Mater. 22, 1579 (2010)
(5) G. Allan, Y. M. Niquet, and C. Delerue, Appl. Phys. Lett. 77, 639 (2000)
(6) C. M. Evans, S. L. Castro, J. J. Worman, and R. P. Raffaelle, Chem. Mater. 20, 5727 (2008)
 A thin silica-over-polymer shell for functionizing colloidal nanocrystals
Paul D. McNaughter,a* Joseph C. Bear,a David C. Steytler,a Thomas Nannb and Andrew G. Mayesa
a School of Chemistry, University of East Anglia, Norwich Research Park, Norfolk, NR4 7TJ, UK
b Ian Wark Research Institute, University of South Australia, Adelaide, SA, SA 5095, Australia
* [email protected]

Modifying the surfaces of nanocrystals is crucial for their incorporation into envisaged nanometer
scale devices or tools. To date, a range of approaches exist for changing the surface properties and
functionalization of the surface of colloidal nanocrystals.1 The goal of these techniques is to alter
the solubility, introduce a pendant chemical functionality or to provide protection from the external
medium.
Often, it is desirable to modify the surface chemistry whilst maintaining the small size of the
particles. Typically, this is sought after for biological applications where the nanocrystals are in the
size domain of proteins and further size increases cannot be tolerated. Thus far, techniques to maintain
the small size whilst controlling surface chemistry have included ligand exchange, thin silica shells
and the formation of a bi-layer using amphiphilic molecules.1
In this work we have developed a generic, thin multi-layered coating applicable to colloidal nano-
crystals coated with hydrophobic ligands, which we have demonstrated on colloidal InP/ZnS and
Fe3 O4 nanocrystals.2 The first layer takes advantage of the established interaction of pro-amphiphilic
polymers and the hydrophobic stabilising ligands on a particle surface. Using the polymer as a found-
ation a thin layer of silica is built upon it forming a cross-linked cage. The resulting particles are
stable in polar solvents and basic aqueous solution. Characterisation of the particles was performed
using HRTEM, DLS, XPS, IR, EELS and EDX. This conclusively demonstrates that the target silica-
over-polymer layered structure was produced. We anticipate that such particle coatings may prove
useful in a wide range of applications for nanocrystals where surface modification is required.

   




 
 
 

 



  


 

   



 


   
 

 



  





 

Figure 1: (Left) A typical colloidal nanocrystal and (Right) the structure of the final thin silica-over-polymer
shell upon the colloidal nanocrystal.

(1) R. A. Sperling and W. J. Parak, Philos. T. R. Soc. A, 2010, 368, 1333–1383.

(2) P. D. McNaughter, J. C. Bear, D. C. Steytler, A. G. Mayes and T. Nann, Angew. Chem. Int. Ed., 2011, 50, 10384–
10387.
 Covalent functionalisation of carbon nanotubes with amphiphilic polymer
coated superparamagnetic nanocrystals
Paul D. McNaughter, Joseph C. Bear, Andrew G. Mayes and Gregory G. Wildgoose*

School of Chemistry, University of East Anglia, Norwich Research Park, Norfolk, NR4 7TJ, UK
* [email protected]

Composite nanomaterials combine the properites of two nanometer scale materials for multi-
functional tools or devices. Structural motifs such as the linking of a pair of nanocrystals, growth of
one nanocrystal from another or core-shell structures have been investigated to combine properties.1
Combining the properties of nanocrystals and carbon nanotubes has been explored by a number of
groups.2 Covalent linkages offer the best stability and avoid complications, caused by (sometimes
unfavourable) equilibria.
In this work, a new method for the covalent attachment of colloidal superparamagnetic nano-
crystals to multi-walled carbon nanotubes (MWCNTs) is presented.3 The nanocrystals are coated with
an amphiphilic polymer and are subsequently functionalised to allow further reaction with defects in
the carbon nanotube structure. The resulting nanocrystal-MWCNT material can be manipulated using
magnetic fields, Figure 1. We have also demonstrated the use of the material as a magnetic electrode
in non-aqueous electrochemistry proving the surface of the nanocrystal is passivated by this coating
and coupling method.4
The chemical strategy and methodology adopted will be presented, together with characterisation
data from a variety of techniques to demonstrate the success of the approach and the behaviour of the
resulting composite material.

Figure 1: Carbon nanotube - nanocrystal composites in the absense of a magnetic field (left) and in the presence
of a magnetic field (right).

(1) P. D. Cozzoli, T. Pellegrino and L. Manna, Chem. Soc. Rev., 2006, 35, 1195–1208.
(2) X. Peng, J. Chen, J. A. Misewich and S. S. Wong, Chem. Soc. Rev., 2009, 38, 1076–1098.
(3) J. C. Bear, P. D. McNaughter, K. Jurkschat, A. Crossley, L. Aldous, R. G. Compton, A. G. Mayes and G. G.
Wildgoose, Nanoscale, 2011, Submitted.
(4) G. G. Wildgoose, E. J. Lawrence, J. C. Bear and P. D. McNaughter, Electrochem. Commun., 2011, 13, 1139–1142.
 The design and control of the self-assembly behaviour of liquid
crystal forming gold nanoparticles
G. H. Mehl1, B. J. Tang1, L. Cseh1, C. H. Yu1, C. Schubert1, X. B. Zeng2, F. Liu2, G. Ungar2, J.
Dintinger3, T. Scharf3

1
Dept. of Chemistry, University of Hull, Hull HU6 7RX, UK
2
Dept. of Engineering Materials, University of Sheffield, Sheffield UK
3
Institute of Microtechnology, EPFL, CH

A considerable research effort has been directed towards the investigation of spherical colloidal
particles dispersed in low molecular liquid crystals. The spatial arrangement of the particles has
often been manipulated by external fields or laser tweezers resulting in chains or raft like
assemblies. The interest in smaller nanometric sized particles in LC matrices has been driven, in
the main, by their ability to alter the dielectric behaviour of LCs, potentially resulting in faster
switching devices or in materials with attractive optical properties such as NLO behaviour. In
recent years concepts for such materials with metameterials properties in the visible range of the
electromagnetic spectrum based on the self-assembly of of hybrid nanocomposites have been
developed.
Recently we started to explore the connection of nematogenic mesogenic units, consisting of
laterally connected aromatic groups to small gold nanoparticles (NPs) with an almost spherical
shape and diameters ranging between 1.4 - 2.5 nm. According to OPM and DSC data we detect
nematic behaviour, however according to detailed temperature dependent XRD and GISAX
experiments which allowed the calculation of electron density maps, two dimensional or three
dimensional superlattices of nanoparticles are formed. The superstructures (2D or 3D) and the
lattice parameters are determined by the spacing filling requirements of the gold particles and the
organic mesogenic groups, alkyl chains and the anisotropy of the nematic ordering field.
For larger NPs (> 3nm) strong dichroic behaviour was found in thin films in the range of the LC
phase behaviour. For NPs larger than 5 nm surface plasmon resonance effects could be detected
easily.
The design and synthesis of the materials and their their chemical and self assembly
characterisation characterisation by NMR, TEM, XRD, DSC and OPM will be reported the design
strategies for particles of different size will be explained. Phase structures, phase transition
temperatures and two dimensional and three dimensional packing of the gold particles will be
discussed and correlated to the size and size distribution of the particles and the size and to the
number of the mesogens attached to the particles.
 Quantum Dots as Donors in single pair FRET studies and 2-Photon
Microscopy
a a b a
Meiling, T.T. ; Hill, D. , Stufler, S. ; Löhmannsröben, H.-G.

a
University of Potsdam , Institute of Chemistry Physical Chemistry, Potsdam-Golm (Germany)
b
Institute for Applied Polymer Research, NanoPolyPhotonics, Potsdam-Golm (Germany)

Due to their unique photophysical properties like high photo-stability, large extinction
coefficients and narrow, size tunable emission spectra, semiconductor quantum dots (QDs)
have become very popular as luminescent labels and as donors or acceptors in
homogeneous Fluorescence Resonance Energy Transfer (FRET) assays [1]. Two-photon
fluorescence microscopy (TPM) possesses several unique advantages enabling noninvasive
study of living specimens in three dimensions with low photodamage and high signal to
background contrast [2]. The combination of QDs, with their high theoretical two-photon
excitation (2PE) cross-sections [3], and TPM will open a new field of for nonlinear
spectroscopy.
In this contribution we present the experimental determination of 2PE cross-sections (V2) of 5
different water soluble, biocompatible commercial QDs (525, 565, 605, 655 and 705, Qdot®
Nanocrystals – InvitrogenTM) and the resulting 2PE spectra over a wavelength range from
700 to 960 nm. The commercial QDs covered by our study display ultra high two-photon
excitation (2PE) cross-sections, at least two orders of magnitude higher than those of
common molecular fluorophor, over a wide wavelength range without impairing their
excellent photophysical properties. In addition, homogeneous 2PE FRET assays will be
shown, using QDs as donors and Alexa Fluor Dyes® (InvitrogenTM) as acceptors.
Finally, we bring these results down to single molecule level by utilizing QDs as luminescent
labels and energy donors in confocal laser scanning microscopy with linear as well as two-
photon excitation. This study can serve as a basis for numerous applications in biological
imaging where, in addition to the established advantages of TPM, molecular recognition and
distance alterations can be sensitively detected via FRET at a resolution far below the optical
diffraction limit.

[1] Algar W. R, et al. Anal. Chem. 2011, 83, 8826-8837

[2] So P. T. C, et al. Annu. Rev. Biomed. Eng. 2000, 02, 399-429
[3] Blanton S. A, et al. Journal of Luminescence, 1996, 70, 253-268
Synthesis and Characterization of Widely Tunable Photoluminescence Emission
CdTe/CdS Core/Shell Quantum Dots under Fully Ambient Atmosphere

Meng-Qiao Dai, Lin-Yue Lanry Yung*

Department of Chemical and Biomolecular Engineering, National University of

Singapore, 10 Kent Ridge Crescent, Singapore119260

*Tel. +65-6516-1699; E-mail address: [email protected]

We reported a facile aqueous synthetic route of CdTe/CdS core/shell quantum dots

(QDs) with widely tunable photoluminescence emission window under ambient air

atmosphere throughout entire fabrication process. The obtained core/shell QDs were

highly luminescent with a widely tunable PL emission window of 535nm-825nm. The

photoluminescence quantum yield of the corresponding QDs was typically at 40% or

higher in red and near-infrared regime (600-825nm) without any post-synthesis

treatment. Based on the systematic studies on the structure and optical properties, we

witnessed the transition of band alignment from type-I to type-II in our aqueous phase

synthesized core/shell QDs with localized holes in CdTe core and electrons in CdS

shell. This electronic alignment transition accounts for the wide photoluminescence

emission window and the evolution of photoluminescence quantum yield upon the

epitaxial overgrowth of CdS shell. The synthesis of such core/shell QDs with widely

tunable PL emission wavelength with under fully ambient air condition can facilitate

the large-scale fabrication of high-quality QDs for the applications in tagging and

photovoltaics.
Optical and electrical properties of individual CdSe nanowires
Alf Mews, Sebastian Schäfer, Zhe Wang, Anton Myalitsin, Tobias Kipp,
Department of Physical Chemistry, University of Hamburg, Hamburg, 20146, Germany

Semiconductor nanowires (NWs) can be prepared by a similar high temperature (TOPO-) method as
nanocrystals, by simply adding Bismuth particles to the reaction solution, which act as a catalyst. In this so
called SLS-method, the Soluble precursors dissolve in the Liquid Bismuth catalyst to form Solid nanowires
upon over saturation. Under different reaction conditions, nanowires with diameters of less than 5 nm, and
also core-shell and block NWs are prepared [1].
In this contribution we will focus on the optical and electrical properties of individual CdSe-NWs. By
employing single NW PL measurements and also TEM studies on the same individual NWs we establish a
detailed structure property relationship. [2] Moreover we present a novel method combining Electrostatic
Force Microscopy (EFM) including tip charging, with simultaneous PL measurements on individual
semiconductor nanowires. We show that the initially homogeneously distributed charge is separated upon
local illumination where the positive charges accumulate in the range of the Laser spot, whereas the
negative charges migrate to the distant end of the NW. [3] Further, we actively charged isolated CdSe
nanowires with a biased AFM tip to investigate the PL behavior in dependence of excess charges. Here
we found that different voltage regimes can be identified which lead to PL enhancement but also to
reversible and irreversible PL quenching. Finally, we investigated axial type-II NW hetero structures from
CdSe and CdTe to demonstrate charge separation across the interface.

[1] Zhe Wang, Zhen Li, Andreas Kornowski, Xuedan Ma, Anton Myalitsin and Alf Mews, Solution–Liquid–
Solid Synthesis of Semiconductor Nanowires Using Clusters as Single-Source Precursors, Small, 7, 2464-
2468 (2011).
[2] A. Myalitsin, Ch. Strelow, Z. Wang, Z. Li, T. Kipp, and A. Mews, Diameter Scaling of the Optical Band
Gap in Individual CdSe Nanowires, ACS Nano, 10, 7920 (2011).
[3] S. Schafer, Z. Wang, T. Kipp, and A. Mews, Fluorescence modulation of single CdSe nanowires by
charge injection through the tip of an atomic-force microscope, Physical Review Letters 107, 137403
(2011).
[4] S. Schäfer, Z. Wang, R. Zierold, T. Kipp, and A. Mews, Laser-Induced Charge Separation in CdSe
Nanowires, Nano Letters, 11, 2672 (2011).
Morphology control, stability and reactivity of semiconductor-metal hybrid na-
nostructures

Michaela Meyns,1 Neus Gomez-Bastús1,2 and Christian Klinke1

1
Institute of Physical Chemistry, University of Hamburg, Grindelallee 117, 20146 Hamburg, Germany.
2
Current address: Institut Català de Nanotecnologia (ICN), Campus UAB, 08193 Bellaterra, Barcelona, Spain.

Inorganic hybrid nanocrystals (HNCs) are a promising category of materials for advanced applica-
tions, as it is possible to combine a large variety of materials with individually tailoredfeatures and
thus design structures with combined or even improved properties. Among all of these systems, the
combination of metal and semiconductor formed by a central semiconductor NCs and several metal-
lic domains quasi-epitaxially grown at its surface is especially interesting. These new HNCs are ideal
candidates for solar energy harvesting applications since the semiconductor domain of the hybrid
can be tailored for optimal light absorption while its combination with a metal facilitates charge se-
paration. Furthermore, the reactive metal surface with a large surface area can serve as both a prop-
er catalytic substrate for the reactions and a self-assembly anchor point.

In order to develop synthetic strategies which allow morphology control duringthe HNC formation
process, it is crucial to understand not only the role of each elemental component employed in the
process but also the reactivity of the final hybrid structure during their full life cycle. In this regard,
we chose bi-pyramidal CdSe nanocrystalsas a model system since its unique surface configuration
and geometry allows i) studying the topological deposition of the metallic components and ii) moni-
tor its reactivity and ripening phenomena caused by heating or by irradiation withan electron
beam.As a result, it was possible to form either several defined and equally sized metal domains with
sizes frombelow 2 up to 5 nm or an unreducedshell of Auon the surface of CdSe NCs in solution. Ad-
ditionally, in the case of the Au shell, it is possible to reduce iteither under the TEM with the electron
beam or directly after the deposition by adding a reducing agent to the reaction mixture. The influ-
ence of the stabilizer and the choice of the precursor on the shell formation as well as the long-term
stability will be addressed. The latter aspect has become a topic of increased interest,3as hybrid
structures are thought of as possible catalysts or components in optoelectronic devices and there-
fore need to be stable during application.

Additionally, a new wet-chemical way of creating semiconductor-metal hybrid structures besides the
classical seeded growth approach will be presented. This method, based on the inherent reactivity of
colloidal NPs against ionic precursor molecules and other NPs in solution allows the epitaxial deposi-
tion of pre-synthesized metal domains onto CdSe NCs by controlling their interactions at the inter-
face.

1) R. Costi et al. Angew. Chem., Int. Ed.2010, 49, 4878–4897.

2) M. Meyns et al.J. Mater. Chem.2010, 20, 10602-10605.
3) M. A. van Huis et al. Nanoletters2011, ASAP.
 Surface modification of inorganic core nanoparticles:
a general route to multifunctional nanodevices

Jose-Maria Montenegro and Wolfgang J. Parak

Philipps University of Marburg, Faculty of Physics, Renthof 7, 35037 Marburg, Germany

The design of nanostructures with potential biochemical applications requires the transfer from the initial
organic colloidal nanoparticle dispersion to water-based solutions. The coating of nanoparticles using
amphiphilic polymers is a general tool that permits the dispersion of nanoparticles in aqueous media and
further functionalization through the specific functional groups located in the hydrophilic polymer coating
part exposed to the aqueous solution.1

The surface modification, that can be done in a controlled way by using polymers with appropriate
molecular weight,2 permits to link organic molecules (fluorophores, ligands, biomolecules) to the
nanoparticle increasing its functionality this way. With this, we can take advantage of the core
functionality (fluorescence: quantum dots; magnetism: iron oxide NPs; thermal properties: Au NPs;
radioactivity: Au198 NPs) introducing a modification in the surface that permits to develop core-shell
systems with dual functionality with potential application as contrast agents in imaging techniques.3

The functionalization of the polymer surface with ion sensing molecules permits its use as nanosensor
with application in living organisms. With this, we take advantage of the multiple functional groups that
are located on the surface to link several fluorophore units per nanoparticle increasing the signal in
comparison with a single fluorophore unit due to the big nanoparticle surface. This high local
concentration and the possibility to attach different sensitive molecules to the same nanoparticle, permits
to perform multiplexed measurements of different analytes with just one nanosystem.4-5

References
1. Pellegrino, T.; Manna, L.; Kudera, S. et al.; Nano Letters 2004, 4, 703.
2. Sperling, R.A.; Pellegrino, T.; Li, J.K. et al.; Adv. Funct. Mater. 2006, 16, 943.
3. Ali, Z.; Abbasi, A.Z.; Zhang, F. et al.; Anal. Chem. 2011, 83, 2877.
4. Jimenez de Aberasturi, D.; Montenegro, J.-M.; Ruiz de Larramendi, I. et al. Chem. Mater. 2012, 24,
738.
5. Abbasi, A.Z.; Amin, F.; Niebling, T. et al. ACS Nano 2011, 5, 21.
Importance of Shape Anisotropy in the Band-Edge Fine Structure of Colloidal
CdSe Quantum Dots

I. Moreels,1,2 G. Rainò,1 R. Gomes,2 Z. Hens,2 T. Stöferle1 and R. F. Mahrt1

1
IBM Research – Zürich, Säumerstrasse 4, CH-8803 Rüschlikon, Switzerland
2
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281–S3, BE-9000 Ghent, Belgium

Colloidal CdSe semiconductor quantum dots (Qdots) offer prospects for photonic applications over a wide
spectral range using a single material composition; consequently, their potential as optical sources in LEDs,
lasers and single-photon emitters is actively explored. In these devices, the Qdot fine structure plays an
important role, as the energy and polarization of the emitted photons are determined by it.
The band-edge fine structure splitting in colloidal Qdots has already been investigated both on an experimental
and theoretical level. However, most experimental studies are focused on the lowest two states, with a
characteristic splitting of 1–5meV between a lower, optically dark state and a higher bright state. Only few
publications have focused on the experimental verification of the entire fine structure of the band edge transition,
which consists of five different states.
Therefore, we aim to extend existing knowledge in this field by comparing the optical properties of small (2-
3.5nm) CdSe/ZnS Qdots synthesized either with a wurtzite (WZ) or a zincblende (ZB) crystal structure.[1] The
photoluminescence (PL) decay as a function of temperature (5K-300K) confirms the presence of the two lowest
states as a lower dark state and a higher bright state, split by 2.4-5.0meV depending on the Qdot size. In
addition, spectrally resolved PL decay traces, collected at 5K with a streak camera, reveal a third state, split from
the lowest energy state by 30-70meV (with a larger splitting corresponding again to smaller a size). The effective
lifetime of this state ranges from 50 to 80ps, which suggests that non-radiative decay into the lowest two states
dominates the relaxation process.
Most importantly, on both the ns- and the ps-timescale, WZ and ZB CdSe Qdots are optically highly similar. In
contrast, theoretical calculations[2] on spherical CdSe Qdots, yield a different fine structure at the band edge.
Experimental and theoretical data only converge when shape anisotropy is taken into account. Indeed, already
for an aspect ratio of 1.15:1, theory predicts that the splitting induced by shape anisotropy dominates over the
crystal field splitting, which eliminates the difference in fine structure between WZ and ZB CdSe Qdots.
Interestingly, the results imply that the lowest state does not have an angular momentum projection of ±2; it
corresponds to the optically dark 0L-state. Both the strong influence of anisotropy-induced splitting in nearly-
spherical Qdots and the nature of the lowest dark state have important consequences for interpreting optical data
related to these systems, as in practice ZB Qdots display a richer fine structure than the expected two-fold
splitting, and excitons in the dark 0L-state can recombine via different phonon-assisted mechanisms compared
the ±2-state.

Figure 1. Left: Streak camera image at 5K, showing a blue shifted, rapidly decaying peak, attributable
to the third (bright) state c. Middle: Experimentally observed fine structure. Right: Calculation of the
ZB CdSe fine structure for an aspect ratio of 1.15:1 (dashed lines: dark states, full lines: bright states).
WZ Qdots show a similar fine structure.[1]

[1] I. Moreels et al., ACS Nano 5, 8033-8039 (2011).

[2] Al. Efros et al., Phys. Rev. B 54, 4843-4856 (1996).
The crystal structure of colloidal nanocrystals is less bulk-like than expected: a
case study of PbSe NCs

Iwan Moreels1, Valeri Petkov2, Zeger Hens1 and Yang Ren3

1
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, BE-9000 Ghent, Belgium.
2
Department of Physics, Central Michigan University, Mt. Pleasant, Michigan 48859, USA.
3
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA.

When the size of a material approaches the nanometer scale, structure and composition start to differ
significantly from its bulk counterpart. Using the example of colloidal PbSe nanocrystals (NCs), we have
investigated this with synchrotron X-ray diffraction measurements and pair-distribution function analysis of
the collected diffractograms.[1] We show that particles with a size less than 10nm typically are, 1: highly
non-stoichiometric, in this case with an excess of Pb-atoms present on the particle surface, 2: larger than
expected, as the lattice constant increases with respect to the bulk value and 3: structurally distorted, as
deviations from the regular atomic positions strongly exceed the variations due to thermal disorder. All three
effects increase with decreasing size due to either an increased surface-to-volume ratio or a reduced number
of atoms (allowing more disorder), and can be consired generally valid for colloidal semiconductor NCs. The
observed Pb cation excess confirms earlier data measured with inductively-coupled plasma mass
spectrometry.[2] Importantly, it is balanced by the organic ligands, which in the case of PbSe are oleic acid
bound as oleate ions.[3]
Our results yield a detailed view on the structure and composition of colloidal NCs and have widespread
consequences. Regarding the theoretical work on their electronic band structure, initial results already
indicate that non-stoichiometric NCs indeed have different optial properties.[4] Furthermore, our model may
lead to an improved understanding of the crystallographic structure of core-shell NCs, where lattice
distortion and strain in the crystal and at the interface play an important role.

Figure 1. Left: Pb/Se atomic ratio, lattice expansion 'a and deviation from their regular position 'r,
as a function of the PbSe diameter. Right: schematic view of the resulting distorted and non-
stoichiometric PbSe nanocrystals, passivated with oleate ligands.

[1] V. Petkov et al., Phys. Rev. B 81, 241304R (2010)

[2] I. Moreels et al., Chem. Mater. 19, 6101-6106 (2007)
[3] I. Moreels et al., J. Am. Chem. Soc. 130, 15081-15086 (2008)
[4] A. Franceschetti, Phys. Rev. B 78, 075418 (2008)
 Engineering the Fine Structure Splitting in CdSe/CdS Dot-in-Rod
Nanocrystals by Precisely Controlling the Wavefunction
Delocalization

G. Rainò1,*, I. Moreels1,2, T. Stöferle1, R. Gomes2, Z. Hens2 and Rainer F. Mahrt1

1
IBM Research – Zurich, Säumerstrasse 4, 8803 Rüschlikon (Switzerland)
2
Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Gent,
(Belgium)

*E-mail: [email protected]

Colloidal semiconductor quantum nanostructures allow controlling the confinement of charge carriers through
material composition and geometry. Besides being a unique platform to study the corresponding opto-
electronic properties, these materials also attract considerable interest due to their potential in photonics and
quantum communication applications.

Hetero-nanostructures like CdSe/CdS offer new prospects to tailor their optical properties as the small
conduction band offset (~ 0.3 eV) allows tuning of the electron delocalization from type-I toward quasi type-
II. Indeed, the energy of the quantized levels and their radiative rates can be controlled by adjusting the core
size and the shell thickness.1

In the present work, we use precisely engineered colloidal CdSe/CdS dot-in-rod hetero-nanostructures to
experimentally demonstrate the tunability of the exciton fine-structure splitting by electron-hole wavefunction
manipulation. We focused our investigation on higher-lying energy states in addition to the more
characterized lower dark-bright states. Our results demonstrate that samples with small core and/or thick-rod
diameters exhibit a strongly reduced fine-structure splitting resulting from a reduced electron-hole exchange
interaction.2 Therefore, our study extends previous work on the ability to tailor the band-edge exciton-fine
structure,3 showing a way to potentially control all electronic energy levels.

The exciting tuning capabilities of colloidal quantum dots now start to extend beyond simple wavelength
tuning by size. Furthermore, understanding and controlling the fine-structure splitting has important
implications in the field of optical quantum communication and could, in particular, pave the way toward a
new source of entangled photon pairs.

References
[1] Rainò G., et al. 2011 ACS Nano 5 4031–4036
[2] Rainò G., et al. 2011 ACS Nano, Submitted.
[3] Brovelli S., et al. 2011, Nature Communications 2 doi:10.1038/ncomms1281


  

  



 
 




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G

CdTe Nanocrystal based Solar Cells

Brandon MacDonald, Gerry Wilsona, Scott Watkinsa, Jacek Jasieniaka, Paul

Mulvaney

School of Chemistry & Bio21 Institute, 30 Flemington Rd., Parkville, VIC, 3010,
Australia;
a
CSIRO Materials Science and Engineering, Clayton, VIC, 3169, Australia,
email: [email protected]

Semiconductor thin films can be easily prepared using nanocrystal inks as precursors.
Such inks contain pre-crystallized nanoparticles and can be annealed at much lower
temperatures than films prepared using standard sol-gel techniques. Consequently,
they may be compatible with polymer based electronics.

Furthermore, the nanocrystals themselves may be crystalline, doped or be core-shell

structures, opening up the possiblity to make films with unusual optical and
electronic properties. Such films can be deposited by various simple and scaleable
chemcial methods such as dip coating or spin coating. In this talk, I will provide an
overview of results on CdTe:ZnO heterojunction based PV solar cells with a quantum
efficiency of up to 9.8%.

References:

1. B. Macdonald et al. Nanoletters, 11, 2856-64 (2011).

2. B. Macdonald et al. ACS Nano (in press), 2012.

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 Photochromic Dendrimers. I.
Synthesis and liquid crystalline properties

Zs. T. Nagya, J. Tomczykb, A. Sobolewskab, B. Heinricha, B. Donnioa, D. Guillona, J. Stumpeb

a
CNRS, IPCMS and Strasbourg University, Strasbourg, France
b
Fraunhofer Institute for Applied Polymer Research, Potsdam, Germany
e-mail: [email protected]

Dendrimers and dendrons are versatile candidates as original scaffoldings for the
elaboration of new liquid crystal (LC) functional materials [1] in which mesomorphism can
be modulated by the modification of the intrinsic dendritic connectivity and the peripheral
groups endowed with various properties (e.g. groups combining liquid crystalline and
optical/electronic properties). Dendrimers, where azobenzene is incorporated as functional
group, display liquid crystallinity can also be of great interest for optical component,
photoalignment of liquid crystals, etc.

Series of dendrimers, where the alkoxy-azobenzene (AZB) functional groups are

present in different molar ratio in one molecule along with different mesogens (alkoxy-
biphenylene (BPH) or alkoxy-cyanobiphenyl (OCB)) (FIG.1.), were synthesized in a
multistep process, which will be presented, and characterized. Photogeneration of angular
dependent optical anisotropy upon polarized irradiation of these dendrimers was carried out
by the collaborative partner (Fraunhofer Institute, Potsdam, Germany). One of the system led
to very promising results: a dichroism of about 0.77 (356nm) was generated [2]. DSC, SAXS,
and POM were used and will be detailed for the determination of the liquid crystal properties
of dendrimers.

FIG.1. Synthesized dendrimers bearing different ratio of photochromic functional group and their mesophase

Acknowledgment: This work was supported by the Marie Curie Actions, Seventh Framework
Programme,“Dendreamers” project

[1] B. Donnio, S. Buathong, I. Bury and D. Guillon, Chem. Soc. Rev., 2007, 36, 1495
[2] J. Tomczyk, A. Sobolewska, Zs. T. Nagy, J. Stumpe, B. Donnio, D. Guillon, Nanax5: Photochromic
Dendrimers. II. Light induced effects
 Luminescent Lanthanide complexes for antibody labelling and
detection of Alzheimer disease biomarkers

Katia NCHIMI NONO,a Alexandre LECOINTRE,a Shakir SHAKIR,a Câline CHRISTINE,a

Laurence SABATIERb and Loïc J. CHARBONNIEREa*

a) Laboratoire d’Ingénierie Moléculaire Appliquée à l’Analyse and b) Laboratoire de Spectrométrie de Masse

Bio-Organique, Institut Pluridisciplinaire Hubert Curien, UMR 7178 CNRS/UdS, ECPM, 25 rue Becquerel,
67087 Strasbourg Cedex, France. [email protected]

There is a growing need in the development of ultrasensitive detection of biomarkers

that should allow an early an accurate follow up of the biomarkers evolution during the first
stages of the pathologies. In the case of Alzheimer disease, an early diagnostic on blood
sample would have a beneficial impact on the potential retardation of the disease and on a
practical ground on the patients well being, the current diagnostic being up to now only viable
via lumbar puncture. If a single blood biomarker of Alzheimer disease is not yet known, the
conjunction of up to five signalling proteins from a pull of 18 was shown to improve
significantly the possibility of a differentiated diagnostic.1
The aim of the NANOGNOSTICs project is to develop an ultrasensitive multiplexed
fluoro-immunoassay for these biomarkers, based on the exceptional photophysical
performances of resonant energy transfer (RET) using lanthanide complexes as energy donors
and Quantum Dots as energy acceptors.2,3
O

?
O N

O O

FRET
Ab
O

N
N

N
N

Tb

H2
N
N

PO 3
H2
PO 3
H2
Ln3+ QD
PO 3
3P
H2 O

H 2O
3P
N
PO
3H
2

N
N
Tb
PO

N
3H
2

N
PO

N
3H
2

N N N
3 H2
O

3 2 PO

N N
N

N
N

PO H
N

Tb

3 2
N

PO H
N

N
3P

Tb
H2 O

N N

H2O3P PO3H2 PO3H2 PO3H2

We here present the results obtained with a new family of lanthanide complexes developed
within the project, which gathers the expected photo-physical properties and stability in
biological media, with a labelling function for grafting on biomolecules such as antibodies.
The labelling and characterization of DREG55 and DREG200, two specific antibodies of
L-selectin, will be presented.

1) Ray et al., Nature Medicine 2008, 13(11), 1359-1362.

2) Charbonnière et al., J. Am. Chem. Soc. 2006, 128, 12800-12809.
3) Geissler, D. et al. Angew. Chem. Int. Ed. 2010, 49, 1396.
 Lanthanide-to-Quantum Dot Förster Resonance Energy Transfer in
protein detection
P. J. Cywinski1, L. Olejko1, T. Hammann1, K. Liermann1, L. J. Charbonnière2, K. Nchimi
Nono2, H. Härmä3 and H.-G. Löhmannsröben1
1
Department of Physical Chemistry, Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24-25,
14476 Potsdam-Golm, Germany
2
Laboratoire d'Ingénierie Moléculaire Appliquée à l'Analyse (LIMAA) IPHC - UMR 7178 - CNRS ECPM, 25 rue
Becquerel, 67087 Strasbourg Cedex, France
3
Laboratory of Biophysics, University of Turku, Tykistökatu 6A, 20520 Turku, Finland

Protein detection is an important subject in molecular diagnostics, biotechnology as well as in

pharmaceutical industry. Currently, sensitive detection and screening techniques are based
on strong and specific antibody-antigen interactions, e.g. used in Enzyme-Linked
Immunosorbent Assays (ELISAs). Homogenous assays based on Förster Resonance
Energy Transfer (FRET) have high potential for use in in-vitro diagnostics. The Alzheimer’s
disease is a severe medical condition of worldwide concern. Protein aggregation has also
been found to be one significant factor in incurable human diseases, such as Alzheimer’s or
Parkinson’s disease. On the other hand, protein aggregation is also important for developing,
manufacturing, storing, and shipping protein-based biopharmaceuticals. In this contribution
we present various lanthanide-to-quantum dot (QD) and lanthanide-to-dye FRET systems
used for specific and non-specific protein detection. These systems are promising candidates
for highly sensitive early-stage diagnostics. The following examples will be discussed: (1)
Endothelial growth factor (EGF) and its vascular form (vEGF) have been chosen to be
targets because they are markers relevant for Alzheimer’s disease. Commercially available
monoclonal EGF and vEGF antibodies were labelled with lanthanide complexes, while
biotinylated polyclonal counterparts were exposed to dye-conjugated streptavidines.
Lanthanide-to-dye FRET was observed upon binding both antibodies to target protein.
Recent results, possible improvements and further perspectives for the use of this FRET
assay in EGF detection are discussed. (2) Another FRET system is associated with protein
total concentration measurement using Europium(III) complex-loaded nanoparticles (donors)
and protein covered QDs (acceptors). Sample BSA inhibits the adsorption and thus FRET as
donor-acceptor distance increases. A sensitive detection of protein aggregation in the range
from 100 to 800 ng/ml was achieved. (3) In next example, two different H1N1 nucleoprotein-
specific aptamers were conjugated to terbium complexes and QDs, respectively. Tb-to-QD
FRET was observed upon binding of the aptamers to H1N1 nucleoproteins, as demonstrated
both by steady-state and time-resolved luminescence spectroscopy. This sandwich aptamer-
based homogenous FRET assay (SABA FRET) was used to determine nucleoprotein
concentrations in vaccine. High sensitivity with detection limits in the low ng/mL range in a
single assay was achieved. This SABA FRET assay can also be extended to the other
biomolecular targets, e.g. Alzheimer’s disease markers. (4) Finally, a newly developed
terbium complex bearing biotin functionality was also tested with dye-conjugated
streptavidines and streptavidine-conjugated QDs. Our results confirm the ability of this newly
developed Tb-biotin to be used both for in-vitro diagnostics and FRET studies in biological
systems.

In summary, we are demonstrating several examples of FRET-based protein detection

formats that can be used for in-vitro diagnostics as well as in lab-on-a-chip platforms.
 pH-sensitive Capsules as Intracellular Optical
Reporters for Monitoring the Lysosomal pH upon
Stimulation

Moritz Nazarenusa , Pilar Rivera-Gila, Sumaira Ashrafa, Wolfgang Paraka

E-mail: [email protected]

a
Fachbereich Physik, Philipps-Universität Marburg, Renthof 7, 35037 Marburg, Germany

Intracellular pH is an important quantity concerning diseases on the cellular level.

Monitoring the pH-value in cells therefore is desired for diagnostic purposes.

We here present a long-term study of the lysosomal pH-value of MCF-7 breast

cancer cells. As sensor we used polyelectrolyte capsules of 2 to 5 Pm in diameter
filled with the pH-sensitive fluorescent dye seminaphthorhodafluor-1 (SNARF-1).
These capsules are fabricated by the layer-by-layer technique and are taken up by
cells spontaneously. They are stored in the lysosomes and passed to daughter cells
upon cell division. This makes them ideal optical reporters for long-term experiments.

The cells were treated with four different agents (Chloroquine, Bafilomycin A1,
Amiloride, and Monensin) for 4 hours. These agents are known to influence pH-
values in cells. We could show that the capsules are an excellent tool to monitor the
pH profile of the lysosomes under influence of these agents for time spans of up to
70h. We could find out that these agents have different kinetics and mechanisms of
action concerning the influence of the lysosomal pH-value.
 DesignofGold(I)ContainingLiquidCrystals

E.Ntararas,G.H.Mehl
DepartmentofChemistry,UniversityofHull,CottinghamRoad,HullHU67RX,UnitedKingdom.
eͲmail.[email protected],[email protected]

Gold containing complexes have attracted considerable interest due to their
solvatochromic behaviour, i.e. the solventͲstimulated luminescence from previously
photoirradiated crystals. However, so far there have been very few reports of gold
containing liquid crystals in the literature. A notable exception is the work on pyrazolato
complexes for which hexagonal columnar mesophase behaviour was detected at
roomͲtemperature and up to 64 oC 1,2 . Conceptually related are the planar pyridine based
goldcomplexesfirstreportedinthe70’s 3,4 ,whichareverypromisingtargetsforexploring
thenanostructuringofgold(I)inorganicmatrices.
In this contribution we report of our synthetic efforts of the
R
pyridineͲbased gold(i) trimer compounds. Hayashi et al. 5  provided
crystallographic evidence about this class of materials to be planar
N
Au Au
thussuitableforcolumnarphasebehaviour.Thestructureisshownin
N Figure 1. The synthesis to this liquid crystal tecton is reported and
Au N R discussedandmiscibilitybehaviourwithothercolumnarliquidcrystals

R
isreported.

Figure1 


1
J.Barberá,A.Elduque,R.Giménez,L.A.Oro,J.L.Serrano,Angew.Chem.Int.Ed.Engl.35(1996)2832Ͳ2835
2
J.Barberá,A.Elduque,R.Giménez,F.J.Lahoz,J.A.López,L.A.Oro,J.L.Serrano,Inorg.Chem.37(1998)
2960Ͳ2967
3
L.G.Vaughan,J.Am.Chem.Soc.92(1970)730Ͳ731
4
G.Minghetti,F.Bonati,Inorg.Chem13(1974)1600Ͳ1602
5
A.Hayashi,M.M.Olmstead,S.Attar,A.L.Balch,J.Am.Chem.Soc.124(2002)5791Ͳ5795
 Polyelectrolyte Microcapsules for
multiple-probe-sensing and drug-delivery applications
M. Ochs, L.L. del Mercato, S. Carregal-Romero, A. Z. Abbasi, X. Yu, W. J. Parak
Philipps Universität Marburg, 35037 Marburg, Germany

In recent years, nano- and microsystems have become very interesting approaches
for sensing and delivery in biological and medical applications. The use of nano- or
microcontainers such as liposomes or polyelectrolyte microcapsules has reached
great interest in this field. Nanoparticle functionalized microcapsules fabricated via
Layer-by-Layer (LbL) adsorption of polyelectrolyte materials and charged gold
nanoparticles1,2 are one promising approach to perform remote-controlled release of
material inside living cells or tissues3.
Furthermore, ion-selective fluorophores embedded into these systems are creating
an interesting tool for extra- and intracellular ion-sensing applications4. The local ion
concentration of various probes can be determined using so-fabricated capsules. In
addition to the local sensing, the delivery of biological active substances or sensitive
dyes to living cells can combine the advantages of delivery and sensor option of such
multifunctional tools.
Microcapsules consisting of polyelectrolyte multilayers on spherical CaCO3 templates
have been fabricated for delivery and sensing applications and characterized via
fluorescence and electron microscopy. Functionalization with fluorescent probes,
metal- and semiconductor nanoparticles and biodegradable materials has been
performed successfully. Ion-sensing of various probes and laser-induced release of
bioactive cargo material in living cells have been shown in recent experiments.

References:
[1] del Mercato, L. L. et al., Nanoscale, 2 (2010), 458-467
[2] Muñoz-Javier, A. et al., Langmuir, 24 (2009), 12517-12520
[3] Carregal-Romero, S. et al., Journal of Controlled Release, (2012), in press
[4] del Mercato, L.L. et al., ACS Nano, 5 (2011), 9668-9674
 RT Synthesis of Air-Stable and Size-Tuneable
Luminescent Core/Shell Cd3P2/ZnS Nanocrystals with
High Quantum Yields
Wilfried-Solo Ojo, Shu Xu, Fabien Delpech, Céline Nayral, and Bruno Chaudret

Laboratoire de Physique et Chimie des Nano-Objets, 135 avenue de Rangueil, F-31077

Toulouse, France

Abstract :
The room temperature synthesis of air-stable, size-tuneable, and high optical quality
ZnS@Cd3P2 quantum dots (QDs) is reported. A large range of emissivity is easily covered
(from 616 nm to 976 nm) thanks to the modulation of the concentration of reactants and of the
temperature (30°C, 90°C). The strategy followed to achieve this two steps synthesis at low
temperature is based on the choice and design of highly reactive and soluble precursors,
Cd(OAc)2(OAm)2 (OAc = acetate, OAm = octylamine) and (TMS)3P
(tris(trimethylsilyl)phosphine) for the formation of the Cd3P2 cores and Zn(OAc)2(OAm)2 and
C2H4S (ethylene sulphide) for the coating process. 1H, 13C and 31P solution and solid-state
NMR studies evidence the presence of a thin layer of oxide at the interface Cd3P2/ZnS and of
tightly bond ligands (acetate and octylamine) at the surface of the QDs.
 A Chloride ion nanosensor for time-resolved fluorimetry and Fluorescence
Lifetime Imaging

Angel Orte,Maria J. Ruedas-Rama, Jose M. Alvarez-Pez,Eva M. Talavera

Department of Physical Chemistry. Faculty of Pharmacy

University of Granada, Campus Cartuja, 18071, Granada (Spain)

e-mail:[email protected]

Fluorescent Quantum Dot nanoparticles have been widely applied for the development of different
ion nanosensors [1-3]. In most of these sensors, the detection signal is the photoluminescence (PL)
intensity. As it is known, the use of PL intensity as detection signal has some drawbacks, especially when
working with nanoparticles into intracellular media, such as excitation power and dye concentration
dependence or interferences from cell autofluorescence. Otherwise, the time-resolved fluorescence
methodology presents many advantages over conventional fluorimetry. For instance, the PL lifetime does
not depend on the total concentration of the dye, and it is also independent of the excitation laser power.
These features allow potential high-sensitivity determinations with low concentration of QD
nanoparticles. Moreover, lifetime-based applications can be expanded imaging techniques, such as
Fluorescence Lifetime Imaging (FLIM), that can be applied to in vivo cell imaging. The PL lifetime of
QDs is rather higher than most of the cell’s autofluorescence background [4], what makes QD signal
easily discernible from the cell emission. In addition, QD nanoparticles are highly resistant to
photobleaching, what allows cell tracking and monitoring of the intracellular environment during long
time processes.
Herein, as a proof of concept, the first CdSe/ZnS quantum dot (QD) photoluminescence lifetime-
based chloride ion nanosensor is reported. The acridiniumdicationlucigenin was self-assembled on the
surface of negatively charged mercaptopropionic acid capped QDs to achieve QD-lucigenin conjugates.
Upon attachment, a drastic decrease of the PL lifetime of both QD nanoparticles and lucigenin is
observed by virtue of a charge transfer mechanism. Since lucigenin is a chloride-sensitive indicator dye,
the PLlifetime of the QDs within the conjugates increases after reacting with Cl-, but also showing a
concomitant decrease in the lucigenin lifetime immobilized on the surface. The PL lifetime of QD-
lucigenin nanosensors shows a linear response in the Cl- concentration range between 0.5 and 50.0mM.
Moreover, a more robust parameter, the ratio WaveQD / Waveluc, can be also used as analytical signal, since
this ratio presents linear response in the same Cl- concentration range. The system also shows good
selectivity towards most of the main anions and molecules that can be found in biological fluids. These
QD-nanosensors have been satisfactorily applied for Cl- determination in simulated intracellular media
with high sensitivity and high selectivity.
Finally, we demonstrate the potential application of the proposed nanosensor in confocal
Fluorescence Lifetime Imaging (FLIM). The results show the promising application of the QD-lucigenin
nanosensors in FLIM, particularly for intracellular sensing, with the invaluable advantages of the time-
resolved fluorescence techniques.
Therefore, this work provides a general framework for the creation of a new type of fluorescent
probes for the detection of different analytes in physiological samples based on the photoluminescence
lifetime of QD nanoparticles. Our work opensdifferent possibilities that may lead to the development of
new nanoscale, photostable, intracellular sensitive probes for the quantification of a wide range of ions
and molecules, just with the proper modification of the QD surface [5,6].

[1] Y. Chen and Z. Rosenzweig, Anal. Chem., 2002, 74, 5132-5138.

[2] M. J. Ruedas-Rama and E. A. H. Hall, Analyst, 2008, 133, 1556-1566.
[3] M. J. Ruedas-Rama and E. A. H. Hall, Anal. Chem., 2008,80, 8260-8268.
[4] M. Dahan, T. Laurence, F. Pinaud, D. S. Chemla, A. P. Alivisatos, M. Sauer and S. Weiss, Opt. Lett., 2001, 26,
825-827.
[5] M. J. Ruedas-Rama, A. Orte, E. A. H. Hall, J. M. Alvarez-Pez and E. M. Talavera, ChemPhysChem, 2011, 12,
919-929.
[6]M. J. Ruedas-Rama, A. Orte, E. A. H. Hall, J. M. Alvarez-Pez and E. M. Talavera, Chem. Commun., 2011, 47,
2898-2900
Optical Sensing of Small Ions with Colloidal Nanoparticles

Dorleta Jimenez de Aberasturi,†,‡ Jose-Maria Montenegro,‡ Idoia Ruiz de Larramendi,†

Teofilo Rojo,†Thomas A. Klar,§ Ramon Alvarez-Puebla,ԋLuis M. Liz-Marzan,ԋand
Wolfgang J. Parak*,‡
†Department of Inorganic Chemistry, UPV/EHU, Bilbao, Spain
‡Fachbereich Physik and WZMW, Philipps Universitaǐt Marburg, Marburg, Germany
§Institute of Applied Physics, Johannes Kepler University, Linz, Austria
ԋDepartmento de Química-Física, Universidade de Vigo, Vigo, Spain

Colloidal nanoparticles, in particular gold nanoparticles and quantumdots, can be used in a

variety of different assays for optical sensing of small ions in solution. In this review, different
detection principles are introduced and their potential use for detection in biological samples
(such as intracellular sensing) is discussed.

Reference: D. Jimenez de Aberasturi, J.-M. Montenegro, I. Ruiz de Larramendi, T. Rojo, T. A.

Klar, R. Alvarez-Puebla, L. M. Liz-Marzán, W. J. Parak, "Optical sensing of small ions with
colloidal nanoparticles", Chemistry of Materials 24,738-745 (2012).
 GOLD NANOPRISMS ( ALSO NANONACHOS, NNS) AS
NANOHEATERS IN CELLS

Beatriz Pelaz, Pablo del Pino, Wolfgang J. Parak, Jesús M. de la Fuente

Instituto de Nanociencia de Aragon (INA), Universidad de Zaragoza, 50018 Zaragoza, Spain

[email protected]

1
The optical properties of metallic nanoparticles (NPs) have been studied intensively. It has not been
until very recently that another physical property related to the optical properties of metallic NPs, light-
2
to-heat conversion, has attracted much interest. In general, metallic nanoparticles can “drive” light-to-
heat conversion very efficiently when they are illuminated at their surface plasmon band as
consequence of their strong absorption of radiation. Metallic NPs are especially suitable for photon-to-
heat conversion as they carry many conduction electrons which can be excited when light couples to
their plasma frequency. Moreover, metallic NPs exhibit a very poor optical quantum yield and since
the heat generated is expected to be linked to the amount of absorbed radiation, they can act as very
3
efficient transducers to generate heat. Photothermal conversation involves the following sequential
processes: (i) conduction electrons couple to the incident electromagnetic wave; (ii) the excited
electron cloud relax through electron–phonon interactions and transfer the gain energy to the NPs
lattice; (iii) and finally, the NPs can transfer heat to the surroundings through phonon–phonon
interactions at the interface.
In this relatively new field of plasmonic heating, gold NPs (Au-NPs) are very popular among other
plasmonic NPs. This trend is motivated by the distinctive properties of Au NPs such as tunable LSPR,
biocompatibility and ease of surface modification by a variety of thiolated molecules.
Herein, we report on the ability of single-crystalline gold nanoprisms to drive light to heat generation.
We evaluate the heating properties of Au nanoprisms that we have called NanoNachos (NNs) due to
4
the characteristic shape they resemble. We evaluated the viability of these particles in VERO cells
using different techniques. Once biocompatibility was demonstrated, we used a diode pumped solid
state (DPSS, 1064 nm, 2W) laser to excite the plasmon bands of the particles inside VERO cells. We
study the thermal response of cells under illumination in terms of viability and morphological changes.

References
[1] Link S and El-Sayed MA (1999) Spectral properties and relaxation dynamics of surface plasmon electronic
oscillations in gold and silver nanodots and nanorods. J. Phys. Chem. B 1999, 103 8410–26.
[2] Kennedy LC et al. (2011) A New Era for Cancer Treatment: Gold-Nanoparticle- Mediated Thermal Therapies.
Small 2011, 7, No. 2, 169–183.
[3] Richardson HH et al. (2009) Experimental and Theoretical Studies of Light-to-Heat Conversion and Collective
Heating Effects in Metal Nanoparticle Solutions. Nano Lett. 2009, Vol. 9, No. 3.
[4] Pelaz, B.; Grazu, V.; Ibarra, A.; Magen, C.; del Pino, P.; de la Fuente, J. M.: Tailoring the Synthesis and
Heating Ability of Gold Nanoprisms for Bioapplications. Langmuir 2012
Pyrene-Functionalysed Quantum Dots: the Excimer and the Monomer
as Two Independent Sensors

Carlos E. Agudelo Morales1, Raquel E. Galian1,2 y Julia Perez-Prieto1

1
Instituto de Ciencia Molecular, Dpto. Química Orgánica, Universidad de Valencia.
2
Dpto. Química Analítica, ICMOL, Universidad de Valencia
E-mail: [email protected]
Pyrene is widely used as a probe because of the information that can be obtained from its
fluorescence emission.[1] Pyrene displays not only a well-defined monomer (M)
emission at 370-430 nm, but at high molar concentrations it also exhibits an efficient
emission at ca. 480 nm due to excimer (E) formation. Pyrene excimer quenching usually
reflects the reduced pyrene singlet excited state population as well as the dynamic
quenching of E itself.[2]
Spherical nanoparticles (NPs) exhibit unique properties, such as a high surface-to-volume
ratio, a large fraction of surface atoms, and high surface energy, among others.
Semiconductor NPs can be capped with ligands which have an anchoring atom (S, P, N,
etc…) at one end which exhibits affinity to the NP surface. The other end of the ligand
can be used for introducing high functionality at the NP periphery. This strategy has
been implemented for the preparation of colloidal solutions of gold NPs with a high local
concentration of pyrene units at their periphery, [3] but no application of NP-pyrene
hybrid systems as fluorescence sensors based on the emission quenching of both M and E
has been described to date.
We report here on highly diluted colloidal solutions of CdSe NPs functionalised with
pyrene units at their periphery and the application of these hybrid systems as dual-
fluorescence sensors. We investigated pyrene fluorescence changes when increasing
amounts of different nitroaromatic compounds were added to toluene solutions of the
hybrid system (1 PM). The quenching effects of two series of nitroaromatic compounds
were examined: i) o-nitroaniline (o-NA), m-nitroaniline (m-NA), and p-nitroaniline (p-
NA); and ii) nitrobenzene (NB), p-nitrotoluene (p-NT), 2,4-dinitrotoluene (2,4-DNT),
and 2,6-dinitrotoluene (2,6-DNT). The selectivity of these hybrid systems in sensing will
be discussed using the quenching efficiency of i) M intensity and ii) E intensity, as well
as the M/E quenching efficiencies ratio (KM/KE).

References
[1] S. L. Murov, I. Carmichael and G. L. Hug, eds., Handbook of Photochemistry, 2nd
edn., Marcel Dekker, New York, 1992.
[2] K.-S. Focsaneanu and J. C. Scaiano, Photochem. Photobiol. Sci., 2005, 4, 817.
[3] B. I. Ipe and K. G. Thomas, J. Phys. Chem. B, 2004, 108, 13265.
Synthesis and characterization of colloidal silver nanoclusters

Christian Pfeiffer1#, Sherry Huang1,2#, Jana Hollmann1, Sebastian Friede1, Justin Jin-
Ching Chen2, Andreas Beyer1, Kerstin Volz1, Wolfram Heimbrodt1, Jose Maria
Montenegro Martos1, Walter Chang3, Wolfgang J.Parak1
1
Fachbereich Physik and WZMW, Philipps Universität Marburg. Marburg, Germany
2
Institute of Polymer Science and Engineering, National Taiwan University, Taipei,
Taiwan
3
Department of Biomedical Engineering, Chung Yuan Christian University, Chungli,
Taiwan
#
both authors contributed equally to this study

Email: [email protected]

The use of (noble) metal nanoparticles (• QP DQG QDQRFOXVWHUV ” QP LQ GUXJ
delivery and/or cell therapy is common in science since years. One aim of all these
particles or clusters is the stability in shape, which is mostly colloidal. This has been
realized by special surfactant ligands for example polymers. Also the fluorescence of
the particles or clusters is an important aim for example for cell experiments. In most
cases a dye is necessary to get the particles or clusters fluorescent. All modifications
of the particle or cluster to get these aims influence the behavior of the particle itself.
The cytotoxicity of the particle for example could be degreased or also increased by
these modifications. Therefore it is good to use as less modifications as possible to
get all these aims.

The synthesis of ultra small, water-soluble and fluorescent silver nanoclusters

(AgNCs) has been shown. All this was realized without using any polymer or dye.
The clusters were characterized by various methods (gel electrophoresis, high
performance liquid chromatography (HPLC), UV-Vis absorption, fluorescence
spectroscopy, dynamic light scattering (DLS), time resolved photoluminescence
(trPL), high resolution – transmission electron microscopy (HR-TEM). Also the uptake
and the cytotoxicity of the AgNCs by MCF-7 human breast cancer cells were shown.
Modeling of Dendromesogens: Self Organization and Phase Transitions, Alignment and
nanoconfinement.

Anant Kumar, Zerihun G. Workineh, Alexandros G. Vanakaras, and Demetri J. Photinos

Department of Materials Science, University of Patras, 26504, GREECE

Liquid crystalline dendrimers (LC-Ds) are large and complex supermolecular entities. Their
molecular size and the usually huge number of accessible conformations preclude, at least for high
generations, a fully atomistic description of their self-organisation in the bulk. Accordingly, the
primary issue in formulating a successful, tractable, model for the mesomorphic behaviour of LC-Ds
is the extent of detail to which the structure, the conformations and the interactions of the dendritic
units are to be described.

The broad range of liquid crystalline materials produced by dendritic systems of different
architectures and chemical structures has made it possible to identify the dominant mechanisms of
supermolecular self-organisation and to derive empirical rules for controlling the ensuing phase
structures. The purpose of the first part of this work is to rationalize such mechanisms and rules
using tractable molecular theory and computer simulation tools

In the second part of the presentation we focus on the technologically important issue of macroscopic
alignment of LC-Ds. Whilst in the common low molar mass mesophases the production of large
scale unidirectional domains through surface alignment is a relatively well understood procedure,
this is not the case for LC-Ds. The main reason for this is that the orientational distribution of the
mesogenic units of a dendrimer near an aligning surface is the result of an interplay between the
mesogen-surface interactions and the intra-dendritic geometrical constraints imposed by the
dendritic connectivity. We present and discuss results of computer simulations of model
dendromesogens of various generations and architectures near directional surfaces and of single
dendrimers trapped into nanopores of various shapes.

Acknowledgment: This research has been funded through the EU 7th Framework Programme
(FP7/2007-2013), Marie Curie Actions, People-ITN, under the project “Functional LC Dendrimers:
Synthesis of New Materials, Resource for New Applications” (DENDREAMERS, proj. #215884).
Pietra et al. - Abstract NaNaX5

GISAX study of the dynamics of self-assembly of CdSe/CdS rods at the liquid-air

interface.

F. Pietra, F. Rabouw, W. H. Evers, D. Byelov, C. de Mello Donega, D. Vanmaekelbergh.

Debye Institute for Nanomaterials Science - Condensed Matter and Interfaces

Utrecht University
Email: [email protected]

The ability to manipulate the chemical and physical properties of anisotropic colloidal
nanocrystals at the atomic level, together with the ability to assemble them into ordered 2-D
membranes and 3-D solids is one of the most fascinating and challenging directions in current
nanoscience. Self-assembly of nanocrystals enables the fabrication of new classes of materials in
which novel collective properties can emerge due to dipolar or quantum coupling. These
properties are hence determined by the individual nanocrystal building blocks and the
periodicity of the assembly. Direct formation of nanocrystal membranes at the liquid-air
interface is currently emerging as a promising method to fabricate functional ultra-thin films1-5.
In this respect, we studied the self-assembly of CdSe/CdSe heterorods, initiated by controlled
evaporation of the solvent from a suspension casted on a glycol substrate.
Here, we present an in-situ study using GISAXS combined with ex-situ TEM of this self-
assembly. We have used CdSe(dot)/CdS rods with diameter of 4 nm and lengths varying from
15 to 50 nm. Both the GISAXS pattern and the TEM study showed that - for a fixed
concentration of rods - the structure of the self-assembled film depends strongly on the length of
the nanorods. Short rods self-assemble into μm long stripes of horizontally bundled wires; the
stripes show long-range order in both lateral directions, while in a bundle the rods are
hexagonally ordered. In contrast, rods with lengths of 20-50 nm are vertically aligned in
membranes with order over micro-meters in the lateral directions. With GISAXS we were able
to follow the dynamics of the self-assembly with time resolution in the minute regime. The
results suggest that the rods form ordered bundles already in the bulk dispersion. In addition it
was found that hexagonally ordered preformed bundles of rods are first horizontally adsorbed at
the toluene-air interface, followed by rotation into the upright position. This mostly happens at
the boundary of already existing domains. The results provide insight into the mechanism of the
nanorod self-assembly at the liquid-air interface, opening the way for fabrication of single-rod
functional materials.

[1] A. Dong et al, Nature Materials, 2010, 466, 474-477.

[2] T. P. Bigioni et al, Nature Materials, 2006, 5, 265-270
[3] W. H. Evers et al, Nano Letters, 2010, 10, 4235-4241.
[4] M. Zanella et al, Advance Material, 2011, 23, 2205–2209.
[5] D. Vanmaekelbergh, NanoToday, 2011, 6, 419-437.
 Capacitance studies of elastic and dielectric properties in an
organosiloxane low-generation dendrimer and related monomers

S. Polineni1,2 ,J. L. Figueirinhas1,2, C. Cruz1,2, D. A. Wilson3 and G. H. Mehl3

1
IST - Technical University of Lisbon, Dep. de Física, Av. Rovisco Pais, P-1049-001 Lisboa,
Portugal
2
CFMC, Av. Prof. Gama Pinto, 2, P-1649-003 Lisboa, Portugal
3
Department of Chemistry, University of Hull, Cottingham Road, Hull, HU6 7RX,
United Kingdom

It is well known that dendrimers may exhibit liquid crystalline properties [1], this feature is an added
asset for the self assembling of regular structures of these materials at the nano scale. Recently a
range of experimental techniques such as DNMR, optical conoscopy and infrared absorption
measurements were employed to detect the uniaxial (NU) and biaxial (NB) nematic phases in some
organosiloxane tetrapodes (low generation dendrimers) connected to laterally attached mesogenic
units [2,3]. The existence of the elusive NB phase has been the subject of much discussion since it
was predicted by Freiser in 1970 [4].
In this work, capacitance measurements carried out with electric fields going above the Freedericksz
threshold were obtained in one of these organosiloxane tetrapodes and associated monomers. Using
this procedure, the determination of the dielectric and relevant elastic constants, controlling the
director’s reorientation in both planar and homeotropically aligned samples, becomes accessible
through the simulation of the underlying process. This technique which has been applied to uniaxial
nematics [5] is used here to analyse also the temperature range where the NB phase was reported for
the organosiloxane tetrapode [3].
The results obtained are discussed in the context of the different NB phases proposed earlier [6] and
considering the previously reported NU-NB phase transition in the pure tetrapode and its absence in
the related monomers.

Acknowledgments: This work was partially supported by the Portuguese Science Foundation through
project PTDC/FIS/65037/2006 and by the European Comission under 7th Framework Programme
through project PEOPLE-2007-1-1-ITN-215884 (Dendreamers)

References

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D. Photinos, Liq.Cryst. 30, 1021 (2003); R. Elsasser, G. H. Mehl, J. W.Goodby, and D. J. Photinos, Chem.
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Pratibha, and N.V. Madhusudana, Phys. Rev. Lett. 99, 247802 (2007).
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S.D. Peroukidis, P.K. Karahaliou, A.G. Vanakaras, D.J. Photinos, Liq. Cryst. 36 727 ( 2009).
 MonofunctionalizedGoldNanoparticlesforinmunodetectionbiosensig

E.Polo,S.Puertas,P.Pina,J.Santamaria,V.Grazu,J.M.delaFuente*

NanoscienceInstituteofAragon(INA),UniversityofZaragoza,EdificioI+D,C/MarianoEsquillor
s/n,50018Zaragoza,(Spain)

Goldnanoparticles(AuNPs)havebeenusedforanalyticalandbiomedicalpurposesformany
years.Recently,goldnanoparticleshavebeenextensivelyutilizedforthefabricationofseveral
biosensing devices owing to their special physical properties.1 The availability of a versatile
chemistry for further functionalization of gold nanoparticles surface allows the coupling of
biomolecules such as antigens or antibodies to gold nanoparticles, and these bioͲconjugates
provideausefulplatformfortheirapplicationinbiodetection.2Thebiomolecularrecognition
eventsoccurringatthenanoparticlessurfacehaveaninfluenceontheopticaland/orelectrical
properties of the system allowing the development of more sensitive and flexible sensing
systems. Gold nanoparticles that are linked to bioreceptors provide labeled conjugates that
can be used to optically follow the biorecognition events at biosensor surfaces. The most
prominentdetectiontechniques,arebasedontheinteractionbetweengoldnanoparticlesand
light, and allow analyzing numerous components in samples directly. The maximum
absorbancewavelengthoftheirlocalizedsurfaceplasmonresonancespectrumissensitiveto
the size, shape, interparticle spacing, and dielectric properties of the material and local
external dielectric environment of the nanoparticle.3 This property has been exploited for
developing new nanoscale affinity biosensors that are based on transducing small changes
near the nanoparticle surface into a measurable wavelengthͲshift response. To identify a
specific antigenͲantibody interaction in immunoassays, gold nanoparticles are used as
molecularlabels,wherethebioͲrecognitioneventistranslatedintogoldnanoparticlegrowth
signalduetothecatalyticreductionofgoldsaltontothegoldnanoparticlesurfaces.4

In this work we incorporate the gold nanoparticle growth with the use of magnetic
nanoparticles,toquantifydifferentanalytes(E.Coli,tumormarkerCEA)inrealsamples,based
on sandwich immune reactions. We functionalize gold nanoparticles with antibodies,
controlling the number of functional Ab molecules conjugated to nanoparticles. These
conjugates(stoichiometryAuNpsͲAb1:1)areusedasalabelfortheamplifieddetectionofthe
analyteonthemagneticnanoparticlesurface.TheimmunoͲrecognitioneventistranslatedinto
the gold nanoparticle growth signal which can be quantitatively measured by an UV–vis
spectrophotometric analysis. As the analyte concentration becomes higher, the absorbance
spectra after gold nanoparticle enlargement, exhibit higher intensity of the surface plasmon
band. Growing small antibodyͲcoated gold nanoparticles, after the antigen recognition,
resultedinanincreaseoftheintensityofthemaximumofthesurfaceplasmonband.Withthis
methodology,wecoulddetectE.Coliinaplasmmatrixat10Ͳ2cfu/mL,andCEAat0.5ng/ml.

1.RosiN.L.;MirkinC.A.;Chem.Rev.2005,105,1547Ͳ1562.
2.Sperfling,R.A;RiveraGil,P.;Zhang,F.;Zanella,M.;Parak,W.J.;2008.Chem.Soc.Rev.37,1745Ͳ2140.
3.Sepúlveda,B.;Angelomé,P.C.;Lechuga,L.M.;LizͲMarzán,L.M.;2009.Nanotoday.4,244Ͳ251.
4.Pavlov,V.;Xiao,Y.;Shlyahovsky,B.;Willner,I.;2004.J.Am.Chem.Soc.126,11768–11769.
 General Methodology for the Homogeneous Deposition of a Wide
Range of Nanoparticulate Materials

Jan Poppe, Stefanie Gabriel, Stephen Hickey, Alexander Eychmüller

Physikalische Chemie und Elektrochemie, TU Dresden

Bergstraße 66b, 01062 Dresden, Germany

The ability to tune the fundamental physical properties of matter through the
synthesis of nanocrystalline materials, simply by variation of the synthetic conditions,
has opened up many possibilities for applications across a wide range of fields such
as catalysis, sensing, solar energy harvesting, light emitting diodes (LEDs) and
optoelectronics. In order to incorporate nanocrystals (NCs) into devices it is often
necessary to deposit them onto a suitable substrate. In this work a simple, versatile
and speedy method by which to attach various kinds of nanoparticulate materials to a
variety of oxidic surfaces is presented. The stabilizing ligand shell of the particles is
first exchanged by MPTMS and the surface modified materials studied by FTIR-
spectroscopy and TEM measurements. The effectiveness of this coating procedure is
compared with other methods described in literature by means of electrochemical
measurements and scanning electron microscopy imaging. The influence that the
ligand exchange has on the optical properties of various types of nanoparticles and
their subsequent attachment to glass was investigated by absorption and
photoluminescence spectroscopy. Furthermore this methodology was extended to
deposit lead sulfide (PbS) nanoparticles onto a silica sphere colloidal crystal in order
to modify its optical properties.
PEBBLES: A Software for Accurate, Unbiased, and Fast Measurement of Nanoparticle Morphology
from TEM Images
Sara Mondini, Anna M. Ferretti, and Alessandro Ponti
Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via G.
Fantoli 16/15, 20138 Milano, Italy

Would nanoscience exist if we were not able to see nano-objects? Surely not. Nanoscience exists
also thanks to the outstanding advancement of microscopy. In the field of nanoparticles (NPs),
“microscopy” mostly means transmission electron microscopy (TEM). When confronted with a
new NP sample, each of us first takes TEM images to see the morphology of the NPs. One has then
to measure many hundreds NPs in order to have a statistically significant morphological
description of the NP population. This task is boring and prone to systematic error and (maybe)
bias. Several contributions to the error in size measurement have been listed.[1] Some are related
to the microscope and must be coped with before the micrograph is taken, other ones are related
to the recognition and measurement of the NPs in the TEM image and must be minimized during
image analysis. Thus, there is a need for an accurate, unbiased, and fast software to recognize and
measure the morphology of NPs in TEM images.
PEBBLES is such a software. It treats a (S)TEM image as an intensity surface (blue surface, left panel)
and measures the morphological parameters of the NP (as projected onto the image, middle
panel) by fitting a theoretical model of the NP image intensity (gray surface, left panel) to the data,
thus yielding accurate and unbiased measurements. PEBBLES can be used both in manual mode,
where the user has full control on fitting and validation, and in automatic mode where human
intervention is minimized. In automatic mode, PEBBLES is very fast: in 10 min it recognizes from
у100 to у1000 NPs, depending on image quality, NP contrast and NP-NP distance (right panel).
Since PEBBLES is based on a local modeling procedure, it successfully treats cases such as low
contrast NPs, NPs with significant Bragg diffraction, and inhomogeneous background, which often
make conventional thresholding procedures fail. At variance with methods based on thresholding
or manual measurement, the present approach bears several advantages: accuracy, speed and
unbiased-ness, no need for pre-processing, no digital resolution limitation.
Effort has been spent to make PEBBLES the most user-friendly and the least user-tedious we could.

>ĞĨƚĂŶĚŵŝĚĚůĞ͗ĚĞƚĂŝůƐŽĨĨŝƚƚŝŶŐĂƐŝŶŐůĞϭϴŶŵɶ-Fe2O3 NP; intensity surface view (left) and image view (middle).
Right: portion of the PEBBLES window showing the automatic analysis of a TEM image of 14 nm spherical MnO NPs.

[1] Pyrz, W. D.; Buttrey, D. J., Langmuir 2008, 24, 11350-11360.

 Carving at the Nanoscale: Galvanic Replacement versus Kirkendall Effect at
Room Temperature
Edgar González1,2, Jordi Arbiol3,4 and Víctor F. Puntes1,2,4*
1
Institut Català de Nanotecnologia (ICN), Campus de la UAB, 08193, Bellaterra, Spain. 2Universitat Autònoma de Barcelona (UAB),
Campus de la UAB, 08193, Bellaterra, Spain. 3Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus de la UAB, 08193
Bellaterra, Spain. 4Institució Catalana de Recerca i Estudis Avançats (ICREA), Passeig Lluís Companys, 23, 08010 Barcelona, Spain.

Production of polymetallic hollow nanoparticles of unprecedented complexity will be

presented, as reported in our recent work [1]. The method relies in the simultaneous or
sequential action of galvanic replacement and the Kirkendall effect. Making few
modifications in the chemical environment it is possible to control the reaction and diffusion
processes at room temperature, opening up a synthetic route for the production of a rich new
family of nanoparticles with very different morphology and composition.

So far, one of the main sources that nourish research programs in nanoscience is the recovery
of "old" problems, processes and protocols that, once applied on a different scale with current
powerful instrumental resources, provide interesting pathways for the production of new and
exotic materials. Thus, Kirkendall effect and galvanic, pitting, etching and dealloying
corrosion processes, all intensively studied in bulk materials, can be examined from a new
perspective at the nanoscale, where, as it has been shown, matter is more reactive and
therefore corrosive and diffusive processes are enhanced. Although the Kirkendall effect was
discovered in the 1940s [2], it took 57 years until the synthesis of hollow nanoparticles
through the nanoscale Kirkendall effect was reported [3]. Similarly, the old problem of
galvanic corrosion was brilliantly reinstated with the production of hollow nanostructures of
controlled shape, size, and composition [4]. Hollow nanostructures are of great interest in
recent years, mainly because of their unique optical, electrical, thermal, and catalytic
properties and their related applications [5-10].

Initially, both methods seemed incompatible. Here, we will show how, by controlling
reaction kinetics via chemical additives and temperature, both phenomena can be
simultaneously or sequentially controlled, leading to a broad range of morphologies with
unprecedented complexity in a context where structure determines properties. These
structures, from monodisperse single and double-walled open nanoboxes to noble metal
fullerenes-like nanoparticles are produced in a simple manner at room temperature, in the
aqueous phase, in high yields, with a large-scalable synthesis

1. E. González, J. Arbiol, V. Puntes, Science 334, 1377 (2011).

2. E. Smigelskas, E. Kirkendall, Trans. AIME 171, 130 (1947).
3. Y. Yin et al, Science 304, 711 (2004).
4. Y. Sun, Y. Xia, Science 298, 2176 (2002).
5. S. Skrabalak et al., Acc. Chem. Res. 41, 1578 (2008).
6. Y. Xia, E. Skrabalak, Nano Lett. 5, 473 (2005).
7. M. Yavuz et al., Nature Materials 8, 935 (2009).
8. J. Chen et al., Nano Lett. 7, 1318 (2007).
9. X. Lou, L. Archer, Adv. Mater. 20, 1853 (2008).
10. Q. Zhao, Y. Gao, X. Bai, C. Wu, Y. Xie, Eur. J. Inorg. Chem., 1643 (2006).
 Multiplicative enhancement of optical responses in metal-
organic nanohybrids integrated with whispering-gallery-mode
microcavities
Yury P. Rakovich1,2, Dzmitry Melnikau3, Diana Savateeva1, Andrey Chuvilin2,3,
Rainer Hillenbrand 2,3
1
Centro de Fisica de Materiales (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-
San Sebastian, Spain
2
IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain
3
CIC nanoGUNE Consolider, Tolosa Hiribidea, 76, 20018 Donostia-San Sebastian, Spain
Phone:(+34) 94301-8831, fax: (+34) 94301-5600, e-mail: [email protected]
We report on enhanced optical effects in novel type of hybrid structures that combine high-
Q spherical microcavities with Ag nanoparticles and organic dye molecules in a J-aggregate
state. A layer-by-layer deposition technique provided controllable coating of the latex
microspheres with a shell of close-packed Ag nanoparticles and J-nano-aggregates.
Developed structures show pronounced whispering gallery modes (WGMs) in
microluminescence spectra (Fig.1), which are electromagnetic waves that circulate and are
strongly confined within the microcavity.
Our experiments revealed that WGMs alone can be responsible for enhancement of optical
responses from J-nano-aggregates. At the same time, coherent coupling between localized
plasmons of the metalic nanoparticles and the exciton in molecular aggregates results in
strongly plasmon-enhanced Raman signal. Owing to the concerted action of “photonic hot
spots” (the locally enhanced electric fields due to WGM resonances in microcavities) and
“plasmonic hot spots” in the Ag aggregates, we observe strongly increased
photoluminescence intensity, intensified spontaneous emission rate and enhanced Raman
scattering from the J-nano-aggregates (Fig.1).

Figure 1. Micro-photoluminescence spectrum of single WGM microcavity with hybrid shell. Insert
shows SEM image (a) and confocal photoluminescence image of microcavity/shell structure.
 Synthesis and Properties of Electron-Donor Functionalized Symmetric
Compounds Containing Aromatic Polycyclic- and Amino- core for Organic
Electronics
Renji R. Reghu*1, Juozas V. Grazulevicius*1, Vygintas Jankauskas2, Valentas Gaidelis2, Karolis
Kazlauskas3, and Saulius Jursenas3,
1
Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254, Kaunas,
Lithuania
2
Department of Solid State Electronics, Vilnius University, Sauletekio al. 9, LT-10222, Vilnius, Lithuania
3
Institute of Applied Research, Vilnius University, Sauletekio al. 9, LT-10222 Vilnius, Lithuania
Email: [email protected] , [email protected]

Research from both academia and industry has been increasing steadfastly in the area of
organic electronics during the past decades because of the great hunt for cost-effective
opto(electronic) devices such as organic light-emitting diodes, field-effect transistors,
photovoltaic cells etc [1]. Symmetrical compounds containing functional chromophores like
perylene bisimide, pyrene or triphenylamine as the central core have been explored
extensively as organic luminescent and charge transporting materials for the fabrication of
aforementioned devices. Moreover, these central cores provide the opportunity for the
multifunctionalization with other conjugated molecular moieties; for example, electron-donor
chromophores and thus, afford the tunability of physical properties important for device
applications.
Herein, we report on the synthesis of a series of perylene bisimide-, pyrene-, or
triphenylamine- core derived compounds containing electron-donor moieties such as
carbazole, fluorene, phenothiazine etc and investigated the effect of the nature of these donor
moieties on the thermal, electrochemical, optical, photophysical and photoelectrical
properties of these derivatives.
Perylene bisimide derivatives exhibit wide absorption window extending to near
infrared region of the spectrum and demonstrate photoinduced intramolecular electron
transfer. Bay carbazolyl substituted perylene bisimides transport both electrons and holes at
ambient conditions as established by xerographic time-of-flight technique. The variation of
the linking topology of carbazolyl moieties to the core of perylene bisimides has furnished
materials with complementary semiconducting properties [2]. Field-effect transistor
fabricated using bay triphenylamino functionalized perylene bisimide displays ambipolar
behaviour with the hole and electron mobilities of 1.5×10-3 and 3.5×10-4 cm2V-1s-1,
respectively [3]. Pyrene derivatives exhibit excellent thermal stability and demonstrate glass
transitions between 32 oC and 232 oC. Pyrene derivatives with carbazole arms are shown to
be highly fluorescent in dilute solution (fluorescence quantum yields; ĭF up to 0.84) and in
rigid polymer matrix (ĭF up to 0.60). Triphenylamine core centered compounds display
monotropic liquid crystalline characteristics and exhibit luminescence.

[1] Strohriegl, P.; Grazulevicius, J. V. Adv. Mater. 2002, 14, 1439-1452.

[2] Reghu, R. R.; Bisoyi, H. K.; Grazulevicius, J. V.; Anjukandi, P.; Gaidelis, V.; Jankauskas, V. J. Mater.
Chem. 2011, 21, 7811-7819.
[3] Pron, A.; Reghu, R. R.; Rybakiewicz, R.; Cybulski, H.; Djurado, D.; Grazulevicius, J. V.; Zagorska, M.; -
Bajer, I. K.; and Verilhac, J.-M. J. Phys. Chem. C 2011, 115, 15008–15017.
Protein conjugation of ligand-free gold nanoparticles by laser ablation
in liquid flow
C. Rehbock, L. Gamrad, S. Barcikowski

Technical Chemistry I, University of Duisburg-Essen and Center for NanoIntegration Duisburg-Essen CeNiDE,
Universtitaetsstrasse 5, 45141 Essen, Germany

[email protected]

Due to the widespread use of medical implants, nanoparticles emitted from them by abrasion are a
severe problem. Since translocation of nanoparticles through biological barriers has been reported, their
unintended influence on germ cell function and embryo development is a growing matter of concern
because in reproduction medicine, already one compromised cell may have severe effects. As artificial
ligands may interfere with toxicity assays [1], ideal nanoparticles reference material should be ligand-free
or solely coated with ligands found in biological systems e.g. serum proteins. Thus, suitable nanoparticles
are not accessible by traditional chemical synthesis as up to date contaminating ligands cannot be
quantitatively exchanged [2] or removed [3]. Laser ablation in liquid is a promising alternative which
requires no artificial ligands, though the control of size and polydispersity is still a limiting factor.
In this work, an advanced synthesis method for ligand-free nanoparticles based on laser ablation in liquid
flow is presented, which partially overcomes the limitations of this technology. After generation, the
particles grow on a millisecond to second time scale in liquid flow while addition of biomolecules at certain
time delays quenches this growth (Figure 1) [4]. Adding Bovine Serum Albumin (BSA) as a biocompatible
ligand with time delays from 0.5 – 4 s tunes the particle size in a range of 15 to 50 nm. Interestingly,
addition of small concentrations of sodium phosphate buffer in the carrier stream significantly decreased
particle size and particle size distribution (Figure 2). This phenomenon offers another opportunity for size
tuning as well as the possibility of increasing colloid quality by significantly reducing the polydispersity.
Furthermore, it provides valuable information on the growth mechanism of laser-generated nanoparticles
in liquid flow and how it is influenced by ionic strength. This study may contribute to insights into
interaction of proteins with bare nanoparticle surfaces and how these are affected by pH, ionic strength
and proteins.
1,6
45
1,4
40
average particle diameter [nm]

1,2
35
1,0
30
-3
O PDI *10

0,8
25

20 0,6

15 0,4

10 0,2

5 0,0
0 5 10 15 20 25 30
buffer concentration [μM]

Figure 1: Delayed bioconjugation in liquid flow Figure 2: Average particle diameters and PDI of Au-BSA
conjugates (disk centrifuge) synthesized at different buffer
concentrations

[1] Uboldi et al., Gold nanoparticles induce cytotoxicity in the alveolar type II cell lines A549 and NCIH441, Particle and Fibre
Toxicology 6:18 (2009)
[2] A. Rostek, D. Mahl, M. Epple Chemical composition of surface-functionalized gold nanoparticles, J. Nanopart. Res., 13, 4809 –
4814 (2011)
[3] J. A. Lopez-Sanchez et al., Facile removal of stabilizer-ligands from supported gold nanoparticles: Nature Chemistry, 3, 551–556
(2011)
[4] C.L. Sajti, A. Barchanski, P. Wagener, S. Klein, S. Barcikowski; Delay Time and Concentration Effects During Bioconjugation of
Nanosecond Laser- Generated Nanoparticles in a Liquid Flow, J. Phys. Chem. C, 115, pp. 5094-5104 (2011)
Charge transport in conjugated polymer/semiconductor nanocrystals hybrid thin films
E. Couderc, A. Lefrançois, N. Bruyant, F. Chandezon, D. Djurado, J. Faure-Vincent, P. Reiss
CEA-Grenoble/INAC/SPrAM (UMR CEA–CNRS–UJF)/LEMOH,
17 rue des Martyrs, 38054 Grenoble cedex 9, France; e-mail: [email protected]
In the quest for cheaper materials used in solar energy conversion, organic thin films based on pi-
conjugated polymers hold the promise of low cost solution processing on large surfaces. Most conjugated
polymers behave in their undoped state as p-type semiconductors. In heterojunctions with conjugated polymers,
semiconductor nanocrystals therefore act as electron acceptors and transporters. Such hybrids combine the
advantage of polymers’ film processibility with the size-tunable absorption and electronic properties of
nanocrystals.[1] In an ideal case, both components constitute an interpenetrated network (bulk heterojunction),
providing a large interface area for efficient exciton dissociation and pathways for the charge carrier transport to
the electrodes. The best power conversion efficiencies reported to date for hybrid solar cells are 3-4%,[2] i.e.
much lower than for all-organic devices (> 8%). Recent studies indicate that charge transport is the limiting
factor in most organic and hybrid solar cells.[3] A more fundamental understanding of the energetics and of the
charge transport properties is therefore needed to improve the efficiency of hybrid photovoltaic devices.
In this contribution we address the question of how the addition of nanocrystals in a matrix of a
conjugated polymer influences the charge carrier mobilities and hence the transport properties. We will present
the electrical characterizations of hybrids made of poly(3-hexylthiophene) and CdSe nanocrystals, one of the
most studied systems in hybrid solar cells. 4.3 nm spherical nanocrystals (nanodots) and branched CdSe
nanostructures (bi-, tri-, tetrapods => nanopods) of similar arm diameter are compared. Current-voltage
characteristics under illumination and in the dark were measured and photocurrent transients were recorded by
means of time-of-flight (ToF) measurements (Fig. 1). In particular we relate the charge carrier mobilities to the
mass (or volume) fraction of nanocrystals in the polymer matrix. For the nanodots, an increase of both electron
and hole mobilities in the hybrid film is observed for ratios up to 75% in weight (36% in volume) of
nanocrystals; higher ratios deteriorate the hole mobility. Comparing the different nanocrystal shapes, at low
nanocrystal ratios the electron mobilities of films with nanopods and nanodots exhibit different field
dependences. Surprisingly, at high nanocrystal ratios (83 wt%/49vol%), the electron mobility is lower for
nanopods than for nanodots. We attribute this behaviour to the reduced percolation in the film containing the
nanopods due to their stronger tendency for aggregation. Summarizing, we show that ToF analysis is an
appropriate tool to investigate the charge transport mechanisms in hybrid thin films, in view of improving and
equilibrating charge carrier mobilities.

Fig. 1. a) ToF curves obtained for different voltages of a sample containing 75 wt% (49 vol%) of 4.3 nm CdSe
nanocrystals in P3HT. Hole (b) and electron (c) mobilities extracted from ToF measurements as a function of the
weight or volume fraction of nanocrystals in the polymer matrix.

[1] a) N. C. Greenham, X. G. Peng, A. P. Alivisatos, Physical Review B 1996, 54, 17628-17637; b) D. S. Ginger, N. C.
Greenham, Physical Review B 1999, 59, 10622-10629; c) W. U. Huynh, J. J. Dittmer, N. Teclemariam, D. J. Milliron, A.
P. Alivisatos, K. W. J. Barnham, Physical Review B 2003, 67; d) P. Reiss, E. Couderc, J. De Girolamo, A. Pron, Nanoscale
2011, 3, 446-489.
[2] a) S. Dayal, N. Kopidakis, D. C. Olson, D. S. Ginley, G. Rumbles, Nano Lett. 2010, 10, 239-242; b) S. Ren, L.-Y. Chang, S.-
K. Lim, J. Zhao, M. Smith, N. Zhao, V. Bulovic, M. Bawendi, S. Gradecak, Nano Lett. 2011, 11, 3998-4002.
[3] R. A. Marsh, C. R. McNeill, A. Abrusci, A. R. Campbell, R. H. Friend, Nano Lett. 2008, 8, 1393-1398.
Optical and Mechanical Properties of Hollow Silica Nanoparticles
M. Retsch1,2, M. Schmelzeisen3, J. Yin4, J.-H. Lee2,5, H.-J. Butt3, M.C. Boyce4, E.L.
Thomas2,5
1
University of Bayreuth, Physical Chemistry Department, 95440 Bayreuth, Germany
2
Massachusetts Institute of Technology, Department of Materials Science and Engineering, Cambridge, MA
02139, USA
3
Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
4
Massachusetts Institute of Technology, Department of Mechanical Engineering, Cambridge, MA 02139, USA
5
Rice University, School of Engineering, Houston, TX 77251, USA

Hollow silica nanoparticles (HSNP) are simple building blocks for mesostructured materials with a
wide range of interesting properties. HSNPs can be readily obtained by a sacrificial templating
method using monodisperse polystyrene latex particles, which gives good control over the particle
geometry, i.e. diameter and shell thickness.1In this contribution we investigate the optical and
mechanical properties of such well-defined HSNP particles and self-assembled arrays.

Amorphous powders consisting of HSNPs with a shell thickness of only 15 nm exhibit an intriguing
color effect, which depends on the particle diameter. This coloration is not caused by absorption or
Bragg scattering, but is a direct observation of Mie resonances. Due to the ultralow refractive index
(n < 1.1) in such disordered powders, multiple light scattering is largely suppressed and muted colors
can be perceived by the naked eye (Figure 1 left).2

Figure 1. Left panel: Direct observation of Mie resonances in disordered hollow sphere powders,
depending on the particle size. Right panel: Stress contours of hexagonally ordered films of HSNPs
upon compression with a spherical indentor.

HSNP particles can also be self-assembled into hexagonally ordered arrays. The deformation of such
well-defined arrays upon mechanical compression has been investigated experimentally,
theoretically and by modeling (Figure 1 right). We find that under the premise of a constant film
density (i.e. ratio of shell thickness to particle diameter is constant), smaller particles result in more
stable films. Furthermore, the collective response of such films can be explained by the sequential
contact and deformation of the spherical indentor with the constituting hollow spheres.3

1. Graf, C.; Vossen, D. L. J.; Imhof, A.; van Blaaderen, A., A general method to coat colloidal particles with silica. Langmuir 2003,19
(17), 6693-6700.
2. Retsch, M.; Schmelzeisen, M.; Butt, H.-J.; Thomas, E. L., Visible Mie Scattering in Nonabsorbing Hollow Sphere Powders. Nano
Lett. 2011,11, 1389-1394.
3. Yin, J.; Retsch, M.; Lee, J.-H.; Thomas, E. L.; Boyce, M. C., Mechanics of Nanoindentation on a Monolayer of Colloidal Hollow
Nanoparticles. Langmuir 2011,27 (17), 10492-10500.
Cell labeling efficiency of oppositely charged magnetic iron oxide nanoparticles – a
comparative study

Raimo Hartmann1, Christoph Schweiger2, , Feng Zhang1, Wolfgang. J. Parak1, Thomas Kissel2,
Pilar Rivera_Gil1,#

1
Biophotonics, Institute of Physics, Philipps University of Marburg
2
Pharmaceutical Technology, Institute of Pharmacy, Philipps University of Marburg
#
corresponding authors: [email protected]

Abstract
The interaction of nanomaterials with cells is a key factor when considering their translocation
into clinical applications. Especially an effective accumulation of nanoparticles inside certain
tissues is beneficial for a great number of applications. Predominantly size, shape and surface
charge of nanoparticles influence their cellular internalization and distribution. To investigate
this, two series of maghemite (J-Fe2O3) nanoparticles were synthesized either aqueous
coprecipitation or thermal decomposition of organometallic precursor molecules. Size and
the spherical shape of both nanoparticle types were kept constant whereas the charge was
changed by modifying the surface of the nanoparticles with polymers of opposite charge, in
detail poly(ethylene imine) (PEI) and a polymaleic anhydride derivative (PMA). The positively
and negatively charged J-Fe2O3 nanoparticles were characterized with respect to size, zeta
potential, colloidal stability and magnetic properties. Furthermore, the uptake rate and
localization of both formulations into A549 carcinoma cells after fluorescent labeling of the
carriers as well as the resulting alteration in MR-relaxation times were evaluated.
Hierarchical Structures of SnO2-based Nanoparticles of Different Morphologies for
Gas-Sensing, Lithium Ion Batteries, and Photocatalysis

Hongkang Wang and Andrey L. Rogach

Department of Physics and Materials Science & Centre for Functional Photonics, City University of Hong Kong,
Hong Kong SAR

Tin dioxide (SnO2) is an important wide band gap semiconductor which has been extensively
studied in view of its potential applications in the field of gas sensing as well as lithium ions
batteries. For nanostructured SnO2, the control of shape and morphology is an important tool
determining physical, chemical, electronic, optical, and catalytic properties. We demonstrate
how the choice of precursor (SnCl4 or SnCl2) and the fluoride additive (NH4F or NaF) governs
the morphology of hierarchical SnO2 microspheres produced by a purely water-based, template-
free hydrothermal synthesis. Either solid or hollow hierarchical SnO2 microspheres composed of
oriented aligned cone-like SnO2 nanoparticles can be obtained based on the Ostwald ripening
processes undergoing different reorganization paths. The solid spheres preferentially recrystallize
starting from the cores and grow by consuming adjacent smaller particles, while the hollow
spheres preferentially recrystallize starting from outer shells and grow by consuming the
entrapped core materials via the mechanism of solid evacuation. When used as the active
materials in gas sensors, both the hierarchical SnO2 solid and hollow spheres response with high
sensitivity and strong selectivity to several hazardous gases, such as formaldehyde, ammonia,
benzene, acetone, and methanol. When used as anode materials in lithium ion batteries, the
hierarchical SnO2 hollow spheres exhibit superior lithium storage capacity and cyclic
performance than the hierarchical SnO2 solid spheres. We further report a facile strategy to
coaxially grow compact SnO2 overlayers on multiwall carbon nanotubes with controlled
thickness via the hydrothermal method, and show the performance of the resulting composite
materials as anode materials for lithium ion batteries. The use of SnCl2 precursor in the
hydrothermal synthesis of SnO2 nanostructures not only changes the morphology of the resulting
nanostructures from spherical to flower-like, but also results in their simultaneous self-doping
with Sn2+, introducing additional energy levels within the band gap and leading to an increased
optical absorption over the full solar spectrum, which renders them promising in photocatalysis.
 Intrinsic magneto-optical response of 3D photonic-crystals infiltrated
with magnetic nanocrystals.

Oana Pascu1, José Manuel Caicedo1, Martín López-García2, Víctor Canalejas2, Álvaro Blanco2,
Cefe López2, Josep Fontcuberta1, Gervasi Herranz1 and Anna Roig1

1
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB,
E0819-Bellaterra, Spain (email: [email protected] )
2
Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3,
E28049-Madrid, Spain

Photonic-crystals are materials in which the permittivity is periodically modulated on the

scale of the optical wavelength modifying their spectral optical response [1, 2]. The addition of
a magnetic component into these structures, the so-called magneto-photonic crystals (MPCs),
has interesting effects as for instance the enhancement of the magneto-optical response at
selected frequencies [3] (figure 1a).
It has previously been demonstrated that the magneto-optical response of one-
dimensional (1D) MPCs is significantly enhanced at band-edge frequencies [4]. The
achievement of high-quality 3D-MPCs is much more complex and the attainment of an optimal
magneto-optical response, comparable to that of 1D-MPCs, remains a challenging issue.
At frequencies close the band edges, the group velocity of light is slowed down and thus
photons of those wavelengths will couple very intensively with the medium. Exploiting this
mechanism, we have achieved enhanced magneto-optical responses at near-band edge
wavelengths in 3D-MPCs. These systems were built by following two strategies: i) by
infiltrating self-assembled direct and inverse opal structures with monodisperse ensembles of
ex-situ synthesized magnetic nanocrystals stabilized as colloidal disperson5 and ii) by
microwave assisted in-situ synthesis of the magnetic nanocrystals coating conformally the
photonic structures6 (figure 1b). In both cases, high magnetic load and long-range order have
been fundamental to obtain large magneto-optical responses at wavelengths near the photonic
band-edges (figure 1c).
Our results demonstrate the potential of exploiting light polarization in photonic
structures as a powerful strategy to customize the magneto-optical spectral response of
magnetic materials and to obtain optimized materials for applications such as sensing or
optical communications.

figure 1 a figure 1b figure 1c

1. E. Yablonovitch, Phys. Rev. Lett. 58, 2059 (1987)
2. S. G. Johnson, J. D. Joannopoulos, Photonic Crystals: The Road from Theory to Practice,
Kluwer, Boston, (2001)
3. K. Takahashi, F. Kawanishi, S. Mito, H. Takagi, K. H. Shin, J. Kim, P. B. Lim, H. Uchida, and
M. Inoue, J. Appl. Phys. 103, 07B331 (2008).
4. M. Inoue, R. Fujikawa, A. Baryshev, A. Khanikaev, P. B. Lim, H. Uchida, O. Aktsipetrov, A.
Fedyanin, T. Murzina, A. Granovsky, J. Phys. D: Appl. Phys. 39, R151 (2006).
5. J. M. Caicedo, O. Pascu, M. López-García, V. Canalejas, A. Blanco, C.López, J.Fontcuberta,
A. Roig*, G. Herranz* ACS Nano 5 4 (2011) 2957–2963.
6. O. Pascu, J.M. Caicedo, M. López-García, V. Canalejas, A. Blanco, C. López, J. Arbiol, J.
Fontcuberta, A.Roig*, G. Herranz*, Nanoscale 3, (2011) 4811.
 Applications of the photoluminescence lifetime of Quantum Dot to sensing

Maria J. Ruedas-Ramaa, Angel Ortea, Elizabeth A. H. Hallb,

Jose M. Alvarez-Peza,Eva M. Talaveraa
a
Department of Physical Chemistry. Faculty of Pharmacy
University of Granada, Campus Cartuja, 18071, Granada (Spain)
b
Institute of Biotechnology, University of Cambridge
Tennis Court Road, Cambridge CB2 1QT (United Kingdom)

e-mail:[email protected]

Semiconductor nanocrystals, quantum dots (QDs), present a set of unique photoluminescence properties,
which has led to increased interest in using them as advantageous alternatives to conventional organic
dyes [1,2]. Many applications of QDs involve surface modification to enhance their solubility and
biocompatibility. One of the least exploited properties of QDs is the very long photoluminescence (PL)
lifetime [3,4], that usually shows complex kinetics owing to the effect of quantum confinement. These
long photoluminescence lifetimes also made them highly sensitive and selective, since they can be easily
distinguished from other interfering short-lived fluorescence, such as cell autofluorescence.
Because the photoluminescence of QDs arises from the recombination of the exciton, all changes
in charge or composition on the surface and environment of QDs could affect the efficiency of core
electron-hole recombination and consequently the luminescence efficiency, PL decays and dynamics. On
these grounds, we show the effect of surface modification on fluorescence properties of QDs of different
sizes, especially focusing on changes on fluorescence lifetimes. In this work we explore the potential of
time-resolved fluorescence measurements for the detection of specific processes that alter QD emission
[5]. Herein, we describe the effect of different surface modifications on the photoluminescence decay
kinetics of QDs. The different surface modifications were carefully chosen to provide lipophilic or water-
soluble QDs with either positive or negative surface net charges. We also survey the effect on the QD
lifetime of several ligands that interact with the QD surface, such as organic chromophores or fluorescent
proteins, by means of electrostatic interactions, charge transfer, or energy transfer.
In particular, from all these examples, two systems were investigated in depth for the development
of the two first CdSe/ZnS QD PL lifetime-based pH and Cl- nanosensors. On one hand, in the pH-
nanosensor, the responsible for the changes in the PL lifetime with pH was the protonation /
deprotonation of the ligand, Mercaptopropionic Acid (MPA) on the surface of QD [6]. On the other hand,
the Cl--nanosensor takes the advantage of the response towards Cl- of a different indicator, lucigenin,
immobilized on the surface of the QD nanoparticles [7,8]. The proposed QD-MPA and QD-Luc
nanosensors have been satisfactorily applied for the determination of Cl- or pH estimation, respectively,
in simulated intracellular media, with high sensitivity and high selectivity toward most of the intracellular
components.
The results obtained demonstrate that time-resolved fluorescence is a useful tool for QD-based
sensing to set the basis for the development of time-resolved-based nanosensors. The excellent
photophysical properties of QDs together with the typical advantages of time-resolved fluorescence
overcome most of the limitations of the use of organic chromophores and steady state fluorescence as
analytical signal, such as variations in the observation pathlength and probe concentration, light
scattering, and photobleaching. We provide an overview of the potential of this technique that will help to
set a basis for the use of modified QDs in fluorescence lifetime-based applications such as Fluorescence
Lifetime Imaging (FLIM).

[1] I. L. Medintz, H. T. Uyeda, E. R. Goldman, H. Mattoussi, Nat. Mater., 4, 435-446 (2005).

[2] W. C. W. Chan, S. Nie, Science, 281, 2016-2018 (1998).
[3] M. Dahan, T. Laurence, F. Pinaud, D.S. Chemla, A.P. Alivisatos, M. Sauer, S. Weiss, Opt. Lett. 26, 825-827
(2001).
[4] P. Michler, A. Imamoglu, M.D. Mason, P.J. Carson, G.F. Strouse, S.K. Buratto, Nature, 406, 968-970 (2000).
[5] M.J. Ruedas-Rama, A. Orte, E.A.H. Hall, J.M. Alvarez-Pez, E.M. Talavera, ChemPhysChem, 12, 919-929 (2011).
[6] M.J. Ruedas-Rama, A. Orte, E.A.H. Hall, J.M. Alvarez-Pez, E.M. Talavera, Chem. Commun. 47, 2898-2900
(2011).
[7] M.J. Ruedas-Rama, E.A.H. Hall, Analyst, 133, 1556-1566 (2008).
[8] M.J. Ruedas-Rama, A. Orte, E.A.H. Hall, J.M. Alvarez-Pez, E.M. Talavera Rodriguez, Analyst,
DOI:10.1039/C2AN15851E (2012).
 Charged-excitons and optical gain in CdSe/CdS nanocrystals

Michele Saba1*, Marco Marceddu2, Francesco Quochi1, Mauro Aresti1, Adriano Lai3, Jing
Huang4, Dmitri V. Talapin4, Andrea Mura1,5 and Giovanni Bongiovanni1,5
1
Dipartimento di Fisica, Università di Cagliari, I-09042 Monserrato (CA), Italy
2
Centro Grandi Strumenti d'Ateneo, Università di Cagliari, I-09042 Monserrato (CA), Italy
3
Istituto Nazionale di Fisica Nucleare, Sezione di Cagliari, I-09042 Monserrato, Italy
4
Department of Chemistry, The University of Chicago, Chicago, IL 60637
5
Istituto Officina dei Materiali del Consiglio Nazionale delle Ricerche (CNR-IOM) Unità
SLACS, I-09042 Monserrato, Italy
* corresponding author e-mail address: [email protected]

Concerning optoelectronic applications for colloidal nanocrystals (NCs), non-radiative

recombination phenomena represent a significant roadblock. Whenever multiexciton states
are generated in NCs, Auger recombination occurs, a process in which one exciton disappears
by conferring its entire energy to another exciton in the NC. As a result, the excited-state
lifetime can be reduced by more than two orders of magnitude (from 10 to less than 0.1 ns), a
detrimental effect that has been linked to phenomena like blinking of photoluminescence,
ultrashort optical gain lifetime and narrow gain bandwidth.
The recent demonstration of core/shell NCs engineered for efficient multiexciton
photoluminescence emission has represented a major advance, with measurements of long
multiexciton decay times in such nanocrystals interpreted as evidence for suppression of
Auger recombination.
We set up ultrafast spectroscopy experiments to spectrally and temporally separate exciton,
charged excitons, biexciton and multiexciton optical transitions in CdSe/CdS core/shell NCs
and directly measure in the time domain their lifetimes. Our time-resolved photoluminescence
and transient absorption measurements directly accessed the lifetime of such excited states,
providing a clear picture of Auger phenomena in CdSe/CdS NCs. Our results highlight the
contribution of charged states to long-lived optical gain.
Excitation with variable repetition rate was employed to study the statistics and dynamics of
photoionization and charge trapping leading to the appearance of charged-exciton states. The
control of the optical excitation rate was used to tune the degree of charge accumulation in the
quantum dot and investigate the charging dynamics and the ensuing effect on the
photoluminescence quenching. For laser fluences much below one exciton per pulse, the
photoluminescence of nanocrystals in solution showed characteristic features of the emission
of negatively charged excitons. The overall trion contribution to light emission increased at
high frequency following a power law, without, however, identifying a distinct lifetime
timescale. In solution, the population of charged states was found to be very low, resulting in
a weak photoluminescence quenching. On the contrary, films of colloidal nanocrystals
showed a strong reduction of the light emission quantum yield in the megahertz excitation
regime, with contributions from both negatively and positively charged nanocrystals.
The composition of multivalent nanoparticle-antibody conjugates and their use in
analytical sensors
I. Safenkova, A. Zherdev, B. Dzantiev
Bach Institute of Biochemistry Russian Acad. Sci., Leninsky prospect 33, 119071 Moscow,
Russia
Proteins-nanoparticles conjugates are widely used for the visualization, delivery and
therapy, as catalysts, and in analytical systems. Among them colloidal gold nanoparticles (GNP)
conjugated to antibodies are preparations of particular interest. GNP conjugates have found
increasing application due to high stability and unique optical properties, but their efficient use
requires an understanding of physicochemical characteristics of their interactions with target
antigens. Knowledge of the structure–property relationship for nanoparticle–protein conjugates
allows one to change their composition for the directed regulation of functional characteristics,
such as affinity, hydrodynamic parameters, etc. The question about the optimal GNP–protein
conjugates still remains open. Quantitative data on the conjugate interactions with corresponding
ligands are lacking in the literature.
The aim of our study was to characterize the dependence of the detection limit of
immunochromatographic flow sensors assay (ICFS) on such factors as the size of GNP used for
the immobilization, the antibody concentration in their conjugation with GNP, the conjugation
technique and the affinity of conjugate. We have developed ICFS with GNP–antibody
conjugates for rapid monitoring of the number of low- and high-molecular-weight analytes. The
relationship between the conjugate composition and its affinity was investigated. A series of
preparations allowed us to compare GNP–antibody conjugates with different surface areas for
immobilization of antibodies, and, consequently, with different valencies. It was shown that the
affinity of the conjugates changes with size of GNP (or other inorganic nanoparticles), i.e. with
their valency. An increase in the conjugate size leads to an increase in its affinity. We have
determined the relationship between the composition of the GNP conjugate and the analytical
characteristics of ICFS with its use. Thus, the sensors detection limit decreases from 80 to 3
ng/mL (for antibodies with KD = 1.0Â-9 Ɇ, ICFS for the detection of plum pox virus in the
stone fruit trees) for a series of GNP with an average diameter from 6.4 to 33.4 nm; in the case of
larger particles, the detection limit increases and reaches 9 ng/mL for particles with a diameter of
52 nm (Fig. 1). The low detection limit combined with high reliability can be attained due to the
careful choice of particular optimal parameters (the composition and concentrations of the
reagents, the conditions for immune interactions) for each system under development. We will
present the design of the conjugate with nanoparticles having the best physical and chemical
properties for the use in analytical flow sensors.
Fig. 1. The detection limit of immunochromatographic flow sensors versus the equilibrium
constant for conjugates of gold nanoparticles having different size (average diameters of the
nanoparticles are shown in the plot)
 Methotrexate-PEG modified superparamagnetic nanoparticles
for MRI and drug delivery
Sara Sánchez Paradinas1, Abuelmagd AbuMoghera1, Daniel Sasse2, Nadja C. Bigall1, Wolfgang
Parak1
1
Fachbereich Physik, Philipps Universität Marburg, Marburg, Germany
2
Klinik für Strahlendiagnostik AG Medizinische Physik, Universitätsklinikum Giessen und Marburg
GmbH, Standort Marburg
[email protected]

Over the past several years, the development of targeted nanoparticles for tumor diagnosis and
therapeutics has generated great interest. Concretely, superparamagnetic iron oxide nanoparticles
have been intensively studied for their applications in biomedical areas such as magnetic resonance
imaging (MRI) contrast agents for target-drug delivery, cancer diagnosis, and therapy1,2.

The physical and chemical properties of inorganic nanoparticles make them ideal elements for the
construction of nanostructured devices. Iron oxide nanoparticles are readily soluble in aqueous
media and easily functionalizable. The phase transfer of the nanoparticles from organic solvents to
aqueous solution is accomplished through a coating process with an amphiphilic polymer,
according to the procedure of Pellegrino et al.3 After solubilization, the binding of PEG molecules
through amidation between the carboxylic acid groups of the hydrophilic backbone on the polymer
and the amine groups on the PEG, may provide a versatile platform for subsequent covalent
attachment to other functional organic molecules, such as methotrexate (MTX), one of the most
widely utilized drugs for the treatment of various forms of cancer. This FeNP-PEG-MTX
nanoconjugate is expected to serve both as a contrast enhancement agent in MRI and as a drug
carrier, which should enable delivering and releasing of the chemotherapeutic agent in cells whose
surfaces are overexpressed by folate receptors.

1
Nathan Kohler, Conroy Sun, Jassy Wang, and Miqin Zhang. Langmuir 2005, 21, 8858-8864.
2
Conroy Sun, Raymond Sze, Miqin Zhang. Wiley Periodicals, Inc. 2006.
3
Teresa Pellegrino, Liberato Manna, Stefan Kudera, Tim Liedl, Dmitry Koktysh, Andrey L. Rogach, Simon
Keller, Joachim Rädler, Giovanni Natile and Wolfgang J. Parak. Nano Lett., Vol. 4, No. 4, 2004.
 Structure and Photoluminescence Properties of Sm3+ Doped TiO2
Nanoparticles

=âDSRQMLü, M. Vranješ, J. Kuljanin--DNRYOMHYLü-1HGHOMNRYLü 00LWULü06WRLOMNRYLü

9LQþD,QVWLWXWHRI1XFOHDU6FLHQFHV%HOJUDGH6HUELD

Abstract

Rare earth doped semiconductors have attracted considerable attention in recent years
due to their high potential of becoming a new class of luminescent materials with a wide
range of applications [1]. The TiO2 is considered as promising host material for sensitizing
luminescence of Sm3+ ions because of its wide band gap, low absorbance in the visible region
and thermal properties.
In this abstract we report on synthesis of Sm3+ doped TiO2 faceted nanoparticles via
shape transformation of hydrothermally treated titania nanotubes in the presence of Sm3+ ions.
Usage of nanotubes as a precursor for synthesis of Sm3+ doped TiO2 nanoparticles opens-up
possibility to prevail problems related to molecular precursors. Titania nanotubes were
synthesized by hydrothermal treatment of commercial TiO2 powder in proton deficient
aqueous solution [2]. Uniform size distribution of the nanotubes diameters (~ 12 nm) and
length until few hundred nanometers were observed by TEM. The average dimension of Sm3+
doped TiO2 nanoparticles was between 10 and 12 nm. The XRD measurements of titania
nanotubes confirmed their quasianatase axially symmetric crystal structure with distorted
octahedral coordination, while for the Sm3+ doped TiO2 nanoparticles the homogeneous
anatase crystal phase independently of the dopant amount was obtained. The percentage ratio
of Sm3+ to Ti4+ ions in doped nanocrystals was determined using ICP emission spectrometer.
The optical characterization was made by fluorescence and UV-vis reflection spectroscopy.
Stable and bright photoluminescence signals in red spectral region, after excitation at 365 nm,
associated with 4G5/2 ĺ6H5/2, 4G5/2 ĺ 6H7/2 and 4G5/2 ĺ6H9/2 transitions of Sm3+ in all samples
at room temperature and independently of dopant concentration were observed. This study
demonstrates possible route to prepare rare-earth element doped faceted titania nanoparticles
using nanotubes as precursor.

[1] Y. H. Li, G. Y. Hong, J. Solid State Chem., 2005, 178, 645

[2] Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1999) Titania Nanotubes
Prepared by Chemical Processing. Adv Mater 11:1307-1311
 Highly-efficient energy transfer in hybrid organic/inorganic semiconductor
nanostructures
Diana Savateeva1, Dzmitry Melnikau2, Yury P. Rakovich1,3
1
Centro de Fisica de Materiales (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018
Donostia-San Sebastian, Spain
2
CIC nanoGUNE Consolider, Tolosa Hiribidea, 76, 20018 Donostia-San Sebastian, Spain
3
IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain
Phone:(+34) 94301-8825, fax: (+34) 94301-5600, e-mail: [email protected]

Abstract
Highly luminescent semiconductor nanocrystals possess a number of interesting and
important properties that are tunable thanks to their size-dependent discrete electronic
spectra characteristic of quantum dots (QDs). In this work we studied the optical properties
of a novel type of hybrid structures that combine CdTe QDs with organic dye molecules
(Pseudocyanine iodide (PIC)) in a J-aggregate state. Due to the excitonic nature of
electronic excitations, J-aggregates have the narrowest absorption and luminescence bands
among organic materials, large oscillator strengths and giant third-order nonlinear
susceptibility. It was found that aggregation of PIC molecules can be efficiently triggered
by fast injection of solution of CdTe QDs into concentrated dye solution resulting in
formation of hybrid nano-structures.
In developed structures optical energy harvested by the quantum dots as artificial
antennas then transferred to J-aggregates to enhance the photostability and efficiency of the
carriers recombination. To fabricate CdTe/J-aggregates hybrid nanostructures we have used
an approach based on electrostatic interaction between the positively charged dye and CdTe
QDs capped with thioglycolic acid and, thus, carrying a negative charge. In order to
develop an efficient hybrid material operating in the FRET regime, we carefully selected
the PL colors (diameters) of the QD (donors of energy) to be optically coupled with
absorption of J-aggregates. Also we took advantage of extremely thin surface ligand shell
(~0.5 nm) of CdTe QDs, which insures high efficiency of energy transfer. Formed QD/J-
aggregate FRET system shows the broadband absorption in the visible and the ultraviolet
part of the spectrum typical of quantum dots, along with the narrow emission linewidths
characteristic of J-band emitters (~15 nm full width at half-maximum). We use absorption
and photoluminescence spectroscopy and photoluminescence lifetime studies to conclude
that efficiency of energy transfer is 95%.

Figure 1. PL spectra recorded using excitation at Figure 2. Comparison of PL decays for the QDs
400 nm. Black line – without QDs. Red line – (green line) and QDs injected in PIC (black
after injection of QDs line).
 Colloidal nanoparticles embedded in monolithic semiconductor epilayers

Oliver Schöps,1+ Erick M. Larramendi,1,2 Mikhail V. Artemyev,3 Detlef Schikora,4 Klaus

Lischka,4 Ulrike Woggon1

1 Institut für Optik und Atomare Physik, Technische Universität Berlin, Strasse des 17. Juni 135,
D-10623 Berlin, Germany
2 Physics Faculty, ICTM, University of Havana, Colina Universitaria, C.P. 10400 Havana, Cuba
3 Institute for Physico-Chemical Problems of Belarussian State University, Minsk 220080, Belarus
4 Department Physik, Center for Optoelectronics and Photonics Paderborn (CeOPP), Universität
Paderborn,Warburger Strasse 100, D-33098 Paderborn, Germany

Self-assembled quantum dots are usually obtained by the Stranski–Krastanov growth mode
where size, shape and size distributions of the 3D islands are determined only by the strain
parameter of the specific heterojunction. Hence, this method is limited in terms of the density
and variety of nanocrystals that can be grown on a given substrate. A complementary
approach to obtain semiconductor nanocrystals is colloidal chemistry, which is ideally suited
to limit the size dispersion and to control the surface of nanocrystals, resulting in optical
properties such as high quantum yield, blinking, and an easy tuning of the emission.
However, in order to exploit the versatility of the colloidal nanocrystals (CNCs) e.g. in the
fabrication of devices, one has to accomplish the challenging task of incorporating them into
high quality epitaxial thin films. While the combination of molecular beam epitaxy (MBE)
growth and CNCs has been reported by our group in its first stage of development [1], here
we present an optimized deposition and incorporation of CdSe CNCs in high quality ZnSe
epilayers. Structural characterizations show that the whole MBE grown structure is epitaxial
and fully strained to the GaAs(001) substrate and furthermore exhibits a high crystalline
quality. The successful integration of optically-active CNCs enabled us to conduct a detailed
study of the photoluminescence of different sorts of CNCs and the temperature dependence of
their emission.
The hybrid colloidal-epitaxial technique was also employed to study an additional aspect of
matrix-host interaction, namely the enhancement of charge transfer from the epitaxial matrix
into the incorporated CNCs by designing a graded energy gap structure. For this study, core
CNCs, which typically suffer from lower PL efficiency and robustness towards processing
conditions, were incorporated in matrices of either ZnSe or ZnMgSe (core-in-matrix) as well
as into a single ZnSe quantum well within a ZnMgSe matrix (core-in-well). While almost no
PL was detected from the core-in-matrix samples, the core-in-well samples’ emission was
clearly observed. This investigation suggests some guidelines for the potential integration of
semiconductor CNCs as active building blocks in epitaxial optoelectronic devices.

[1] U. Woggon, E. Herz, O. Schöps, M. V. Artemyev, Ch. Arens, N. Rousseau, D. Schikora, K. Lischka, D.
Litvinov, D. Gerthsen, Nano Letters 5, 483-490, (2005)

+ Author for correspondence: Oliver Schoeps

Email: [email protected]
Institut für Optik und Atomare Physik
Technische Universität Berlin, Berlin, Germany
Topics: nano particles, epitaxial structures, optical properties
Preference: oral presentation
(Top left): 0HDVXUHG DQG VLPXODWHG  Ȧ-2T scans of a monolithic ZnSe/CNCs/ZnSe/GaAs(001) hybrid
sample. (Top right): Asymmetric reciprocal space map of ZnSe/CNCs/ZnSe/GaAs(001) around the 224 RLP of a
hybrid sample. (Bottom left): Temperature dependent shift of the PL peaks associated with embedded CNCs
(open circles) and the epitaxial ZnSe matrix (solid circles). The black and gray solid lines represent the
temperature dependence of the free exciton peak energy in ZnSe and zinc-blende CdSe (vertically shifted for
clarity), respectively. The inset shows the PL spectrum of the hybrid sample at 5 K. (Bottom right): PL spectra of
matrix and incorporated core CNCs for hybrid samples with CdSe bare core NC in different matrices. The insets
sketch the grown layer structures.
Thin films of Gold Nanoparticles via Layer-by-Layer Spin-Coating:
Preparation, nanomechanical properties and vapor sensitivity
Jan H. Schroeder1,2, Alexey Petrov1, Natalia Olichwer1, HendrikSchlicke1,
Martin Trebbin2, Stephan Foerster2, Horst Weller1 and Tobias Vossmeyer 1
1
Institute of Physical Chemistry, University of Hamburg, 20146 Hamburg, Germany
2
Bayreuth Center for Colloids, University of Bayreuth, 95447 Bayreuth, Germany

Films comprised of nanoparticles crosslinked by organic molecules have been

studied intensively in the recent past. Vapor sensitivity and charge transport
properties of thin and freestanding films of these systems have been investigated.
The electrical properties of these films depend on the crosslinking molecule used.
The chemical structure and the length of the crosslinkers as well as the chemical
environment have an influence on the conductance. Therefore, these films can be
used as chemical sensors by taking advantage of the altered chemiresistance to
varying specimen of vapors.

Gold nanoparticles of differing sizes have been formed together with the use of
organic dithiols of different lengths and kinds as a linking molecule in our research
project.The mechanical tenability of sensors is important. Instrumented Indentation
Testing has been chosen to perform the mechanical testing of these ensembles of
nanoparticles. A Micro Materials NanoTest was used to measure the
nanomechanical properties of broad regions of nanoparticles by nanoindentation.
Films of varying thicknesses have been characterized as well as films crosslinked by
different dithiols. The results show a dependency on the length and the chemical
structure of the crosslinker and the size of nanoparticles: The hardness of the films
varies inGPa regime just by the change of the length of the alkylene chain. Small
angle x-ray scattering was used to investigate the spacing of the gold nanoparticles
in the films: The length and the chemical structure of the linkers do have a direct
influence on the spacing and the mechanical properties of the film, independent of
the film thickness: A greater distance between the particles results in a lower
hardness of the film.

Additionally, the preparation of these films has been studied intensively.[1]The film
preparation can be very time-consuming. Our method is based on the combination of
the layer-by-layer technique and spin-coating. UV/vis spectroscopy, atomic force
microscopy, and conductivity measurements indicate films prepared via layer-by-
layer spin-coating being of the same quality as coatings prepared via layer-by-layer
self-assembly using laborious immersion baths. This method is extremely efficient to
fabricate crosslinked nanoparticle films: several tens of nanometers in thickness can
be deposited reproducibly within a few minutes. These are not bound chemically to
the substrate and can be lifted-off and transferred. Comparative measurements of
sheet resistances evince that the transfer process does not compromise the film
quality. Electrically addressable, freely suspended films on 3d-electrodes have been
produced for our further research projects and development.

[1] H. Schlicke, J. H. Schröder, M. Trebbin, A. Petrov, M. Ijeh, H. Weller, T. Vossmeyer,

Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating,
Nanotechnology2011, 22, 1–9.
 The Design, Synthesis & Properties of Axially Chiral Liquid Crystalline Materials for
Application in Gold Nanoparticle Materials

C. J. Schubert, C-H. Yu, M. G. Tamba, G. H. Mehl

Department of Chemistry, University of Hull, Hull, UK, HU6 7RX

[email protected]

The assembly of metallic nanoparticles has been shown to be of particular interest for
electronic, optical and photonic applications.1 The employment of organic liquid crystal
materials has proven effective in inducing self-assembly of nanoparticles in complex
geometries.2, 3
The introduction of chiral liquid crystal materials, possessing asymmetric
chiral carbon centres, in non-metallic systems has also revealed interesting and complex
macrostructures. However, it is expected that the introduction of liquid crystal materials
possessing increased powers of helical induction, over the traditional centrally chiral carbon
materials, are required.

Axially chiral materials have long been employed for their superior power of helical
induction over traditionally chiral materials.4, 5
However, their often bulky and three-
dimensional structural geometries are generally not favourable towards liquid crystalline
phase behaviour. Efforts to induce liquid crystalline phase behaviour in materials possessing
the chiral binaphthalene core have found limited success.6, 7

The design, and development of axially chiral binaphthalene materials possessing mesophase
properties is described. Investigation of the properties, based on optical polarising
microscopy, differential scanning calorimetry and x-ray diffraction techniques, will be
reported.

1. X. Zeng, L. Feng, A. G. Fowler, G. Ungar and L. Cseh, Adv. Mater., 2009, 21, 1746.
2. L. Cseh and G. H. Mehl, J. Am. Chem. Soc., 2006, 128, 13376.
3. L. Cseh and G. H. Mehl, J. Mater. Chem., 2007, 17, 311.
4. B. L. Feringa and R. Eelkema, Org. Biomol. Chem., 2006, 4, 3729.
5. G. Solladie and R. G. Zimmermann, Angew. Chem. Int. Ed., 1984, 23, 348.
6. M. Goh and K. Akagi, Liq. Cryst., 2008, 35, 953.
7. A. Yoshizawa, Y. Kogawa, K. Kobayashi, Y. Takanishi and J. Yamamoto, J. Mat.
Chem., 2009, 19, 5759.
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Formation and dynamics of multiple electron-hole pairs in
quantum dot arrays and nanorods
Laurens D.A. Siebbeles
Optoelectronic Materials Section, Dept. of Chemical Engineering, Delft University of Technology,
The Netherlands

E-mail: [email protected]

The generation of two or more electron-hole pairs for the absorption of a single energetic photon is of
interest for development of highly efficient (up to 44%) solar cells. This process of carrier multiplication
is schematically shown in Figure 1 for a thin film array of semiconductor quantum dots (QDs). It has been
established previously that a single energetic photoncan generate multiple excitons in QDs in colloidal
solution.1 We have extended studies oncarrier multiplication tolead chalcogenide quantum dot arrays and
nanorods.The studies were carried out using(ultrafast) pump-probe laser spectroscopy. Neutral excitons
and mobile charges could be distinguished from each other by combining optical detection with terahertz
and microwave conductivity measurements.
Photoexcitation of an array of PbSe QDs with ethanediamine surface ligands was found to directly
yield free mobile chargeswith 100% quantum yield.2 The charges move according to a band-like
mechanism with an almost temperature independent mobility, which is as high as 3 cm2/Vs.On increasing
the photon energy above twice the band gap the process ofcarrier multiplication was found to occur. For
photoexcitation at six times the band gap energy the yield of charges is as high as 300%.3These
chargesare readily available for use in optoelectronic devices even without employing any complex
donor/acceptor architecture or electric fields.Effects of variation of the size and chemical composition of
the surface ligands on carrier multiplication and charge mobility will be discussed.
Photoexcitation of PbSe and CdS nanorods was found to result in formation of charges that can freely
move within a rod. The effects of length and diameter of PbSe nanorods on the efficiency of carrier
multiplication will be discussed.At higher photoexcitation density the terahertz photoconductivity
becomes independent on the number of charges in a CdS nanorod. The cause of this peculiar behavior
will bediscussed on basis of theoretical calculations and computer simulations.

Figure 1.A single energetic photon can produce multiple pairs of free charge carriers in a thin film array of quantum
dots. The seminar reports studies on carrier multiplication in arrays of quantum dots and in nanorods.

References
[1] Beard M C 2011 J. Phys. Chem. Lett.2 1282
[2] Talgorn E, Gao Y, Aerts M, Kunneman L T, Schins J M, Savenije T J, van Huis M A,
van der Zant, H S J, Houtepen A J, Siebbeles L D A 2011 Nature Nanotechnology6 733
[3] Aerts M, Suchand Sandeep C S, Gao Y, Savenije T J, Schins J M, Houtepen A J, Kinge S,
Siebbeles L D A 2011 Nano Lett.11 4485
 Spin Dynamics in CdSe/CdS colloidal nanocrystals
Benjamin Siebers

In recent years, semiconductor colloidal nanocrystals have attracted much attention due to their importance
in fundamental research on zero-dimensional structures and great potential in a variety of applications, such
as quantum information, light emitting diodes, spintronics and biolabeling. With the progress of fabrication
technology, chemically synthesized CdSe colloidal nanocrystals show great superiority in cost, quantum yield
and the ability to tune optical properties by controlling the size, shape and the surface condition precisely.

Although the exciton fine structure in CdSe colloidal nanocrystals has been extensively studied in the past
years, the discussion about the origin of the photoluminescence (PL) in thick-shell nanocrystals (shell
thickness > 5 nm) remains controversial. While it has been proposed by Dubertret et al.1 that the PLin thick-
shell nanocrystals arises from either neutral or charged excitons, Klimov suggested that the PL arises from
thermally mixed bright and dark excitonstates2.

We systematically studied the spin dynamics in CdSe/CdS core/shell nanocrystals, by applying polarization-
resolved static PL and PL decay techniques in high magnetic fields at low temperature. Our results suggest
that the emission of an ensemble of nanocrystals mainly arise from charged exciton states. Furthermore, we
directly measured the spin relaxation rate of charged excitons in these thick-shell nanocrystals. The spin
relaxation rate surprisingly shows a quadratic magnetic field dependence and is considerably lower
compared to spin relaxation rate in thin-shell CdSenanocrystals.Our experimental results can successfully be
described by a model proposed by Efros3, if a magnetic field dependent spin relaxation rate is introduced.

(1) Mahler, B.; Spinicelli, P.; Buil, S.; Quelin, X.; Hermier, J.-P.; Dubertret, B. Nature materials2008, 7, 659-64.

(2) Brovelli, S.; Schaller, R. D.; Crooker, S. a; García-Santamaría, F.; Chen, Y.; Viswanatha, R.; Hollingsworth, J. a;
Htoon, H.; Klimov, V. I. Nature communications2011, 2, 280.

(3) Johnston-Halperin, E.; Awschalom, D. D.; Crooker, S. A.; Efros, A. L.; Rosen, M.; Peng, X.; Alivisatos, A. P.
Physical Review B2001, 63, 205309.
 NaNax5:7Ͳ11may2012
Fuengirola,Spain
“LIQUIDCRYSTALDENDRIMERSBASEDFUNCTIONALSYSTEMS:FROMCONDUCTIVE
MATERIALSTOGENECARRIERS”.
ElisabettaFedeli,1AlexLancelot,1PilarCalvo,1MadalinaBucos,2MercedesMarcos,2Pilar
Romero,2TeresaSierra,2JulieMovellan,3JoséLuisSerrano,3

1
PharmaMarGrupoZeltia,AvdadelosReyes1,Pol.Ind.LaMina,28770ColmenarViejo(Madrid),Spain.
2
InstitutodeCienciadeMaterialesdeAragón,QuímicaOrgánica.FacultaddeCiencias,UniversidaddeZaragozaͲCSIC.50009
Zaragoza,Spain
3
InstitutodeNanocienciadeAragón,QuímicaOrgánica.FacultaddeCiencias,UniversidaddeZaragozaͲCSIC.50009Zaragoza,
Spain
[email protected]

Dendrimers, as compounds with multiple functionalisable terminal groups, are suitable
platforms for the combination of promesogenic units, providing order and orientation, with
other functional units incorporating other physical property1Ͳ4. The resulting combination
‘function+orientation’withinonematerial,makesliquidcrystaldendrimersaveryconvenient
tool for the accomplishment of multifunctional materials with preferent macroscopic order
andorientation.Moreover,whenthesecompoundsarefunctionalisedwithunitsthattendto
segregate, these units are forced to be located in neighbouring positions, giving rise to
unexpectedstructuresandsingularproperties.Takingintoaccountthesecharacteristicsofthe
dendrimerswearepreparingmultifunctionalmaterialsforapplicationsinoptoelectronicsand
solarcells5,6.

On the other hand, other fundamental property of dendrimers is their high
biocompatibility. The size of the compounds, as well as their globular structure and their
external functionality, makes dendrimers suitable materials for biological applications7,8.
Taking into account this we are investigating some biomedical applications using these
materials. We are working in three fundamental objectives: i) applications of dendrimers as
gen transfection agents for adenovirus and plasmids9, ii) synthesis and preparation of JanusͲ
typedendrimersforthetransportandcontrolleddeliveryofdrugs10,andiii)evaluationofnew
syntheticderivativesandchemicallymodifieddendrimersasantiͲmalariaagents11.

1.Donnio,B.,Guillon,D.(2006)Adv.Polym.Sci.201,45.
2.Marcos,M.,MartínͲRapún,R.,Omenat,A.,Serrano,J.L.(2007)Chem.Soc.Rev.36,1889.
3.Donnio,B.,Buathong,S.,Bury,I.,Guillon,D.(2007),Chem.Soc.Rev.36,1495.
4.Rosen,B.M.,Wilson,C.J.,Peterca,M.,Imam,M.R.,Percec,V.,(2009)Chem.Rev.109,6275.
5.Percec,V.,Glodde,M.,Bera,T.K.,Miura,Y.,Shiyanovskaya,I.,Singer,K.D.,Balagurusamy,V.S.K.,
Heiney,P.A.,Schnell,I.,Rapp,A.,Spiess,H.ͲW.,Hudsonk,S.D.,Duank,H.(2002)NATURE41,384.
6.Bagui,M.,Dutta,T.,Chakraborty,S.,Melinger,J.S.,Zhong,H.,Keightley,A.,Peng,Z.(2011)J.Phys.
Chem.A,115,1579.
7.Astruc,D.,Boisselier,E.,Ornelas,C.(2010)Chem.Rev.110,1857.
8.Caminade,A.M.,Turrin,C.O.,RégisLaurent,R.,Ouali,A.,DelavauxͲNicot,B.(2011)Dendrimers:
TowardsCatalytic,MaterialandBiomedicalUses,JohnWiley&Sons,Ltd.
9.N.Feliuetal.,Biomaterials(2012),33,1970Ͳ1981
10.S.Venkataramanetal.,Adv.DrugDeliv.Rev.(2011),63,1228Ͳ46.
11.D.Bhadraetal.Pharm.Res.2006,23,623Ͳ633

 Moiré Pattern formation in Self Assembled Sheets of Vertically
Assembled Semiconductor Nanorods Superstructure
Ajay Singh1, 2, Calum Dickinson2 and Kevin M. Ryan1, 2
1
SFI-Strategic Research Cluster in Solar Energy Conversion
2
Materials and Surface Science Institute and Department of Chemical and Environmental
Sciences, University of Limerick, Limerick, Ireland,
University of Limerick, Limerick, Ireland

Self and directed assembly of nanocrystals into ordered superstructures is an area of intense
research interest as in such architectures, the discrete size defined properties of each
nanostructure can be collectively harnessed at a scale amenable to real application. In
nanocrystal,semiconductor nanorods have attracted considerable interest as building blocks
for a variety of applications ranging from biomedical diagnostics to next generation
electronics. The formation of vertically aligned nanorods into hexagonal superlattices is a
recent development leading to structured arrays suited for high density applications.
Spontaneous supercrystal organisation in nanorods requires low polydispersity in both
diameter and length which can complicate the assembly compared to that of spherical
nanocrystals. These nanorods can be pre-assembled as 2D sheets in solution by either
depletion attraction or by controlling optimum concentration of nanorods in solution.
Further, 2D sheets can be deposited in any substrate to form micrometre sized superlattice.
When these superstructures viewed under TEM, the misorientation between these
multilayers becomes apparent by generating moiré patterns. The hexagonal motifs from the
moiré patterns are found to be directly related to the misorientation angle, which could be
measured from the SAED or FFT patterns. In this work, we focus on understanding how
different moiré pattern arise from vertically aligned nanorods superstructure. The moiré
patterns in nanorod superlattice were extensively studied by HRTEM, STEM, HESEM and
SAED.
 Quantum Dot Nanocrystals for Displays and Lighting

Jonathan Steckel, Co-founder & Director, Materials Development and Manufacturing, QD

VISION, INC. (Contact Author, Presenting Author)

Quantum dot (QD) semiconductor nanocrystals have been considered in a broad range of
applications, from biological tagging to LEDs, lasers, displays, lighting and solar cells. In their
photoluminescent mode of operation, QDs are currently in lighting products, and have the
promise to be in liquid crystal display products in the near future. In electroluminescent mode,
quantum dot light emitting devices (QLEDs) are an emerging class of thin-film hybrid organic-
inorganic structures that can potentially achieve best-in-class performance amongst large-area
emissive light sources. Market research projects world-wide QD production to increase from
~1kg today to ~1000 kg by 2015. This talk will focus on the design and synthesis of QDs
specifically for lighting and display products.
From Nano- to Bio-Interfaces, Lessons Learned.

Francesco Stellacci
Institute of Materials, Ecole Polytechnique Fédérale, Lausanne (EPFL), Switzerland

A bird eye view of any folded protein shows a complex surface composed of
hydrophobic and hydrophilic patches closely packed. To date little is known on the
fundamental properties that such packing determines. In this talk I will present my
group’s endeavor into the synthesis, characterization, and understanding of a family
of nanomaterials (mixed monolayer protected nanoparticles) that posses a surface
coexistence of patches of opposite hydrophilicity resembling that present on folded
protein. I will show that these materials are ideal model compound to uncover the
basic properties that such coexistence determines at the solid liquid interface, and
will conclude with example of application of these nanoparticles when used as
mimic of biological entities (e.g. as cell penetrating peptides, as nano-enzymes, etc.).
 Colloidal Nanocrystals Coupled to Optical Semiconductor Microtube Resonators
Ch. Strelow, R. Seher, A. Mews, and T. Kipp
Institute of Physical Chemistry, University of Hamburg, Germany

Semiconductor microcavities confining light on a length scale of its wavelength have gained
considerable interest in the last years for both, possible applications and fundamental research. Of
special interest are microcavities which are coupled to quantum emitters. Such systems might be
applicable in e. g. low-threshold lasers or single-photon sources. Furthermore they offer the
fascinating possibility of cavity quantum electrodynamics experiments in solid-state systems.

Recently we demonstrated that self-supporting microtubes can act as novel kinds of optical
microcavites [1,2]. These microtubes are fabricated from epitaxially grown strained semiconductor
layer systems by utilizing the self-rolling mechanism of strained bilayers lifted-off from the substrate.
Such microtubes have typically a diameter of about 5 µm and wall thicknesses of about 100 nm.
In this contribution, we show that after bringing colloidal PbS nanocrystals into the core of a microtube,
these quantum emitters couple to optical modes of the passive microtube resonator [3]. The coupling
is extraordinary efficient due to the long ranging evanescent fields of optical modes guided in the very
thin walls of the microtube. Our experiments open up perspectives of using nanocrystals of different
size, shape, and material in semiconductor microcavities. Such hybrid systems of microstructures
resulting from epitaxially grown layer systems and chemically synthesized nanocrystals offer a
fascinating variety of experiments on light-matter interaction and possible applications, for example as
new light sources.

[1] T. Kipp et al., Phys. Rev. Lett. 96, 077403 (2006).

[2] Ch. Strelow et al., Phys. Rev. Lett. 101, 127403 (2008).
[3] K. Dietrich et al., Nano Letters 10 (2), 627-631 (2009).
 Light–induced orientation and mass transport of dendritic LC materials

J. Tomczyk, E. Heydari, A. Sobolewska and J. Stumpe,

Fraunhofer Institute for Applied Polymer Research, Geiselbergstr. 69,

14476 Potsdam, Germany, [email protected]

Modern technologies require advanced materials allowing efficient processing to achieve more efficient,
smaller/thinner and multifunctional devices. This is especially true for optical technologies, whereas LCDs,
diffractive optical elements or organic laser are examples for this trend. Advanced oligomers and polymers
combine extremely large opportunities in variations of structures and tuning of properties with cost efficient
polymer like processability. In most cases device functions are based on the structuring of material. All-
optical methods for nano- and micropatterning are required to overcome restrictions of lithographic
processing. The aim of our project was to investigate the specific properties of liquid crystalline dendrimers
concerning the formation of polarisation and diffraction elements.

The defined preparation of anisotropic films of functional polymers is of great interest for optical
applications. The irradiation of photochromic polymers with linearly polarized light offers a new approach to
induce anisotropy in polymer films. In addition to the reversible photoorientation process based on the E/Z
photoisomerisation of azobenzene containing polymers, a new polymer systems were developed for this
purpose in which the anisotropy is generated by the angular-selective photo-cycloaddition. Under this aspect
the photocycloaddition of cinnamates derivatives were studied. In contrast to azobenzene containing
polymers the new materials do not absorb light in the visible range. Extraordinary high values of optical
anisotropy were achieved using related liquid crystalline dendrimers. In this case the photo-induced
anisotropy generated in the glassy state was used as starting point for the subsequent alignment of the film by
annealing. Thus, the final order is established by the combination of the two ordering principles, whereas the
self-organization of the LC dendrimers starts from the small photo-induced anisotropy. Depending on the
type of the photoreaction and on the irradiation conditions an orientation parallel or perpendicular to the light
polarization can be “developed”. This process works co-operative, i.e. the other non-photosensitive, but
mesogenic side groups are aligned as well.

The same azobenzene containing materials form surface relief gratings by mass transport upon
continued holographic exposure. Disadvantages of functional polymers are expensive synthesis, required
purification, bad solubility and a broad distribution of molar masses. Additional requirements are good film
forming properties, high efficiency of grating formation and high stability of induced structures. Overcoming
drawbacks of conventional photochromic polymers, new concepts based on azobenzene functionalized
dendrimers and systems, in which the photochromic moieties are attached by non-covalent interactions to the
dendritic core or the backbone of polyelectrolytes were investigated, which were synthesised by the partner
groups in the framework of the Dendreamer project. The new concepts work with a broad variety of
azobenzene materials. Especially such ionic systems and glass forming low molecular materials require
further investigation.
HOLOGRAPHIC PATTERNING OF ORGANIC-INORGANIC NANOCOMPOSITES

J. Stumpe, O. Sakhno, L. Goldenberg and E. Heydari

Fraunhofer Institute for Applied Polymer Research, Geiselbergstr. 69, 14476 Potsdam, Germany
[email protected]

Organic-inorganic nanocomposites containing inorganic nanoparticles (NP) embedded in a photo-

processable organic matrix have been the subject of significant interest in optics and photonics. Such
nanocomposites combine the advantages of organic and inorganic systems in new hybrid materials useful for the
creation of efficient and multifunctional holographic elements for optical, electro-optical and photonic
applications.
The developed holographic nanocomposites are based on photo-polymerisable acrylate monomers and
organically capped inorganic NPs. The key problem, the compatibility of the inorganic NPs with the organic
monomers was successfully solved by capping the NP surface with properly designed organic shells. In this way,
inorganic NPs up to 50wt% are introduced in photo-processable organic media. Different inorganic NPs such as
TiO2, ZrO2, SiO2, LaPO4:Ce3+,Te3+, Au or Ag with sizes of 1-14 nm, having refractive indeces ranging from 1.4
to 2.5 and different organic shells were investigated. These optically transparent nanocomposites were
successfully used for the effective inscription of periodic volume structures by holographic photopolymerisation.
The different nanocomposites, their holographic performance and some examples for functional polymer-NP
structures will be discussed.
The formation of periodic volume structures is based on the photopolymerisation induced diffusion
mechanism, where the periodical distribution of the NP having higher or lower refractive index (RI) compared to
the original polymer matrices, provides structures with high RI contrast in the spatial period range of 0.4-5 μm.
The optimization of the composite properties (nature of core and shell, NP size and concentration, properties of
reactive part) and parameters of holographic exposure allows to obtain permanent high efficient transmission
gratings with low optical losses. Application of specially designed functional NPs makes it possible not only to
record effective diffractive volume structures, but also to introduce other physical properties into the holograms
such as light-emission or NLO properties. Moreover, 2D volume structures recorded by three laser beams were
also fabricated in a ZrO2 containing composite. Using the photoluminescent LaPO4:Ce3+,Te3+ NP, volume
transmission holograms with a diffraction efficiency up to 80% and simultaneously performing a local light-
emission in the grating planes were also developed.
The combination of easy photo-patterning of soft organic compounds with physical properties of
inorganic substances in new nanocomposite materials and the flexibility of the holographic patterning method
allow the fabrication of mono- and multifunctional 1D and multi-dimensional passive or active optical and
photonic elements.

[1] T. Smirnova, O. Sakhno, V. Bezrodnyi, J. Stumpe, Appl. Phys. B. 2005, 80, 947.
[2] O. Sakhno, L. Goldenberg, J. Stumpe, T. Smirnova, Nanotechnology 2007, 18, 105704.
[3] O. Sakhno, T. Smirnova, L. Goldenberg, J.Stumpe, Mater. Sci. Eng. C, 2008., 8, 28,
[4] G. Garweitner, L. Goldenberg, O. Sakhno, M. Antonietti, J. Stumpe. Small, 2007, 9, 1626.
[5] O. Sakhno, L. Goldenberg, J. Stumpe, T. Smirnova, J. Opt. A: Pure Appl. Opt. 2009, 11, 024013.
Photocatalytic water splitting mediated by nanocrystal colloids: synthetic control
over interfacial hole transfer.

Yogesh Surendranath‡, A. Paul Alivisatos†‡§

Efficient methods for storing solar energy in the form of chemical fuels are
needed to enable widespread solar utilization. A cost-effective method for
effecting this overall solar-to-fuels conversion entails combining the disparate
functions of light capture, charge separation, photovoltage generation, and
electrochemical water-splitting catalysis into one or more colloidal constructs.
While cadmium-chalcogenide nanocrystals possess tunable band gaps and high
extinction coefficients well suited to photoelectrochemical water splitting they are
limited by two key challenges: (1) they undergo rapid oxidative photo-corrosion
and (2) their excited state lifetimes (~5-30 ns) are too short to mediate fuel
forming electrochemical reactions which take place on the micro and millisecond
time scale. The present work addresses both of these problem simultaneously by
decorating CdSe/CdS heterostructure surfaces with alkyl ferrocene moieties
which will serve as efficient hole transfer relays. The surface coverage and
derivitization of the ferrocene moieties are independently modulated to effect
systematic control over the charge separation lifetime. Furthermore, by
encouraging rapid hole transfer to ferrocenes of modest oxidation potential, the
CdSe/CdS surface is effectively protected from photocorrosion while still enabling
oxidation chemistry in solution. Transient absorption studies isolate the driving
force/rate relationships for hole transfer and provide a rational framework for
optimization. Coupling these surface functionalized heterostructures with
hydrogen evolution catalysts will therefore enable stable, efficient, colloidal water
splitting.
†
Department of Materials Science and Engineering and ‡Department of
Chemistry, University of California, Berkeley, California 94720, United States
§
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley,
California 94720, United States
Title
Photogeneration of Charges in Blends of Quantum Dots and Organic Semiconductors

Authors
S. ten Cate, J. M. Schins, and L. D. A. Siebbeles

Abstract
Lead-chalcogenide quantum dots are of interest for highly efficient solar cells, where one
photon can produce multiple charges by means of multiple exciton generation. To extract
these charges, we blend PbS quantum dots, with the hole-accepting conjugated polymer
P3HT, and the electron-accepting material PCBM. Ultrafast transient absorption is used
to monitor the exciton population, and ultrafast terahertz spectroscopy to determine the
photoconductivity. It is shown that charges are indeed extracted from the quantum dots,
but, unexpectedly, they are not mobile. This result can be explained with an electrostatic
model, in which the PbS polarizability causes extracted charges to be strongly Coulomb-
attracted to their induced image
charges.
 Cation exchange in CdSe nanocrystals controlled by the basicity
hardness of a ligand mixture
Mykhailo Sytnyk,a Daniel Primetzhofer,b Dominik Goebl,b Peter Bauer,b and Wolfgang Heissa
a
Institute of Semiconductor and Solid State Physics, University Linz, Linz, Austria
b
Institute of Experimental Physics, University Linz, Linz, Austria

Cation exchange (CE) has been demonstrated to be a versatile tool for manipulating the
properties of colloidal nanocrystals by completely exchanging the materials,1 by formation of a
shell,2 or by alloying.3 The CE process, which depends on concentration of precursors, time of
CE process, and on reaction temperature, can be a rather uncontrolled process in several cases.
The treatment of CdSe nanocrystals with AgNO3 in methanol, for instance, results in an
immediate total CE within a few seconds. Thus, it is difficult to obtain a controlled alloying of
the CdSe nanocrystals by the CE, e.g., to tune their band gap energy. Here we show that the
addition of ligand mixtures to the reaction mixture gives an additional powerful tool to adjust the
degree of CE, enabling the alloying of CdSe nanocrystals with predictable compositions. The
cases of CdSe nanocrystals alloyed in a concentration range between 0 < x < 0.4 with either Hg
or Zn are demonstrated.
According to the hard and soft acid and base theory from Pearson,4 Hg2+ and Zn2+
represent two opposite cases, since Hg2+ is a relatively soft acid in comparison to Cd2+ while
Zn2+ is a harder acid. For alloying of CdSe nanocrystals in a controlled way, the basicity
hardness of the added ligand mixtures is adjusted to promote/inhibit CE. For that purpose
mixtures of oleylamine, a hard base, with trioctylphosphine, a soft base, are applied. The CE
process, performed at room temperature for 5 hours, results in a linear dependence of the
concentration of exchanging ions in the nanocrystals x as function of the ligand mixture ratio.
Oleylamine rich ligand mixtures promote exchange of Cd2+ by Hg2+ while trioctylphosphide rich
mixtures promote CE of Cd2+ by Zn2+. The CE process is conveniently monitored by the shifts of
the nanocrystal band gap energy (Figure 1a,c) and quantitatively proven by Rutherford
backscattering measurements (Figure 1b). After CE treatment neither size nor shape of the
nanocrystals is changed. While the versatility of the CE has been demonstrated for different
nanocrystal materials, the concept of adding ligand mixtures with adjusted basicity hardness to
control the speed of CE process, demonstrated here for CdSe nanocrystals, could be beneficial
also for other pairs of soft and hard metal-ion acids used for CE.

Figure1. a) Optical absorbance of CdSe nanocrystals treated with Hg2+, b) Rutherford

backscattering data confirm the CE process and evidence Hg concentrations up to 40% relative
to Cd. c) Optical absorbance of Cd1-xZnxSe nanocrystals obtained by CE.

1. D.H. Son, S.M. Hughes, Y. Yin, A. P. Alivisatos, Science, 306, 1009 (2004).
2. J. Zhang, Y. Tang, K. Lee, M. Ouyang, Science, 327, 1634 (2010).
3. A. M. Smith and S. Nie, J. Am. Chem. Soc., 133, 24 (2011).
4. R. G. Pearson, , J. Am. Chem. Soc., 85, 3533 (1963).
 Next Generation of Magnetic Nanoparticles for Biomedical Applications
Nguyen TK Thanh
Reader/Associate Professor
1
The Davy-Faraday Research Laboratory, The Royal Institution of Great Britain, 21 Albemarle Street, London W1S
4BS, UK, 2Department of Physics & Astronomy, University College London, Gower Street, London, WC1E 6BT, UK
* Email: [email protected] http:www.ntk-thanh.co.uk
We have used different wet chemical methods to synthesise magnetic nanoparticles of different compositions, size,
shapes and surface chemistries for biomedical applications. Here are a few examples:
1. Tunable shapes of magnetic nanoparticles: Fe-Pt, Fe-Pd and Fe-Pt-Pd alloys:.We achieved the controlled syntheses
of Fe-Pt, Fe-Pd and Fe-Pt-Pd nanoparticles having different isolated shapes including sphere, cube, octopod-cube, star,
rod, bilobe, tetrahedron, or multipod with size of 5-50 nm. The as-synthesised NPs are homogeneous and no further size
selection is needed.
2. Synthesis of magnetic nanoalloys from bimetallic carbonyl clusters: Here we report the synthesis of FeCo3, FeNi4,
Fe3Pt3 and Fe4Pt alloy magnetic nanoparticles with average diameters of 7.0 nm, 4.4 nm, 2.6 nm and 3.2 nm, respectively,
by the thermal decomposition of bimetallic carbonyl clusters.
3.Facile synthesis of stable water-soluble magnetic CoPt: solid, nanochains/wires and hollow NPs: We present a novel,
facile, template-free synthetic method of water-soluble CoPt NPs by simultaneous reduction of cobalt and platinum salts
in water in the presence of polymer and/or peptide ligands.
4. Synthesis of Magnetic Co Nanoparticles by Pulsed Laser Irradiation of Cobalt Carbonyl in Organic Solution:
Here, we report the synthesis of sub 4 nm cobalt nanoparticles by using pulsed laser irradiation to decompose cobalt
carbonyl in a solution of stabilising ligands.
5 .Fabrication of water-soluble magnetic nanoparticles by ligand-exchange with thermo-responsive polymers:
In this work, water-stable Co and J-Fe2O3 nanoparticles were synthesised using a two-step method involving the
thermal decomposition of the organometallic complexes in the presence of oleic acid followed by a ligand-exchange
process with thermo-responsive polymers.
6. Superparamagnetic Fluorescent Nickel-Enzyme Nanobioconjugates:We report, for the first time, the synthesis of
superparamagnetic and fluorescent nickel (Ni) nanoparticles (consisting of a single material) directly conjugated to an
enzyme, bovine pancreatic a-chymotrypsin (CHT), by chemical reduction in aqueous solution.
7. Synthesis of core-shell gold coated magnetic nanoparticles and their interaction with thiolated DNA: Here, the
synthesis and characterization of bimetallic nanoparticles containing a magnetic core and a gold shell are discussed.
8. Magnetic CoPt nanoparticles as MRI contrast agent for transplanted neural stem cells detection: The results
showed that MRI could efficiently detect low numbers of CoPt-labeled NSCs with the enhanced image contrast. Our
study demonstratedthat MRI of grafted NSCs labeled with CoPt NPs is a useful tool to evaluate organotypic spinal cord
slice models and has potential applications in other biological systems
9. One-pot Synthesis and Characterization of Well Defined Core@Shell Structure of FePt@CdSe
Nanoparticles:Magnetic fluorescent FePt@CdSe core-shell nanoparticles were directly synthesized. The CdSe shell
thickness also could be varied. They exhibited superparamagnetic behaviour at room temperature.
 Study of a single colloidal core/shell CdTe/CdTexSe 1-x quantum dot with thin
alloy shell
J. Tilchin*, G. I. Maikov*, R. Vaxenburg,* A. Brusilovski*, A. Sashchiuk*, A. Neuwmann**,
A. Hoegele** and E. Lifshitz*
*
Schulich Faculty of Chemistry, Russell Berrie Nanotechnology Institute, Solid State Institute,
Technion, Haifa 32000,Israel
**
Ludwig-Maximilians-UniversitätMünchen, München80539, Germany

E-mail: [email protected]

Colloidal quantum dots (CQDs) with a core/shell structure are a focus of special scientific and
technological interests, due to their chemical and electronic tunability – as contorlled by the variation of
the chemical components or/and core-to-shell volume ratio. A micro-photoluminescence (μ-PL) of
asingle CdTe/CdSe and CdTe/CdTexS1-x CQD recently explored[1] their unique property, enabling the
generation ofsingle and multiple excitons with a blinking-free behavior. However, the identification of
the exciton states requires further investigation, exploring the core/shell band off-set (e.g., type I, type-II
or quasi-type-II), angular momentum of electronic states, and the corresonding radiative lifetime.
The present work focuses on the optical polarizaton properties of the μ-PL spectra of an
individual CdTe/ CdTexSe 1-x CQD, with a thin shell (< one monolayer), behaving as a type-I
semiconductor, which is close to the behaviour of a core-only CQD, however, rendering the dot with a
chemical and photochemical stability over a length of time. The spectra were recorded at 4.2K, using a
fibre-based μ-PL magneto-optical set-up (calibrated
appropriately for the polarization measurements). The spectra 30

were examined when recorded under various excitation powers,

with/without the influence of an external static magnetic field. 25

The spectra changed their pattern with the increase of

the excitation power, evolving from an isolate band of the 20
I transition
II transition
Intensity (arb. units)

single-exciton, to a rich spectrum, comprised of multiple-bands

to lower and higher energy sides of the single-exciton. Some 15

of those bands also showed satellite bands, related to the

interaction of each electron-hole pair with other carriers in the 10

dot (so-called spectators), and a few of which showed

additional split by the magnetic field. As a representative case, 5

the optical polarization properties of the single-exciton

emission band is elaborated here. In all recorded spectra (see 0
figure), the single-exciton emission appeared as a doublet band, 1.89 1.9 1.91
Energy (eV)
1.92 1.93

when the low energy wing showed a linear polarization, while

the high energy side has circular polarization. Figure: Circular (blue) and linear (red)
emission of single exciton emission
The experimental results were supported by a theoretical recordet at 4.2 K. Calculated linear (red
model based on k•p method, considering a zinc–blende line) and circular (blue line) polarized
crystallographic structure with an axial approximation. The calculated results are in a good agreement
transitions.
with the measured energy structure (see figure). Thus, the optical polarization properties revealed
information about the shape anisotropy of the CQD, as well as explore the fine structure (e.g., angular
momentum) of the electron states, with significant contribution to the implementation of CQDs in gian
devices or photovoltaic cells.

References

[1] Osovsky R, Cheskis D, Kloper V, Sashchiuk A, Kroner M and Lifshitz E 2009 Physical Review Letters102 197401.
FROM HOT-INJECTION SYNTHESIS TO HEATING-UP SYNTHESIS OF
MONODISPERSE COBALT NANOCRYSTALS

Jaakko V. I. Timonen,* Eira T. Seppälä, Olli Ikkala and Robin H. A. Ras

Department of Applied Physics, Aalto University School of Science, P.O.B. 15400, FI-
00076 Aalto, Finland
*Current address: Debye Institute for Nanomaterials Science, Utrecht University,
P.O.B. 80.051, 3508 TB Utrecht, The Netherlands
Email: [email protected]

Colloidal nanocrystals of well-defined size and shape are required in several emerging
applications that take advantage of size-dependent properties such as quantum
confinement, superparamagnetism or surface plasmon resonance. Accurate tuning of the
nanocrystal size requires understanding in the physicochemical mechanisms involved in
the nucleation and growth of the crystals. In spite of extensive ongoing research, these
mechanisms are still not fully understood owing to their complexity.

We studied nucleation and growth of cobalt nanocrystals in the well-known hot-

injection synthesis method, in which thermally unstable cobalt precursor (cobalt
carbonyl) is injected into hot organic solvent (o-dichlorobenzene) containing surfactants
(oleic acid and trioctylphosphine oxide).[1] We found that the nucleation does not take
place during the precursor injection as has been believed, but is instead delayed for even
a few minutes, after which the growth of the nanocrystals takes place quickly within
tens of seconds.[2] The number of formed nuclei, and hence the size of the mature
nanocrystals, can be tuned by changing the heating rate after the temperature drop
induced by the precursor injection: rapid heating results in a larger number of nuclei and
smaller mature nanocrystals, and vice versa. Since the overall reaction is endothermic, a
second drop in temperature of approximately 10ºC is observed during the nanocrystal
growth. This second drop can be understood to be due to decomposition of the cobalt
carbonyl and the effect of the heating rate after the first temperature drop on the
nucleation rate can be qualitatively understood in terms of classical nucleation theory.

The delayed nucleation suggests that the precursor injection is not important for the
formation of monodisperse cobalt nanocrystals. We show that by mixing the cobalt
precursor with the same solvent and the surfactants as in hot-injection method at room
temperature and heating the solution up to the decomposition temperature of the
precursor leads to formation of monodisperse cobalt nanocrystals identical to those
made by the hot-injection method.[2] This ‘heating-up’ method is more accurately
controllable than the hot-injection method, easier to upscale to industrially relevant
scales, and may even eventually lead to a highly desirable continuous fabrication
process of monodisperse cobalt nanocrystals.

[1] V.F. Puntes, K.M. Krishnan and A.P. Alivisatos, Science 291, 2115 (2001)
[2] J.V.I. Timonen, E.T. Seppälä, O. Ikkala and R.H.A. Ras, Angew. Chem. Int. Ed. 50,
2080 (2011)
 Photochromicdendrimers.II.Lightinducedeffects
JaroslawTomczyka,b,AnnaSobolewskaa,ZsuzsannaT.Nagyc,BertrandDonnioc,
DanielGuillonc,JoachimStumpea,b
a
FraunhoferInstituteforAppliedPolymerResearch,Geiselbergstrasse69,14476Potsdam,Germany,
b
UniversitätPotsdam,DepartmentofChemistry,KarlǦLiebknechtǦStrasse24Ǧ25,14476Potsdam,Germany
c
CNRS,IPCMSandStrasbourgUniversity,23rueduLoess,67034Strasbourg,France

eǦmail:[email protected]

Dendrimers showing a highly controlled molecular structureafter functionalization with various

photosensitive and/or liquid crystalline groups can become new multifunctional anisotropic materials with wide
variety of physical properties thereby they can be considered as advanced materials with possible applications
especiallyinopticaltechnologies.
The light induced anisotropy and formation of the diffraction grating were investigated in newly
synthesizedfirstgenerationstarǦlikedendrimersfunctionalizedwithazobenzenegroupsandmesogenes(Fig.1)[1].
The dendrimers were synthesized and characterized by CNRS/IPCMS group (Strasbourg, France) in the frame of
European “Dendreamers” project. The measurements of the angular dependent optical anisotropy reveled a
dichroismashighas0.77(366nm)forthecompoundshowninFig.1whencombinedthematerialwithmultiǦstep
irradiation procedure (Fig. 2). The diffraction gratings were recorded using the holographic technique [2]. The
measurementswereperformedatroomtemperatureandattemperaturesofLCstateofstudieddendrimers.There
weresomedifficultiesinobtainingthegoodopticalqualityfilmsnecessaryforsuchmeasurements(filmsrevealed
very fast crystallization thereby significantly hindering the optical measurements) therefore gratings were
successfully recorded only in few dendrimers. The high diffraction efficiency (| 13 %, room temperature) was
obtainedonlyformentionedabovecompound.Increaseofthetemperaturetotheliquidcrystallinephasedidnot
cause the enhancement of the diffraction signal. A surface relief grating with very low amplitude was observed.
Furtheropticalstudiesofsuchmaterialsrequiretheimprovementofthefilmformingproperties.
C11H23
O

N
N

O O
O O

NC CN

 
Fig. 1. Exemplary structure of the first generation dendrimer Fig. 2. Polar plots of the absorbance at 366 nm of the dendrimer with
functionalized with the azobenzene (red) and 4Ǧcyanobiphenyl azobenzene and 4Ǧcyanobiphenyl mesogenes in the initial state and
mesogenes(darkblue). afterlinearpolarizedirradiation.


Acknowledgment:ThisworkhasbeensupportedbytheMarieCurieActions,SeventhFrameworkProgramme,“Dendreamers”
project.

[1] Zs. T. Nagy, J. Tomczyk, A. Sobolewska, B. Heinrich, B. Donnio, D. Guillon, J. Stumpe, NaNaX5: “Photochromic
dendrimersI.Synthesisandliquidcrystallineproperties”.
[2]L.Kulikovsky,O.Kulikovska,L.M.Goldenberg,J.Stumpe,ACSAppl.Mater.Interfaces2009,1,1739.
 One Phase Growth of Fluorescent Metal (Au or Ag) Nanoclusters

Laura Trapiella-Alfonso,a,b M. A. Habeeb Muhammed,a Fadi Aldeek,a and Hedi Mattoussia

a
Florida State University, Department of Chemistry and Biochemistry, 4006 Chemical Science Building,
Tallahasse, Florida 32306,
b
Oviedo University, Department of Physical and Analytical Chemistry, Faculty of Chemistry, Julian Claveria,
33006 Oviedo, Spain.

Nobel-metal nanoclusters NCs (e.g., those made of Au and Ag) consisting of tens of
atoms in the core are a new class of nanomaterials exhibiting distinct optical, electrical, and
chemical properties; this makes them promising materials for developing a new generation
of sensors, catalysts, and for use in biological applications. With a size comparable to the
Fermi wavelength of the electron , NCs in general can exhibit luminescence from ultra violet
(UV) to the near infra-red (NIR) regions with change in core size.1 They offer an alternative
to quantum dots (QDs) or organic dyes. They are highly attractive for bio-imaging and bio-
labeling due to their very small size and because they do not face the stigma of potential
toxicity often encountered by luminescent QDs. They also offer a great and challenging
fundamental problem to understand cluster growth, stability, and functionality.
Herein, we demonstrate a simple and efficient one phase synthetic route to prepare
red emitting Au and Ag NCs. NCs are synthesized by reducing gold or silver precursors
(HAuCl4 or AgNO3, respectively) in the presence of thioctic acid (TA)-appended
poly(ethylene glycol) (PEG), either as or mixed with other molecular scale hydrophilic
ligands (Figure 1). The TA -appended PEG ligand acts as a strong metal affinity anchor onto
the metal surface while promoting aqueous compatibility over a broad range of conditions.
We found that aqueous dispersions of fluorescent Au are stable over long period of time
and over broad pH range (from 2 to 13); Ag NCs emission properties though less effective
than those of Au they can be enhanced by additional surface treatment. The above route
also allows easy surface- functionalization of the NCs with reactive groups (e.g., carboxylic
acid or amine). These NCs exhibit luminescence with high yields (QY = 10-15 %), high
colloidal stability and long luminescent lifetime (Wrad = 300 ns). We will describe the synthetic
route along with the
structural, optical and
spectroscopic
characterization of these
materials. We will also
present our initial attempt
to integrate these materials
in biological structures and
their use to probe energy Figure 1: Schematic depiction of the one phase synthesis of
transfer phenomena. fluorescent water-soluble Au or Ag nanoclusters.

Reference

1. Zheng, J., P.R. Nicovich and R.M. Dickson, Ann. Rev. Phys. Chem., 58 (2007), 409.
SILICON NANOCRYSTALS: Why do some colloidal Si-NCs
exhibit size dependent photoluminescence while others simply
have the blues?
Jonathan G.C. Veinot
<[email protected]>, Department of Chemistry, University of Alberta, Edmonton, AB.
www.chem.ualberta.ca/~jveinot

Semiconductor nanocrystals (NCs), commonly known as quantum dots (QDs),

are unique materials that exhibit size and shape dependent optical, electronic, and
chemical properties. The chemistry and photophysics of prototypical CdSe-QDs are well
developed and largely understood. Consequently, these materials, and their core-shell
heterostructure counterparts, show great promise as active systems in many
applications. Despite their favourable properties, legislation already exists, or is pending,
in numerous jurisdictions that restricts, and in some cases bans, heavy metals in many
industrial and consumer uses. While some debate exists over the validity of these
regulations, they do pose a tremendous barrier to the integration of CdSe-QDs into
consumer products and biomedical uses.
Silicon NCs offer a variety of benefits over the QDs noted above, not the least of
which is their biocompatibility. Adding to their appeal, Si-NCs are also compatible with
standard electronics and communications platforms, some exhibit size dependent
photoluminescence throughout the visible and NIR spectral regions, and evidence to
date suggests stabilizing surface groups are not labile. Unfortunately, Si is not
compatible with traditional solution-based precipitation reactions that afford exquisite
tunability of nanoparticle dimensions and by extension their properties. In this regard,
numerous innovative solution-, gas-, and solid-phase methods have been developed to
realize size-controlled Si-NC synthesis. Existing preparative procedures may be broadly
classified into low-temperature solution and high-temperature methods. All reported
procedures afford Si-NCs that appear seemingly identical. However, based upon their
optical response it is clear they are not. Si-NCs prepared using high-temperature
methods routinely exhibit relatively low quantum yield photoluminescence that follows
the predictions of the effective mass approximation. Si-NCs prepared via solution
methods exhibit comparatively high quantum yield blue emission that is independent of
particle size. Despite many creative proposals, a concrete explanation for this difference
has eluded the nanomaterials community for no less than a decade. This apparent
dichotomy brings into question our understanding of Si-NC optical and electronic
properties and potentially limits the full scope their applications.
This presentation will introduce Si-NCs and many of the standard literature
procedures used for their preparation. Focus will then shift to oxide-embedded and
surface functionalized freestanding Si-NCs prepared using procedures developed in the
Veinot Laboratory and how a methodical investigation of these materials and their
reactivity has led to the important identification of the origin of the blue emission noted
above. A detailed comparison of blue-emitting solution modified Si-NCs and Si-NCs
synthesized by the Kauzlarich (UC Davis) and Tilley (Victoria University of Wellington)
groups will also be described.
JOINING NANOMATERIALS AND DENDRIMERS: APPLICATIONS IN DIAGNOSTICS.

Yolanda Vida1, Antonio Jesus Ruiz-Sanchez1, Maria Isabel Montañez*,2, Seda Kehr3, Daniel
Collado1, Francisco Najera1, Luisa de Cola3, Ezequiel Perez-Inestrosa*,1
1
Organic Chemistry Department, University of Malaga, 29071 Malaga, Spain
2
Research Laboratory, IMABIS Foundation-Carlos Haya Hospital, 29009 Malaga, Spain.
3
Physikalisches Institut, Universität Münster, Mendelstrasse, 7, D-48149, Münster, Germany
E-mail: [email protected]

The design of new nanomaterials for bioapplications is an important topic nowadays, mainly in
phototherapy, bioanalysis or diagnosis. 1,2 In particular, complex functional materials consisting of
bioactive molecules immobilized on solid supports present potential practical biosensor
applications. Advances in hybrid materials that combine the high functionality of surfaces with
defined size and controlled peripheral multivalence components are for instance needed. The solid
support used must satisfy certain conditions, must be robust and able to carry the active component.
Silica nanoparticles and zeolites have excellent biocompatibility and virtually no toxicity and posses
surrounding reactive groups that allows surface functionalization. Additionally the synthesis of
those nanomaterials with controlled size and shape is easily achieved.
On the other hand we exploit dendrimers as versatile biomimetic macromolecules for templating
sensor surfaces. The controlled peripheral multivalence of dendrimers allow us to obtain well-
defined building blocks as a scaffold with reactive chemical functionalities to couple the desired
haptens over a solid phase. The critical role of immobilization of the dendrimers protocol in
supports has been evaluated.
The in vitro testing of allergic reactions by RAST is based on the amount of IgE (present in
the human serum) reacting specifically with the allergens attached on a solid support. Different
studies and modification of this kind of test has been reported by our group.3 The use of silica
nanoparticles or zeolites and improvements in the immobilization process in supports should
increase the efficiency of the system.
We report the synthesis and characterization of surface modified silica nanoparticles and zeolites
with functionalized dendrimers that will be used in the in vitro WHVWLQJ RI DOOHUJLF UHDFWLRQ WR ȕ-
lactams antibiotics. The ability of those hybrid nanomaterials in such biosensing applications has
been evaluated. The specificity and improved sensitivity of the dendrimer-modified supports make
these strategies versatile for different bioactive molecules and could have significant implications
for the quantification of a wide range of specific IgE antibodies and other biomolecules of interest
in diagnosis.

[1] Strassert, C.A., Otter, M., Albuquerque, R.Q., Höne, A., Vida, Y., Maier, B., De Cola, L.
Angew. Chem. Int. Ed. 2009, 48, 7928-7931.
[2] a) Yan, J., Estévez, M. C., Smith, J. E., Wang, K., He, X., Wang, L., Tan, W Nano Today 2007,
2, 44-50. b) Achatz, D. E., Mezó, G., Kele, P., Wolfbeis, O. S. ChemBioChem 2009, 10, 2316-2320.
[3] Montañez, M. I., Perez-Inestrosa, E., Suau, R., Mayorga, C., Torres, M. J., Blanca, M.
Biomacromolecules 2008, 9, 1461-1466.
 Structures and Mechanisms in the Growth of Hybrid Ru-Cu2S
Nanoparticles; From Cages to Nanonets
Kathy Vinokurov, Janet E. Macdonald and Uri Banin
Institute of Chemistry, The Hebrew University of Jerusalem

Combining metal and semiconductor materials with well defined morphologies on a

single hybrid nanoparticle provides functionality benefiting from the joint and possibly
also synergetic properties of the disparate components. We have recently reported the
synthesis of a novel family of Ru Nano-Inorganic Caged (NICed) copper (I) sulfide
hybrid nanoparticles, which were grown through a mechanism of selective edge growth
of the Ru on the copper(I) sulfide seeds.1 We investigate the effect of reaction conditions
on the Ru-Cu2S products. There is an extraordinary sensitivity to reaction temperature in
which four product structures were discovered upon varying the reaction temperature
from 190oC to 220oC. The products changed from homogeneous nuclei of Ru along with
the free Cu2S seed at lower temperature, to Ru Nano-Inorganic Caged copper(I) sulfide,
to long thin Ru structures growing from the seed surface at the higher temperature range.
The resulting materials were imaged and characterized by Transmission Electron
Microscopy (TEM), High Resolution TEM (HRTEM) and High Angle Annular Dark
Field-Scanning TEM (HAADF-STEM). Differential Scanning Calorimetry (DSC) of the
Cu2S template nanoparticles revealed an endothermic peak at the specific temperature for
selective edge growth of Ru, and was assigned to a surface change on the seed particle.
Competition between homogeneous nucleation of the secondary material Ru and
heterogeneous nucleation on the seed Cu2S nanoparticle leading to a rich reaction
landscape will be presented.

1
Macdonald, J.E; Bar Sadan, M; Houben, L; Popov, I; Banin, U, Nature Materials, 2010, 9, 810-815
 Surface Chemistry of InP Nanocrystals Unraveled by Coupling X-Ray Photoelectron and NMR
Spectroscopies

Héloïse Virieux,a Arnaud Cros-Gagneux,a Wilfried-Solo Ojo,a Marianne Le Troedec,b Alfonso Cornejo,a Fabien
Delpech,a Céline Nayral,a Hervé Martinez,b Yannick Coppel,c Bruno Chaudret.a
a
Laboratoire de Physique et Chimie des Nano-Objet, 135 avenue de Rangueil, F-31077 Toulouse, France, bUniversité de Pau et des
Pays de l’Adour, Hélioparc-2av. Président Angot, F-64053 Pau, France, cLaboratoire de Chimie de Coordination, UPR-CNRS
8241, 205 route de Narbonne,F- 31077 Toulouse, France

Among all II-VI and III-V semiconductors, indium phosphide (InP) is probably the only one which could offer
a compatible, or even broader, emission color range similar to that of CdSe quantum dots (QDs) but
without intrinsic toxicity since InP has neither Class A elements (Cd and Hg), nor Class B elements (As and
Se).1 This, in particular, opens up applications to in vivo bio-detection using QDs emitting in the range of
maximum transmissivity of organic tissue (700-900 nm).2 However, the synthesis of InP QDs proves to be
much trickier than CdSe one, and developments remain one step behind compared to the II-VI
counterparts. The major drawback of the strategies developed so far for InP is the lack of method allowing
access to large QDs (diameter larger than 4-5 nm) and thus, the intrinsic limitation to emission at
wavelength lower than 730 nm due to unexplained growth inhibition phenomenon. We will present here,
thanks to advanced solution and solid-state NMR experiments as well as XPS measurements, a
comprehensive study on the compositional characteristics, including the surface chemistry, of InP QDs
prepared in non-coordinating solvents. We will, in particular, show that, besides the classical role of
capping ligand, palmitic acid is also involved in an organic side reaction and that species which are not
initially present but are formed in situ during the reaction course have a key role in the chemical features
(e.g., QDs growth inhibition) as well as the optical characteristics of the as-synthesized InP NCs.3

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R. Xie, D. Battaglia, X. Peng. Colloidal InP nanocrystals as efficient emitters covering blue to near-infrared.
J. Am. Chem. Soc., 2010, 132, 18147. 2 A. J. Tavares, L. Chong, E. Petryayeva, W. R. Algar, U. J. Krull.
Quantum dots as contrast agents for in vivo tumor imaging: progress and issues. Anal. Bioanal. Chem.,
2010. 3 A. Cros-Gagneux, F. Delpech, C. Nayral, A. Cornejo, Y. Coppel, B. Chaudret. Surface chemistry of InP
quantum dots: a comprehensive study. J. Am. Chem. Soc., 2010, 132, 18147.
White organic light-emitting diodes combining emission from both excitons
and exciplexes
Asta Michaleviciute1, Egle Gurskyte1, Juozas V. Grazulevicius1*, Dmytro Yu. Volyniuk1,2,Pavlo
Y. Stakhira2*, Vladyslav V. Cherpak2, Gjergji Sini3
Email: [email protected]
1
Department of Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas,
Lithuania
2
Lviv Polytechnic National University, S. Bandera 12, 79013 Lviv, Ukraine
3
Laboratoire de Physicochimie des Polymères et des Interfaces, EA 2528 Université de Cergy-Pontoise, 5 mail
Gay-Lussac, 95031 Cergy-Pontoise Cedex

Recently, much attention is paid to the development of white organic electroluminescent

devices (WOLEDs) with the aim of their application in display technologies and lighting
systems. 1 One approach to obtain white (broadband EL emission) is based on mixing of
several colors, which result from exciton relaxation in different functional layers.2 Despite
significant progress in the practical implementation of this type of the devices the
characteristics and reliability of modern multilayer WOLEDs are considerably inferior with
respect to those of single color OLEDs. They require high applied driving voltage
forobtaining of high luminescence efficiency with good colour rendering.
One of the most simple, cheap and technologically conceptual approach for the development
of WOLEDs is mixing of molecular emission (usually blue) and exciplex or electroplex
(bimolecular excited species) emission (usually orange).3 Unfortunately, red-shifted broad
band emission of electroplexes or exiplexes usually are achieved at high values of applied
voltage (12-20 V) which leads to the increase of the temperature of the devices and to the
decrease of their life time.3 There is still a large potential for the improvement of WOLEDs
based on exciplex or electroplex emission. Usually, organic materials emitting in the blue
spectral region still suffer from low levels of efficacy and short lifetimes as compared to
those emitting in green and red. Among the most promising organic materials emitting in the
blue spectral region are glass-forming carbazole derivatives, and star-shaped compounds in
particular.4 They are characterized by good charge-transporting properties and high
photochemical stability.
Star-shaped carbazole-based compounds were synthesized by Buchwald-Hartvig method.
The materials were examined by various experimental and theoretical methods,including
differential scanning calorimetry, UV spectrometry, electron photoemission, time of flight
techniques, and DFT (B3LYP) calculations. The synthesized compounds showed high
thermal stability with the initial weight loss temperature higher than 400 °C. The star-shaped
compounds were used for the preparation of bilayer white organic light-emitting diodes
which combine emission from both pure excitons and exciplexes. The brightness of white
organic light emitting diode at 7 V is 300 cd/m2 with current efficiency 2.3 cd/A and CIE
coordinates (0.37, 0.35) which are very close to the equienergy white point (0.33, 0.33).
[1] B. Torriss, A. Hache and S. Gauvin, Organic Electronics,2009, 10, 1454–1458.
[2] M.S. Kim, J.T. Lim, C.H. Jeong, J.H. Lee and G.Y. Yeom, Thin Solid Films,2006, 515, 891–895.
[3] H. Zhu, Z.Xu, F. Zhang, S. Zhao, Z. Wang and D. Song, Synth. Met.,2009, 159, 2458–
[4] 13. V.V. Cherpak, P.Y. Stakhira, D.Yu. Volynyuk, J. Simokaitiene, A. Tomkeviciene, J.V. Grazulevicius,
A. Bucinskas, V.M. Yashchuk, A.V. Kukhta, I.N.Kukhta, V.V. Kosach andZ.Yu. Hotra, Synth. Met., 2011, 161,
1343–1346.
 LABELING CHOLINESTERASES USING SEMICONDUCTOR
NANOPARTICLES FOR BIOLOGICAL APPLICATIONS

Nir Waiskopf 1,2, Rany Rotem1, Itzhak Shweky1, Uri Banin1, Hermona Soreq2
1
The Institute of Chemistry and 2The Silberman Institute of Life Sciences, and the Interdisciplinary
Center for Neural Computation
The Hebrew University of Jerusalem, Edmond J. Safra Campus - Givat Ram, Jerusalem 91904

Acetylcholinesterase (AChE) and Butyrylcholinesterase (BChE) are the major acetylcholine

hydrolyzing enzymes in mammalian systems. In humans, impaired cholinesterase functioning is
causally involved in many pathologies, including Alzheimer´s and Parkinson´s diseases, anxiety, etc.
Recombinant cholinesterases have been developed for therapeutic use and for biomedical research;
however, there is still an unmet need for methods to follow the in vivo path, location and interactions of
these important enzymes. Synthesis and surface engineering of semiconductor nanoparticles with
unique and controlled physical and chemical properties emerges as a powerful approach for biological
and medical research. Novel works using semiconductor nanoparticles, such as quantum dots, as
fluorescent agents revealed their advantages in comparison to the traditional labeling methods. First,
they have high fluorescent quantum yield and molar extinction coefficients, which provide high
sensitivity. Second, they have a broader absorbance spectrum and a controlled, size-dependent narrow
photoluminescence spectrum which allow less complicated parallel multilabeling experiments. Third,
they are better amenable for dynamic high resolution imaging and direct follow-up in biological
milieus, due to higher thermal and photochemical stability which extend their detection time.

Given these advantages, we introduce and develop a toolkit for semiconductor nanoparticles labeling of
the recombinant cholinesterases. Separation between the different fractions, identification of labeled
and non-labeled enzymes and analysis of their biological activities were performed following gel
electrophoresis. Various characterizations of the bio-conjugates and demonstration of live cell imaging
using the conjugates will be shown.

The development of a toolkit for semiconductor nanoparticles labeling of proteins in general and of the
recombinant cholinesterases in particular, can open new venues to address key biological questions,
improve understanding of the underlying mechanisms of diseases associated with impaired functioning
of such proteins and develop the recombinant proteins for therapeutic applications.
Quantum Dots as Simultaneous Acceptors and Donors in Time-Gated Förster
Resonance Energy Transfer Relays: Characterization and Biosensing

W. Russ Algar,1 David Wegner,2 Alan L. Huston,1 Juan B. Blanco-Canosa,3 Michael H. Stewart,1
Anika Armstrong,1 Philip E. Dawson,3 Niko Hildebrandt,2* and Igor L. Medintz2
1
U.S. Naval Research Laboratory, Washington DC, United States. 2 Université Paris-Sud, Orsay,
France. 3 The Scripps Research Institute La Jolla, California, United States.
*
[email protected]

Due to its extremely sensitive distance dependence in the 1 – 20 nm range, Förster resonance
energy transfer (FRET) plays an important role in nanobiotechnology. The combination of FRET
with semiconductor quantum dots (QDs) has many advantages because QD absorption and
emission wavelengths can be tuned by QD size, the absorption spectra are very broad and the
emission peaks are very narrow. Thus, QDs can be adapted to almost any available FRET partner
in the visible and NIR spectral region. QDs are most often used as FRET donors with many
different fluorescent dyes or fluorescent proteins. Using them as FRET acceptors is much more
complicated because QDs are usually more efficiently excited by almost any wavelength than the
possible FRET donor. Lanthanide complexes can efficiently overcome this problem because their
excited state lifetimes are much longer than the ones of QDs, which makes FRET from
lanthanides to QDs very efficient after a time delay of several microseconds. In this contribution
we will demonstrate the application of QDs as a central nanoscaffold for the co-assembly of Tb-
donors and AlexaFluor acceptors such that the QDs function simultaneously as FRET acceptors
and donors. A detailed steady-state and time-resolved spectroscopic analysis of the nanobio
hybrid system confirmed the presence of the two FRET pathways. The two independent FRET
mechanisms were used for a kintetic analysis of protease activity and for single target as well as
duplexed nucleic acid hybridization assays. The results demonstrate the possibility of very
sensitive multiplexed detection of several individual biological events purely based on spectro-
temporal discrimination without different QD colors.

Further details: Algar, W. R. et al., J. Am. Chem. Soc., 2012, 134 (3), 1876-1891.
 Precise Assemblies, Clusters, Superatoms, and Cluster-Assembled Materials

Paul Weiss
California NanoSystems Institute, University of California, Los Angeles

Precise clusters offer a new set of building blocks with unique properties that can be
leveraged both individually and in materials in which their coupling can be controlled
by choice of linker, dimensionality, and structure. Initial measurements in both of
these worlds have been made. Isolated adsorbed or tethered clusters are probed
with low-temperature scanning tunneling microscopy and spectroscopy. Even closely
related elements behave differently on identical substrates. Surprising spectral
variations are found for repeated measurements of single isolated, tethered clusters.
In periodic solids, precise clusters joined by linkers can be measured experimentally
and treated theoretically with excellent agreement, in part due to the relatively weak
coupling of the clusters. This coupling can be controlled and exploited to produce
materials with tailored properties. Some of the rules of thumb for predicting these
properties are being developed through these initial studies and the limit to which
they can be applied is being explored.
 Programmed Nanostructures of Metal and Semiconductor Nanoparticles: From
Molecular Machinery Topologies to Sensor Applications

Itamar Willner
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel
([email protected])

Semiconductor quantum dots (QDs) and metal nanoparticles (NPs) exhibit unique size-
controlled photophysical and electronic properties. These properties are implemented to
develop unique sensing platforms and functional biomachineries.
Different photophysical mechanisms for the development of QDs-based sensors will be
addressed. These include the design of fluorescence-, fluorescence resonance energy transfer
(FRET)-, chemiluminescence resonance energy transfer (CRET)- and electron-transfer
quenching-based sensors. Luminescence or photocurrents will provide the readout signals of
the devices. Different QD-based sensors and biosensors will be described (detection of
explosives, DNA, aptamer-substrate complexes and enzymes). A variety of amplification
means to amplify the sensing platforms will be discussed, including the application of
enzymes or DNAzymes as catalytic labels, or the recycling of the analytes by the use of
exonucleases or endonucleases.
The intracellular application of functionalized QDs for optical monitoring of cell
metabolism and for the screening of drugs affecting the cell metabolic pathway will be
presented.
The use of biomolecules as templates for growing metal nanostructures, for activating
programmed switchable topologies of metal NPs, and for the engineering of nanoscale
devices will be presented. The systems that will be addressed include:
(i) The biocatalytic growth of Au or Ag NPs, and the dip-pen nanolithographic synthesis
of metal nanowires.
(ii) The assembly of DNA catenane systems and the application of this biomolecular
scaffold as functional machine for the reversible organization of pre-designed Au NPs
topologies, including chiral nanostructures.
(iii) The preparation of actin/Au-nanowire hybrids and their application as ATP-driven
nanotransporters.
Photoconductance spectroscopy of nanocrystalline semiconducting assemblies

Omri Wolf1,3, Yuval Ben-Sahar2,3, Uri Banin2,3, Yitzhak Balberg1,3 , Oded Millo1,3
1
Racah Institute of Physics, The Hebrew University of Jerusalem, Israel
2
Institute of Chemistry, The Hebrew University of Jerusalem, Israel
3
The Hebrew University Center for Nanoscience and Nanotechnology

Abstract

We performed photoconductance spectroscopy measurements on three types of

nanocrystalline semiconductor composites: Si-SiO2 nano-composites prepared using
co-sputtering from Si and SiO2 targets, and arrays of colloidal CdS and Au-tipped
CdS nanorods. The photo-current spectrograms measured on the Si-SiO2 nano-
composites exhibited considerably richer structure compared to the corresponding
optical absorption spectra. In particular, at least two distinct peaks were observed in
the photo-conductance data, with relative strengths that largely varied with the
volume content of the Si nanocrystalline phase and temperature. These observations
are attributed to parallel contributions to the photo-transport from sub-ensembles of
crystallites having different sizes within each sample. We can also distinguish
between the contribution of transport through an amorphous phase and percolations
paths through the Si nanocrystallites via the size-dependent quantum-confinement
effect observed for the latter.
In contrast to the above results, the photoconductance spectrograms acquired
on the colloidal CdS nanorods were remarkably similar to the absorption spectra
measured on nanorods in solution. This may reflect the higher homogeneity in these
ensembles compared to the Si-SiO2 nano-composites. However, differences between
the optical and transport spectra were observed for Au-tipped CdS nanorods (a CdS
nanorod with a gold quantum-dot grown on its apex) due to the different contributions
of Plasmon excitation to the different types of spectra.
Surface Alignment and Nanoconfinement of Liquid Crystal Dendrimers. A Monte Carlo Study

Zerihun G. Workineh and Alexandros G. Vanakaras

Department of Materials Science, University of Patras, 26504, GREECE

Liquid crystal dendrimers combine the highly controlled molecular structure of dendrimers and the
directional properties of liquid crystals (LC). The ability to control the macroscopic alignment of
these anisotropic materials is a key factor for many of their potential applications. For low molar
mass LCs, robust and well established techniques/materials are available for precise alignment of the
LC medium through surface mediated interactions. Through controlling the surface-LC interactions,
usually by means of chemical and/or mechanical treatment of the substrate, a variety of alignments
(homeotropic, planar, tilted, etc) of the LC medium with respect to the substrate are possible. In the
case of LC dendrimers, however, the mechanism behind surface alignment does not involve only the
orientational restrictions imposed by the substrate to its vicinal mesogens but also the
positional/orientational correlations among mesogens that belong to the same dendrimer. In this
work we apply a coarse grained description of single LC dendrimer molecules using a combination
of spherical and non-spherical potentials. Using Monte-Carlo computer simulations we study the
behavior of globular LC dendrimers near substrates as a function of the dendritic generation and
functionality for several types of anchoring conditions of the mesogenic units to the substrate. We
present also simulation results of the conformational properties of dendrimers confined into
nanopores of various sizes and morphologies.

Acknowledgment: This research has been funded through the EU 7th Framework Programme
(FP7/2007-2013), Marie Curie Actions, People-ITN, under the project “Functional LC Dendrimers:
Synthesis of New Materials, Resource for New Applications” (DENDREAMERS, proj. #215884).
 QDs-Based Sensing Platforms

Itamar Willner
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel
([email protected])

The following new developments in the NANOGNSTICS project will be described:

(i) The development of a general chemiluminescence resonance energy transfer (CRET)
sensing platform using hemin/G-quadruple as chemiluminescence generator, and QDs as
energy acceptor. The method will be implemented to develop aptasensors, DNA-sensors and
enzyme sensors. Multiplexed analysis by this sensing platform will be presented.
(ii) Amplification of the sensing platforms through the regeneration of the target analyte
will be presented. The regeneration of the analyte will be demonstrated by using
Exonuclease III or endonucleases as catalysts.
(iii) Four different aptamer-based sensing platforms for VEGF, an Alzheimer’s disease
biomarker, will be introduced, and the practical utility of the systems will be discussed.
 Internalization of polyelectrolyte microcapsules in

human epithelia cells

V. Wulf1, D. Sasse1,H.-P. Elsässer2, W. J. Parak1, P. Rivera Gil1

1Fachbereich Physik, Philipps-Universität Marburg, Marburg, Germany

2Fachbereich Medizin, Institut für Zytobiologie und Zytopathologie, Philipps-Universität Marburg,

Marburg, Germany

Contact: [email protected]

Polyelectrolyte Microcapsules could be used as multifunctional microcontainers for example for drug
delivery and drug release in nanomedicin or ion-sensoring in medical diagnostic in specific cells. A
requirement for this would be the voluntary uptake of polyelectrolyte microcapsules by the cells.
[1][2] A better understanding of the uptake mechanisms could lead to a cell type dependent drug
deliver and drug release by polyelectrolyte microcapsules.[3] [4]

The size independent uptake of polyelectrolyte microcapsules could be proven via confocal
fluorescence microscopy and transmission electron microscopy (TEM). Further intracellular
localization of microcapsules in lysosomal structures was visualized by specific antibody staining of
lysosomal associated membrane proteine 1 (LAMP1). An approach for the characterization of the
internalization pathway of polyelectrolyte microcapsules was done by evaluating the effects of
different specific chemical inhibitors whose cytotoxicity on MDA-MB 231 was tested. The applied
inhibitors were known to inhibit different components of the cells such as enzymes (e.g. V-ATPase,
Na+/H+-Exchanger), actin filament depolymerisation or cholesterol, that take part in endocytic
pathways.

[1] B. G. De Geest, Soft Matter 2009, 5, 282.

[2] J. Peteiro-Cattelle Nanomedicine 2009, 4, 967.

[3] A. M. Javier, Advanced Materials 2008, 20, 4281.

[4] P. Rivera-Gil, Nano Letters 2009, 9, 4398.

In vivo enhancement in bioavailability using
Mesoporous Materials

Xin Xia, Chunfang Zhou, Lluis Ballell-Pages and Alfonso E. Garcia-Bennett

More than 40% of new drug developed are poorly water-soluble resulting in inferior
drug adsorption and bioavailability.[1] Recently, mesoporous silica carriers have
drawn attention as a delivery vehicle for poorly water-soluble drugs.[2,3] The large
surface area and large pore volume allow drugs to be encapsulated within the pores.

Worldwide, over 40 million people are infected with HIV. Atazanavir (ATV) is an
antiretroviral drug to treat HIV-infected patients, which is a lipophilic drug compound
with partition constant, log P of 5.20. It’s bioavailability is between 60-68% when
administered orally.[4] However, the bioavailability of ATV is severely hampered, by
78% reduction in plasma concentration, when this is co-administered with proton-
pump inhibitors that is used to treat the secondary effects after HIV medication (i.e.
heartburn and stomach pains).[5]

The aim of the study is to investigate the solubility enhancement of atazanavir and
the pharmacokinetic behavior by using mesoporous silica as carrier. Three ordered
mesoporous silica materials with varying pore width (7.8 nm, 4.3 nm and 2.5nm) and
pore structure are chosen as carriers. Dissolution experiments a clear solubility
enhancement of atazanavir in simulated intestine fluid. An in vivo pharmacokinetic
study was conducted in order to validate the enhancement in dissolution observed
for ATV, in the context with co-administration with proton-pump inhibitors, for the best
performing mesoporous silica NFM-1. In a single administration study in rats, the
bioavailability of atazanavir enhanced with the presence of proton-pump inhibitor by
using mesoporous silica.

[1] M. Hite, S. Turner, C. Federici, "Part 1: Oral Delivery of Poorly Soluble Drugs", to
be found www.scolr.com/lit/PMPS_2003_1.pdf, 2003.
[2] A. R. Mohammed, N. Weston, A. G. A. Coombes, M. Fitzgerald, Y. Perrie, Int. J.
Pharm. 2004, 285, 23-34.
[3] M. T. Morgan, Y. Nakanishi, D. J. Kroll, A. P. Griset, M. A. Carnahan, M. Wathier,
N. H. Oberlies, G. Manikumar, M. C. Wani, M. W. Grinstaff, Cancer Res. 2006, 66,
11913-11921.
[4] C. A. Lipinski, F. Lombardo, B. W. Dominy, P. J. Feeney, Adv. Drug Delivery Rev.
2001, 46, 3-26.
[5] Reyataz (atazanavir sulfate) capsules [prescribing information]. Princeton, NJ:
Bristol-Myers Squibb; July 2004.
 “Tunnel Barrier” Colloidally Synthesized Quantum Dots

Olesya Yarema, Deniz Bozyigit, and Vanessa Wood

Laboratory for Nanoelectronics

Department of Information Technology and Electrical Engineering
ETH Zurich, Switzerland

Colloidally synthesized quantum dots (QDs) are considered promising for solid state devices
and have been successfully integrated in transistors, LEDs, solar cells [1,2]. The goal of our
work is to develop “tunnel junction” coatings for QDs that can facilitate our understanding of
the behavior of charge carriers in QD-based solid state devices, particularly as their
performance relates to electron injection, transport, and extraction. We will present our work
on synthesizing SiO2 shells around QDs while maintaining their optical properties (absorption
and luminescence). The thickness of the SiO2 shell can be tuned by means of reaction
parameters (concentration of precursors, reaction time, etc). We have expanded upon previous
work [3] to achieve shell thicknesses as small as 6 nm, which enables us to draw analogies
with SiO2 tunnel barriers in traditional silicon-based solid state devices. We demonstrate the
use of these QDs with tunnel barriers in the context of QD light emitting devices.

Figure 1. Absorption and luminescence spectra of uncoated (A) and coated CdSe/CdS
core/shell QDs (B), showing that the SiO2 coating does not affect the optical properties. TEM
images showing 6 nm thick SiO2 shells on CdSe/CdS QDs (C) and 11 nm-thick shells on CdSe
QDs (D).

References:
[1] Caruge, J. M.; Halpert, J. E.; Wood, V.; Bulovic, V.; Bawendi, M. G. Nat. Photon. 2008,
2, 247.
[2] Pattantyus-Abraham, A. G.; Kramer, I. J.; Barkhouse, A. R.; Wang, X.; Konstantatos, G.;
Debnath, R.; Levina, L.; Raabe, I.; Nazeeruddin, M. K.; Grätzel, M.; Sargent, E. H. ACS Nano
2010, 4, 3374.
[3] Koole, R.; van Schooneveld, M. M.; Hilhorst, J.; de Mello Donegá, C.; Hart, D. C.; van
Blaaderen, A.; Vanmaekelbergh, D.; Meijerink, A. Chem. Mater. 2008, 20, 2503.
 CdSe Magic-Sized Nuclei, Magic-Sized Nanoclusters and Regular
Nanocrystals: Monomer Effects on Nucleation and Growth

Kui Yu
Steacie Institute for Molecular Sciences, National Research Council Canada. 100 Sussex Drive; Ottawa,
Ontario, Canada K1A 0R6. Business Phone: 613-993-9273; Email: [email protected]

Following our investigation on “In Situ Observation of PbSe Nucleation and Growth
of Magic-Sized Nanoclusters and Regular Nanocrystals” (Small 2011, 7, 2250), I
will discuss CdSe colloidal nanocrystals as a model system for the fundamental
understanding of regular and magic-sized nanocrystals. I will address several debating
topics in the present quantum dot area including the formation mechanism of
monomers. Next, I will introduce recent advances in our labs in the synthesis of
colloidal CdSe magic-sized nuclei (MSN) exhibiting sharp bandgap emission. I will
introduce a model proposed to illustrate the nature of monomers and their degree of
supersaturation (DS) affecting the formation of various CdSe MSN, magic-sized
nanoclusters (MSCs), and regular nanocrystals (RNCs). Also, I will use this model to
address tuning the CdSe RNCs into the CdSe MSN with the presence of cadmium
acetate (Cd(OAc)2) affecting the nature of the monomers. Such a discussion should
bring insight into nucleation/growth of both regular and magic-sized nanocrystals for
better quality control.
NANOSTRUCTURED MESOPOROUS MATERIALS IN DRUG DELIVERY
C.F. Zhou,† A.E. Garcia-Bennett†§
†
Nanologica AB, Drotting Kristinas Vag 45, 11428, Stockholm, Sweden.
†,§
Nanotechnology and Functional Materials, Department of Engineering Sciences, Uppsala University,
SE - 751 21 Uppsala, Sweden

Nanoporous silica based particles are structurally unique, exhibiting porous order on the
mesoscopic scale (2-50nm) and disorder on the atomic-scale. The channels; cages or pores,
formed within the materials are supported by an amorphous silica wall and are arranged
periodically offering extremely high surface areas and sharp pore size distributions.[1,2]
Mesoporous nanoparticles are of applied interest and have shown tremendous potential for
the sustained release of pharmaceutical active drugs.[3,4] The adsorption of active
pharmaceutical molecules into stabile, non-erosive nanoporous materials has been explored.
The potential to control (delay) drug release, enhance drug dissolution, promote drug
permeation across the intestinal cell wall (bioavailability) and improve drug stability under the
extreme environment of the gastro-intestinal tract when administered orally has been
shown.[5,6]
Our efforts concentrate in solving four distinct problems aided by these novel materials; (i)
the delivery of poorly soluble drugs, (ii) the sustained release of potent pharmaceutical drugs,
(iii) drug stability in oral deliver, and (iv) drug targeting to specific cellular types.
We will offer our results towards achieving these goals, together with our vision for
these exciting and novel pharmaceutical delivery vehicles and immunotoxicological
data.

Figure 1: TEM images of cubic

mesoporous nanoparticles

Figure 2: TEM images of cubic

mesoporous nanoparticles internalised
within human dendritic cells.
Figure 3: Release profile of model drug from the
internal pore spaces of mesoporous materials
with different structural pore arrangements

1. Y. Wang, D. Y. Zhao, Chem. Rev., 107, 2821 (2007).

2. R. Atluri, N. Hedin, A. E. Garcia-Bennett, J. Am. Chem. Soc. 2009, 131,3189.
3. A. E.Garcia-Bennett, K. Lund, O. Terasaki, Angew. Chem. Int. Ed., 45, (15), 2434 (2007).
4. H. Vallhov, S. Gabrielsson, M. Strømme, A. Schenynus, A.E. Garcia-Bennett Nanoletters, 7 (12),
3576 (2007).
5. J. M. Rosenholm, A. Meinander, E.Peuhu, R. Niemi, J. E. Eriksson, C.Sahlgren, M. Linden, ACS
Nano, 3 (1), 197, (2009).
6. M. Vallet-Regı, J. Intern. Med., 267, 22, (2010).
 SURFACTANT FREE SYNTHETIC APPROACHES TO
METAL NANOPARTICLES

Christoph Ziegler, Alexander Eychmüller

Physical Chemistry, TU Dresden, Bergstraße 66b, 01062 Dresden, Germany

Metallic nanoparticles have attracted considerable interest in many fields of modern nano science.
Especially in plasmonic related topics, gold and silver nanostructures directly come into mind. For
sophisticated applications of these nanoparticles, reliable and simple synthetic methods are as
desirable as the possibility to modify the surface and therefore enable a wide field of post-processing.
In our recent work we found a simple seeded growth approach to obtain gold nanoparticles with
[1]
diameters between 15 nm and 300 nm (figure 1). The method produces particles with uniform
spherical shape and narrow size distributions. Using ascorbic acid as a reductant and sodium citrate
as stabilizer we utilize biocompatible and easy to exchange substances. The investigation of the
growth process via TEM-measurements revealed the formation of small gold clusters on the surface of
the seeds, which subsequently grow and result in a “blackberry like” intermediate shape of the gold
nanoparticles. Applying heat caused an intraparticle ripening process, which finally lead to a smooth
spherical particle shape. Furthermore the optical properties of the resulting gold sols were discussed
in the light of Mie theory and an influence of the polydispersity was found for large particles.
Another recent research interest was the utilization of tetrazole derivatives as a new group of
[2]
stabilizer molecules to obtain silver sols. Due to the property of tetrazole to completely decompose at
moderate elevated temperatures, this new group of stabilizers offer a great potential for further post-
processing work and applications in sensing and catalysis. Depending on the utilized 5-R-tetrazole (R
= CH3, NH2), different agglomeration kinetics could be observed. Long term stability and
agglomeration processes have been in situ investigated by the use of UV/Vis- and SERS-
spectroscopy. Using 5-methyl-tetrazole it was possible to adjust the degree of agglomeration resulting
in stable, different coloured silver sols (figure 2).
Our newest results, that have not been published yet, reveal innovative possibilities to form also
other structures like star-shaped gold nanoparticles without the need for any kind of surfactants like
CTAB.This may offer novel approaches towards functionalization and application of gold
nanoparticles.

Fig. 1: From the TEM images one caneasilysee the Fig. 2: Different colors of the solutions reveal the possibility of
wonderfuluniformity and amazinglynarrow size precisely tuning the agglomeration state of the silver
distribution of the gold nanoparticlesrangingfrom 15 to sol.
300 nm in diameter.

References

[1] C. Ziegler, A. Eychmüller, J. Phys. Chem. C2011, 115, 4502–4506.

[2] C. Ziegler, M. Klose, S. V. Voitekhovich, N. Gaponik, A. Eychmüller, Zeitschrift für Physikalische
Chemie2011, 225, 363–371.
 Focusing Light on Gold Nanoparticles

Jochen Feldmann

Chair for Photonics and Optoelectronics

Nanosystems Initiative Munich (NIM)
Ludwig-Maximilians-Universität (LMU)
Munich, Germany

Gold nanoparticles experience strong optical forces when placed into laser foci. Depending on
wavelength single nanoparticles can be either trapped or pushed forward by the respective gradient
and scattering forces. I will demonstrate several new concepts of optically trapped gold
nanoparticles partly combining the effects of optical forces with those of optothermal heating.
Applications range from optical printing [1,2] to the detection of acoustic signals [3].

1. A. Urban, A. Lutich, F. Stefani, and J. Feldmann, Nano Letters 10, 4794 (2010)
2. S. Nedev, A. Urban, A. Lutich, and J. Feldmann, Nano Letters 11, 5066 (2011)
3. A. Ohlinger, A. Deak, A. Lutich, and J. Feldmann, Physical Review Letters 108, 018101
(2012)
 HEROES OF NANOSCIENCE

Dear colleagues and friends. We have allowed ourselves to include a

little card game. All data are of course taken from a public database. As
some of you have "complicated" names we apologize in case we should
have gotten some numbers wrong. This "game" is meant as a friendly
joke. Maybe most of you played something similar as little children for
example with cars. We all know, there is no "best" car. Some are faster,
some have more horse power, and some are most expensive. That's
exactly the charm of the game. I hope you enjoy it as we do! But, be
aware, for Nanax 6 we may think to extend the "hero" cards with the
following categories:

- maximum times felt asleep as chairman

- longest time overdrawn in a talk

- maximum number of nasty questions to young innocent researchers

per conference

- self-estimated maximum number of years until being awarded the

noble prize

- quota of rejecting manuscripts

- maximum number of talks attended per day (excluded the own one)

- years since last self-performed experiment

 T. Aida M.G. Bawendi F. García de Abajo

Mapping surface plasmons on a

single metallicnanoparticle,
Nature Physics, 2007
Synthesis and Characterization of Nearly Monodisperse
Molecular ordering of organic molten salts triggered by CdE(E = S, Se, Te) Semiconductor Nanocrystallites,
single-walled carbon nanotubes, Science, 2003 JACS, 1993

( Papers found: 916 ( Papers found: 331 ( Papers found: 196

( Times Cited without self-citations: 17529 ( Times Cited without self-citations: 36136 ( Times Cited without self-citations: 5302
( Average Citations per Item: 21 ( Average Citations per Item: 113 ( Average Citations per Item: 30
( Most cited item: 428 ( Most cited item: 4388 ( Most cited item: 359
( h-index : 68 ( h-index : 87 ( h-index : 43
(Web of Knowledge) (Web of Knowledge) (Web of Knowledge)

L. Josephson H. Mattoussi C.B. Murray

Superparamagnetic-Tat Peptide

Bioconjugate Chemistry, 1999

Magnetic Labeling with Novel

Structural diversity in binary

High-Efficiency Intracellular

nanoparticle superlattices,
Nature, 2006
Conjugates,

Quantum dot bioconjugates for imaging, labelling and

sensing, Nature Materials, 2005

( Papers found: 160 ( Papers found: 157 ( Papers found: 206

( Times Cited without self-citations: 9645 ( Times Cited without self-citations: 12700 ( Times Cited without self-citations: 21038
( Average Citations per Item: 63 ( Average Citations per Item: 87 ( Average Citations per Item: 104
( Most cited item: 766 ( Most cited item: 1758 ( Most cited item: 4388
( h-index :51 ( h-index :48 ( h-index :50
(Web of Knowledge) (Web of Knowledge) (Web of Knowledge)

P.S. Weiss “ HEROES OF J. Feldmann

NANOSCIENCE”
Conductance switching in single

Object: Collect all the “heroes of

conformational changes,

nanoscience” cards
molecules through

Science, 2001

How to play:

1. Look for some friends

2. Deal all the cards
3. The first player choose a category
4. Compare the heroes number in Biomolecular Recognition Based on Single Gold
Nanoparticle Light Scattering, Nano Letters, 2003
that category, the player with
( Papers found: 409 the highest value in that category ( Papers found: 566
( Times Cited without self-citations: 6958 will keep the cards of the rest of ( Times Cited without self-citations: 12902
( Average Citations per Item: 21 players ( Average Citations per Item: 24
( Most cited item: 971 5. Who has collected most cards at ( Most cited item: 708
( h-index :41 the end wins ( h-index : 56
(Web of Knowledge) (Web of Knowledge)
 H.E. Gaub N.A. Kotov P. Mulvaney

nanoparticlesinto luminescent nanowires,

Spontaneous organization of single CdTe

core-shell particles, Langmuir, 1996

Surface Assembly, Science, 2008

Synthesis of nanosized gold-silica

Single-Molecule Cut-and-Paste

Science, 2002
( Papers found: 201 ( Papers found: 334 ( Papers found: 243
( Times Cited without self-citations: 15329 ( Times Cited without self-citations: 13795 ( Times Cited without self-citations: 14696
( Average Citations per Item: 81 ( Average Citations per Item: 44 ( Average Citations per Item: 63
( Most cited item: 1494 ( Most cited item: 1000 ( Most cited item: 1388
( h-index :58 ( h-index :63 ( h-index :64
(Web of Knowledge) (Web of Knowledge) (Web of Knowledge)

F. Stellacci I. Willner J.M. de la Fuente

Low-voltage organic transistors with an

Hybrid Systems: Synthesis, Properties,

amorphous molecular gate dielectric,

Integrated Nanoparticle–Biomolecule

Angewandte Chemie, 2004

and Applications,
Nature, 2004

Tailoring the Synthesis and Heating Ability of Gold

Nanoprisms for Bioapplications, Langmuir, 2012
( Papers found: 640 ( Papers found: 75
( Papers found: 108
( Times Cited without self-citations: ( Times Cited without self-citations: 1486
( Times Cited without self-citations: 2859
25565 ( Average Citations per Item: 22
( Average Citations per Item: 28
( Average Citations per Item: 49 ( Most cited item: 225
( Most cited item: 392
( Most cited item: 1178 ( h-index :21
( h-index :26
( h-index :91 (Web of Knowledge)
(Web of Knowledge)
(Web of Knowledge)

W.J. Parak L.M. Liz-Marzan A.P. Alivisatos

Hydrophobic Nanocrystals Coated with an

Route to Water Soluble Nanocrystals,

Amphiphilic Polymer Shell:ௗ A General

Nano Letters, 2004

Tailoring Surface Plasmons through the Morphology and Semiconductor clusters, nanocrystals, and
Assembly of Metal Nanoparticles, Langmuir, 2006 quantum dots, Science, 1996

( Papers found: 148 ( Papers found: 260 ( Papers found: 373

( Times Cited without self-citations: 7031 ( Times Cited without self-citations: 11951 ( Times Cited without self-citations: 53947
( Average Citations per Item: 51 ( Average Citations per Item: 51 ( Average Citations per Item: 148
( Most cited item: 670 ( Most cited item: 880 ( Most cited item: 5683
( h-index :41 ( h-index :63 ( h-index :106
(Web of Knowledge) (Web of Knowledge) (Web of Knowledge)
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 LIST OF PARTICIPANTS

Number Name e-mail Abstract Page

Sofie Abé [email protected] 21, 22
AbuElMagd AbuMoghera [email protected] 195
Alexander Achtstein [email protected] 24, 38
A Ahmed 23
Takuzo Aida [email protected] 25
David Alcantara Parra [email protected] 26
Dmitry Aldakov [email protected] 27
Teresa Alejo [email protected] 28
Alina Aluculesei [email protected] 29
Nicole Amecke [email protected] 30
Faheem Amin [email protected] 31
Didier Astruc [email protected] 32
Mostafa Baghbanzadeh [email protected] 33
Lluis Ballell-pages [email protected] 232
Moungi Bawendi [email protected]
Brandon Beberwyck [email protected] 36
Yehonadav Bekenstein [email protected] 37
Amelie Biermann [email protected] 38, 133
Nadja Bigall [email protected] 23, 39, 195
Simon Boehme [email protected] 40
Emmanuel Bois [email protected]
Klaus Boldt [email protected] 41
Paola Borri [email protected] 42, 146
Virginia Bouzas [email protected] 43
Deniz Bozyigit [email protected] 44, 235
Dirk Broer [email protected] 45
Anna Brusilovski [email protected] 46, 217
Madalina Bucos [email protected] 47, 206
Michele Buscema [email protected] 49
Nani Caballero [email protected] 50
Andreu Cabot [email protected] 51
Luigi Carbone [email protected] 52
Carregal - [email protected]
Susana 53, 169
Romero marburg.de
Sergio Carrillo [email protected] 54
Eudald Casals [email protected] 35, 55
Castellanos
Idoia [email protected] 56
Rubio
Alina Chanaewa [email protected] 58
Loïc Charbonnière [email protected] 64, 165
Gaelle Charron [email protected] 59
Agathi Christofidou [email protected] 60
Climente
Juan Ignacio [email protected]
Plasencia
Mirjana Comor [email protected]
Carlos Cruz [email protected] 29, 63, 75, 178
Piotr Cywinski [email protected] 64, 166
Mita Dasog [email protected] 65
de
Antoine [email protected] 66
Kergommeaux
Leonor De la Cueva [email protected] 69, 113
Frans Dekker [email protected] 68
70, 91, 161, 173,
Jesús M. de la Fuente [email protected]
179
Pablo del Pino [email protected] 70, 173
James Delehanty [email protected] 71
Richard Dennis [email protected] 84
Jens Dernedde [email protected] 111
Zvicka Deutsch [email protected] 72
[email protected]
Cristina Domínguez 73, 74
strasbg.fr
Bertrand Donnio [email protected] 73, 74, 164, 219
Leonas Dumitrascu [email protected] 75
Alexander Efros [email protected] 76
Joren Eilers [email protected] 77
Even pascale.even-hernandez@univ-
Pascale 144
Hernandez rennes1.fr
Weil Evers [email protected] 78, 93, 177
Elisabetta Fedeli [email protected] 206
[email protected]
Jochen Feldmann 239
muenchen.de
Rute Fernandes [email protected] 80
Ana Ferreira [email protected] 81
Anna Ferretti [email protected] 82, 181
Yuliar Firdaus [email protected]
Sandra Flessau [email protected]
Dmitry Gakamsky [email protected] 84
Raquel Galian [email protected] 83, 174
Juan Gallego [email protected] 113
Yunan Gao [email protected] 49, 85, 104
Javier García de Abajo [email protected]
Hermann Gaub [email protected] 86
André Geßner [email protected] 87
Carlo Giansante [email protected] 88
María González-Béjar [email protected] 89
Neus Gómez-Bastús [email protected] 35, 106, 156
Bruno Grandidier [email protected] 90
Valeria Grazú [email protected] 91, 179
Jouzas Grazulevicius [email protected] 92, 128, 184, 225
Dominika Grodzinska [email protected] 93
Esther Groeneveld [email protected] 77, 94
Marcin Grzelczak [email protected]: 95, 123
Andres Guerrero [email protected] 95, 96, 123
Shira Halivni [email protected] 97
Harri Härmä [email protected] 98, 166
Antti Hassinen [email protected] 99, 100
Wolfgang Heiss [email protected] 101, 215
21,22, 38, 90, 99,
100, 101, 102,
Zeger Hens [email protected] 103, 104, 112,
119, 133, 158,
159, 160
Hernández-
Beatriz [email protected] 58, 69, 106, 113
Juárez
[email protected]
Anne-Kristin Herrman 105
dresden.de
Heuer-
Amelie [email protected] 107
Jungemann
Esmaeil Heydari [email protected] 108, 211, 212
Niko Hildebrandt [email protected] 87, 109, 227
Jane Hordern [email protected]
40, 49, 85, 104,
Arjan Houtepen [email protected]
110
Thomas Hug [email protected] 111
Dominik Hühn [email protected] 59, 112
Ionut Ichim [email protected] 114
Sarah Jaber [email protected] 115
Jiménez de
Dorleta [email protected] 116, 172
Aberasturi
Lee Josephson [email protected] 26, 118
Yolanda Justo [email protected] 90, 104, 108
Cheri Kagan [email protected] 120
Antonios G Kanaras [email protected] 60, 80, 107, 121
Adis Khetubol [email protected]
Calum Kinnear [email protected] 121
Tobias Kipp [email protected] 95, 123, 155, 210
Christian Klinke [email protected] 58, 124, 156
Joanna Kolny-Olesiak [email protected] 125
Rolf Koole [email protected]
Nick Kotov [email protected]
Maksym Kovalenko [email protected] 126
Roman Krahne [email protected] 127
[email protected]
Cornelius Krasselt 128
chemnitz.de
Nadzeya Kukhta [email protected] 129
Anant Kumar [email protected] 130, 176
Lucas Kunneman [email protected] 85, 131
Sébastien Lamarre [email protected] 132
Alexandre Lancelot [email protected] 206
Holger Lange [email protected] 38, 133
Marc-Antoin Langevin [email protected] 134
Anna Laromaine [email protected] 135
Jannika Lauth [email protected] 136
Aurélie Lefrancois [email protected] 137, 186
Raphael Levy [email protected] 138
Konstanze Liermann [email protected] 139, 166
Efrat Lifshitz [email protected] 46, 140, 217
43, 95, 96, 123,
Luis Liz-Marzán [email protected]
172
Isabel López Tocón [email protected] 141
Rainer Mahrt [email protected] 142, 158, 160
Karthish Manthiram [email protected] 143
Beatriz Martín García [email protected] 145
Francesco Masia [email protected] 42, 146
Hedi Mattousi [email protected] 147
Axel Maurice [email protected] 148
Paul McNaughter [email protected] 150, 151
29, 75, 81, 114,
Georg Mehl [email protected] 152, 168, 178,
201
Till Meiling [email protected] 153
Dai Mengqiao [email protected]
Alf Mews [email protected] 95, 123, 155, 210
Michaela Meyns [email protected] 156
Montenegro 23, 31, 116, 157,
Jose María [email protected]
Martos 172, 175
Juan juanantonio.moralesnavarro@gmail.
Morales 174
Antonio com
42, 99, 158, 159,
Iwan Moreels [email protected]
160
Julie Movellan [email protected] 206
Paul Mulvaney [email protected] 116, 162
Paul Mundra [email protected]
Christopher Murray [email protected]
Zsuzsanna Nagy [email protected] 73, 74, 164, 219
Céline Nayral [email protected] 170, 224
Moritz Nazarenus [email protected] 167
Evangelos Ntararas [email protected] 168
Markus Ochs [email protected] 53, 169
Wilfried-Solo Ojo [email protected] 170
Angel Orte [email protected] 171, 191
23, 31, 39, 50,
53, 59, 112, 116,
[email protected]
Wolfgang J. Parak 157, 167, 169,
marburg.de
172, 173, 175,
188, 195, 233
Beatriz Pelaz [email protected] 70, 173
Julia Pérez Prieto [email protected] 83, 184
Christian Pfeiffer [email protected] 50, 175
Demetri Photinos [email protected] 130, 176
Francesca Pietra [email protected] 93, 177
Srinath Polineni [email protected] 178
Ester Polo [email protected] 179
Alessandro Ponti [email protected] 82, 181
Jan Poppe [email protected] 180
Victor Puntes [email protected] 35, 55, 181
Yury Rakovich [email protected] 183, 197
Renji Reghu [email protected] 184
Christoph Rehbock [email protected] 185
27, 66, 137, 148,
Peter Reiss [email protected]
186
Markus Retsch [email protected] 187
Pilar Rivera-Gil [email protected] 53, 167
Andrey Rogach [email protected] 189
Anna Roig [email protected] 190
Francisco Rubio [email protected]
Maria Jose Ruedas Rama [email protected] 171, 191
Michele Saba [email protected] 192
Irina Safenkova [email protected] 193
Sara Sanchez [email protected] 195
Claudio Sangregorio [email protected] 57
Rubén Santos [email protected]
Zoran Saponjic [email protected]
Diana Savateeva [email protected] 183, 197,
Oliver Schöps [email protected] 198
Jan Schroeder [email protected] 200
Chris Schubert [email protected] 152, 201
Jose-Luis Serrano [email protected] 47, 206
Alexey Shavel [email protected]
40, 49, 85, 104,
Laurens Siebbeles [email protected]
131, 204, 214
Benjamin Siebers [email protected] 205
Teresa Sierra [email protected] 206
Ajay Singh [email protected] 207
Desmond Smith [email protected] 84
Anna Sobolewska [email protected] 164, 211, 219
Jonathan Steckel [email protected] 208
Francesco Stellacci [email protected] 135, 209
108, 164, 211,
Joachim Stumpe [email protected]
212, 219
Yogesh Surendranath [email protected] 213
Mikhailo Sytnyk [email protected] 214
Sybren ten Cate [email protected] 104, 214
Nguyen Thanh [email protected] 215
Dries van Thourhout [email protected] 104
Jenya Tilchin [email protected] 46, 217
Jaakko Timonen [email protected] 218
Jaroslaw Tomczyk [email protected] 164, 211, 219
Laura Trapiella [email protected] 220
Wilfried van Sark [email protected]
Daniel Vanmaekelbergh [email protected] 40, 78, 93, 177
Jonathan Veinot [email protected] 65, 221
Yolanda Vida [email protected] 222
Kathy Vinokurov [email protected] 37, 223
Heloise Virieux [email protected] 224
Dmytro Volynyuk [email protected] 225
Nir Waiskopf [email protected] 226
David Wegner [email protected] 109, 139, 227
Paul Weiss [email protected] 228
Itamar Willner [email protected] 229, 232
Omri Wolf [email protected] 230
Zerihun Workineh [email protected] 176, 231
Verena Wulf [email protected] 233
Xin Xia [email protected] 235
Olesya Yarema [email protected] 44, 101, 235
Kui Yu [email protected] 236
Chunfang Zhou [email protected] 234, 237
[email protected]
Christoph Ziegler 238
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