Colloids 15

Paschalis Alexandridis Review

Department of Chemical and
Biological Engineering,
Gold Nanoparticle Synthesis, Morphology
University at Buffalo – The State
University of New York (SUNY),
Control, and Stabilization Facilitated by
Buffalo, USA.
Functional Polymers
Gold nanoparticles exhibit novel optical and catalytic properties, are nontoxic
and biocompatible, and attract considerable interest in a range of applications,
e.g. photonics, diagnostics, and therapeutics. The morphology (size and shape) of
the nanoparticles and their surface/colloidal properties are very important in the
various applications. A methodology for the synthesis in aqueous media of gold
nanoparticles with controlled size and shape and exceptional colloidal stability is
reviewed. This methodology is based on designer polymers that can exhibit mul-
tiple functions on the basis of the polymer intramolecular and supramolecular
organization. In addition to being water based, this methodology requires no ex-
ternal energy input and employs commercially available polymers, e.g., poly(ethy-
lene oxide) containing Pluronics or Poloxamers, resulting in low cost and poten-
tial environmental benefits.

Keywords: Colloids, Metals, Particles, Polymers, Reduction, Surfactants

Received: August 04, 2010; revised: October 15, 2010; accepted: October 20, 2010
DOI: 10.1002/ceat.201000335

1 Introduction emerges as a result of a competitive growth of different crystal-

lographic surfaces. This is typically achieved by altering the rel-
Nanoparticles such as nanospheres, nanorods, nanocubes, na- ative growth rates of different facets by the selective localiza-
noplates, nanotetrapods, and nanoprisms can serve as building tion of surface-modifying or capping agents, but also by the
blocks for the synthesis of advanced materials, in a way analo- modulation of nucleation and reaction parameters such as
gous to that of atoms or molecules forming the basic constitu- time, temperature, reagent concentration, and pH [14].
ents of matter. The size-dependent optical, magnetic, electron- The preparation of metal nanoparticles in solution is most
ic, and catalytic properties of metal nanoparticles have commonly based on the chemical reduction of metal ions and
attracted significant attention in the literature [1–5]. Metal invariably involves organic solvents and ligands. For example,
nanoparticles, particularly gold, are being considered in wide- in the widely used Brust method for gold nanoparticle synthe-
ranging applications, such as photonics, information storage, sis [15], AuCl4– is transferred into toluene or chloroform using
electronic and optical detection systems, therapeutics, diagnos- tetraalkylammonium bromide and is reduced there with so-
tics, photovoltaics, and catalysis [1–11]. While the chemical dium borohydride in the presence of alkylthiols. The gold
composition of a nanoparticle is important, even more impor- nanoparticles thus synthesized are covered with strongly
tant is the morphology (size and shape) of the nanoparticle bound ligands that render them difficult to disperse in water
and its surface/colloidal properties. and may hinder further surface modification and functional-
The development of simple and versatile methods for the ization of particles for particular applications.
preparation of nanoparticles in a size- or shape-selected and Compared to such a synthesis method, a methodology based
-controlled manner has been a challenging but intellectually on the use of water as the solvent should provide an environ-
rewarding task [12, 13]. The nanoparticle morphology often mentally benign route to the production of gold nanoparticles
and result in a product that can be easily integrated in applica-
tions involving aqueous media. In aqueous solutions [16–19],
gold nanoparticles have been typically produced from the
– chemical reduction of AuCl4– ions by reducing agents such as
Correspondence: Prof. P. Alexandridis ([email protected]), citric acid and ascorbic acid. Such reduction takes place in the
Department of Chemical and Biological Engineering, University at presence of one or more water-soluble polymers, surfactants
Buffalo – The State University of New York (SUNY), Buffalo, NY 14260- or capping agents, and with the aid of externally supplied ener-
4200, USA. gy such as photoirradiation [16], ultrasound irradiation [17],

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
16 P. Alexandridis

or heating [18]. These methods allow for adequate control of composite material [26–30]. Self-assemblies of block copoly-
the size and concentration of the dispersed particles [16–19]. mers of the PEO-PPO family [31, 32] have been used success-
Moreover, the surface-modifying or capping agents confer col- fully for templating the synthesis of inorganic nanomaterials
loidal stabilization and prevent nanoparticle aggregation [2, [33–35]. For example, PEO-PPO-PEO block copolymers have
10]. While the most common strategy to achieve colloidal sta- been recently utilized as templates for semiconductor nanoma-
bility proceeds via the chemical binding of ligands at the sur- terials synthesis and organization [36–40]. Variation of the
face of the nanoparticles, a covalent linkage between the ligand block copolymer molecular characteristics (e.g. block length,
and the nanoparticle may alter the properties of the nanoparti- block ratio), concentration, solvent quality (e.g. solvent type,
cles through a modification of their electronic density and the mixtures of solvents), and temperature allows for a unique
dielectric constant of the surrounding medium [20]. A strategy tunability of the phase behavior and corresponding nanostruc-
based on the physical adsorption of ligands on the surface of ture [41–43]. Self-assembled PEO-PPO-PEO block copoly-
the nanoparticles may be preferable, in order to maintain the mers can transform from spherical micelles in an aqueous so-
intended properties of the nanomaterial [21]. Despite the lution (water is a selective solvent for PEO) to lyotropic liquid
progress achieved, concerns and problems with the prepara- crystals (ordered spheres, cylinders, or lamellae) with an
tion of metal nanoparticles remain, such as the byproducts increase in the block copolymer concentration (at a fixed
from the reducing agent, the multiple steps often required, and temperature) [44–46]. Replacement of part of the water with
the high concentration of protective agents. an organic solvent that has more favorable interactions with
The utilization of nontoxic chemicals, environmentally be- PPO can result in the evolution of structure from water-con-
nign solvents, and renewable materials are emerging issues that tinuous to organic solvent-continuous (water-in-oil or reverse)
merit important consideration in the development of synthetic [47–51].
strategies [22, 23]. Moreover, to facilitate systematic investiga- To realize the full potential of the functional polymer ap-
tion on the morphology-property relationship, it would be proach for nanoparticle synthesis, a better insight into the rela-
highly desirable if one reaction system can be engineered to tionship between polymer characteristics and particle forma-
yield as many different shapes as possible [14]. tion is required. Such fundamental information will enable
In recent years, the challenges and opportunities outlined rational design of polymers to meet specific needs. Following
above have attracted the attention of many researchers, in- the initial reports from our group on the promise of PEO-
cluding our group. In particular, it has been discovered that PPO block copolymers in gold nanoparticle synthesis, several
poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block research groups have pursued green, water-based synthetic
copolymers can act as very efficient reductants and stabilizers routes for the synthesis of gold nanomaterials, using nontoxic
in the single-step synthesis and stabilization of gold nano- polymers as both reductants of the gold salt and capping
particles from hydrogen tetrachloroaureate (III) hydrate agents of the gold nanocrystals. Here, literature is reviewed
(HAuCl4·3H2O) in air-saturated aqueous solutions, at ambient that discusses the synthesis, morphology control, and colloidal
temperature, in the absence of any additional reductants or en- stabilization of metal nanoparticles in aqueous media, distinct
ergy input [24]. This synthesis proceeds fast to completion (in functions that can be conferred by the same macromolecule.
less than 2 h) and is environmentally benign and economical The emphasis is on the use of PEO-PPO block copolymers as
since it involves only water and nontoxic, commercially avail- reductants and stabilizers for gold nanoparticles. Other poly-
able polymers (Pluronics or Poloxamers). The gold nanoparti- mers that offer comparable advantages are also discussed.
cle dispersions can remain highly stable for several years. The review closes with a discussion of future prospects in this
Further, the same ingredients can lead to a variety of nanopar- area.
ticle morphologies (e.g. spheres, plates, prisms) depending on
the polymer PEO-PPO composition, molecular weight, and
concentration. Compared to other methods for gold nanopar-
ticle synthesis [1, 9, 12], the functional polymer-based meth-
2 Spontaneous Synthesis of Metal
odology that we have invented [25] offers the advantages of Nanoparticles in Aqueous PEO-PPO-
ambient conditions, fast completion, minimal number of PEO Solutions
reactants, being economical, and resulting in a ready-to-use
product. The latter feature is particularly advantageous in bio- 2.1 Mechanism of Gold Nanoparticle Formation in
logical and biomedical applications of gold nanostructures. Functional Polymer Solutions
There are additional potential benefits emanating from the
use of functional polymers, such as block copolymers, not only The mechanism of gold nanoparticle formation in aqueous
as structure-directing agents but also as templating or struc- PEO-PPO-PEO block copolymer solutions was advanced by
turing media. Templates generated by the self-assembly of Sakai and Alexandridis [52] on the basis of systematic studies
amphiphilic molecules are particularly attractive for materials on the block copolymer concentration dependence of absorp-
synthesis because of their reproducible (thermodynamically tion spectra, the time dependence (kinetics) of the HAuCl4 re-
driven) formation and tunable structure, and their charac- duction, and the block copolymer concentration dependence
teristic dimensions in the nanoscale. In particular, block co- of the particle size. In these studies, the preparation of
polymer templates can form matrices that afford processabili- gold nanoparticles consisted of simple mixing of an aqueous
ty, mechanical and chemical stability, and morphological 2 · 10–3 mol L–1 HAuCl4·solution with an aqueous solution of
versatility, as well as novel properties of the resulting nano- PEO-PPO-PEO block copolymer or PEO homopolymer, so

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 17

that the HAuCl4 concentration in Table 1. Properties of various PEO-PPO-PEO block copolymers.
the reaction medium was 2 · 10–4
mol L–1. Following agitation by Pluronic Molecular PEO PPO block PEO block cmc [mM] Nominal
weight [wt-%] molecular weight molecular weight (25 °C) formula
vortex mixer for 10 s, the solutions
were left standing at 25 °C for 2 h L43 1850 30 1295 555 EO6PO22EO6
for the reaction to proceed; the ab-
L44 2200 40 1320 880 EO10PO23EO10
sorbance spectra remained almost
unchanged after 2 h, indicating L62 2500 20 2000 500 EO6PO34EO6
completion of the reaction within L64 2900 40 1740 1160 26.3 EO13PO30EO13
this timeframe. Various PEO-PPO-
PEO block copolymers (Pluronic P65 3400 50 1700 1700 38.2 EO19PO29EO19
L43, L44, L62, L64, P65, F68, P84, F68 8400 80 1680 6720 320.5 EO76PO29EO76
P85, F88, P103, P104, P105, F108,
P123, and F127; all from BASF P84 4200 40 2520 1680 6.19 EO19PO43EO19
Corp.) were considered in order to P85 4600 50 2300 2300 8.69 EO26PO40EO26
examine the effects of block co-
F88 11 400 80 2280 9120 11.5 EO103PO39EO103
polymer molecular weight, PEO
block length, PPO block length, P103 4950 30 3465 1485 0.14 EO17PO60EO17
PEO/PPO block ratio, and pres- P104 5900 40 3540 2360 0.51 EO27PO61EO27
ence of block copolymer micelles
(above the critical micelle con- P105 6500 50 3250 3250 0.46 EO37PO56EO37
centration (cmc) of the amphiphil- F108 14 600 80 2920 11680 3.08 EO132PO50EO132
ic block copolymer) on the synthe-
P123 5750 30 4025 1725 0.05 EO19PO69EO19
sis of gold nanoparticles [52].
Tab. 1 provides composition and F127 12 600 70 3780 8820 0.55 EO100PO65EO100

cmc information for the various PEO-

PPO-PEO block copolymers.
It was proposed that the formation of
gold nanoparticles from gold ions com-
prises three main steps: (1) initial reduc-
tion of metal ions in crown ether-like do-
mains formed by block copolymer in
solution, (2) absorption of block copoly-
mer on gold clusters and further reduction
of metal ions on the surface of these gold
clusters, and (3) growth of metal particles
stabilized by block copolymers (Fig. 1)
[52]. While both PEO and PPO blocks
contribute to the HAuCl4 reduction
(step 1), the PEO contribution appears to
be dominant. In step 2, the adsorption of
block copolymers on the surface of gold
clusters takes place because of the
amphiphilic character of the block co-
polymer (hydrophobicity of PPO). The
size of the gold nanoparticles produced
tends to increase with increasing reaction
activity caused by the block copolymer
molecular weight, but can be limited by
block copolymer adsorption due to its am-
phiphilic character. Various results that
support the proposed mechanism are pre-
sented below.

Figure 1. Scheme of the mechanism of gold nanoparticle formation mediated by PEO-

PPO-PEO block copolymers [52]. (Reprinted with permission from [52]. Copyright 2005
American Chemical Society)

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
18 P. Alexandridis

2.2 Reduction of Gold Ions to Form Gold PEO block length (molecular weight) [52]. The PEO in PEO-
Nanoparticles – the Key Role of PEO PPO-PEO block copolymers forms cavities (pseudo-crown
ether structure) that can bind metal ions [53], and reduction
According to the proposed formation mechanism of gold of bound AuCl4– ions can proceed via oxidation of the oxy-
nanoparticles, an increase in the concentration of the PEO- ethylene and oxypropylene segments by the metal center. The
containing polymer enhances the particle formation because cyclization of the PEO chain is induced by ion-dipole interac-
of the formation by PEO of more crown ether-like cavities tions between the templating ion and the electron lone pairs of
[53] that can accommodate AuCl4– ions. Indeed, as shown in the ethylene oxide linkages [55]. Several oxygen atoms in the
Fig. 2, the absorbance at 240 nm (due to AuCl4–) decreased PEO chain interact with one metal ion, and therefore the
gradually with block copolymer concentration up to about strength of the attraction depends on the length of the PEO
1 mM, and then the value decreased abruptly. This decrease in chain. Thus, this mechanism is supposed to be primarily re-
AuCl4– concentration with increasing polymer concentration sponsible for metal ion reduction by PEO-containing polymers
coincides with an increase in the surface plasmon band cen- [52].
tered at 540 nm (see inset of Fig. 2). This indicates that gold Valuable insights into the initial stages of gold nanoparticle
nanoparticles were formed following the reduction of AuCl4– formation by the reduction of AuCl4– in aqueous PEO-PPO-
[52]. Time-dependent UV spectra reported by Chen et al. [54] PEO block copolymer solutions have been recently provided
provided further evidence that the very first step of the synthe- by Polte et al. [56], who developed to this end a combined X-
sis was the formation of primary gold clusters composed of a ray absorption spectroscopy (XAS) and small-angle X-ray scat-
few gold atoms, in agreement with the three-step gold nano- tering (SAXS) setup with a time resolution of 2 min. XAS
particle formation mechanism of Fig. 1. probed in situ the reduction of gold from Au(III) to Au(0),
The proposed reaction mechanism also suggests that an in- while SAXS simultaneously recorded the size distribution of
crease in PEO chain length (molecular weight) favors the re- the formed nanoparticles. According to this study, the reduc-
duction of AuCl4– and formation of particles. PEO-PPO-PEO tion of Au(III) to Au(0) commences immediately upon mixing
block copolymers having different PEO block lengths but the the HAuCl4 solution with the block copolymer (in this case,
same PPO block length (Pluronic P103, P105, F127 and F108) Pluronic F127) solution. The nanoparticles form in a burst
are compared in Fig. 2. The absorbance changes indicative of process, whereby the final particle number is reached quickly.
AuCl4– reduction and nanoparticle formation followed the or- Subsequently, only the particle size increases over time. Com-
der of the PEO block molecular weight (P103 < P105 < F127 parison of X-ray absorption near-edge structure and SAXS
< F108). Furthermore, the average nanoparticle size increased showed that, while the particles are growing, the quantity of
in the order P103 < P105 < F127 < F108, which is consistent Au(0) is higher than the quantity of gold located in the nano-
with an increase in reaction activity effected by the increasing particles. More specifically, the quantity of Au(0) that is not
found in the nanoparticles exhibits a maximum of about 30 %
at t ∼200 s, and then decreases continuously until the particle
growth has been completed. Finally, all the Au(0) is located in
the nanoparticles. This finding was attributed to the pseudo-
crown ether effect of the PEO-PPO-PEO block copolymers
which kinetically stabilize gold atoms when formed from gold
ions within their protecting cavity (for a period of about 600 s
until they coalesce with a gold nanoparticle in the vicinity)
[56].
The same study [56] revealed also aspects of the internal
structure of the gold nanoparticles. The SAXS data were con-
sistent with a structure in which the gold atoms in the interior
of the particles are less densely packed compared to those lo-
cated closer (about 1–2 nm) to the surface. The structure of
this shell region remains unchanged as the particles grow.
Small-angle neutron scattering (SANS) and dynamic light
scattering (DLS) studies, under conditions where the HAuCl4
concentration was varied at a fixed block copolymer (in this
case, Pluronic P85) concentration in order to identify the max-
imum yield [57], suggested that most of the block copolymers
formed their own micelles and that only a very small fraction
Figure 2. Absorbance at 240 nm recorded at 2 h after mixing of of block copolymers were associated with the gold nanoparti-
aqueous AuCl4– ion solution and aqueous Pluronic P103 (䊊),
cles. This situation led to a low yield; thus, a step-addition
P105 (䊉), F127 (䊐), and F108 (䊏) block copolymer solutions,
plotted as a function of block copolymer concentration. Also method was used to enhance the yield of gold nanoparticles by
shown are data for PEO homopolymer solutions (~). Inset: Ab- a factor of 4, whereby HAuCl4 was added in sufficiently small
sorbances at 540 nm for the same systems and conditions [52]. steps to maintain a higher value of the block copolymer-to-
(Reprinted with permission from [52]. Copyright 2005 American gold ion ratio, and therefore to continuously form nanoparti-
Chemical Society) cles [57].

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 19

2.3 Contribution of the Hydrophobic Block to AuCl4– ing functional polymers was further explored by Goy-Lopez et
Reduction and Nanoparticle Size Determination al. [58] who compared PEO-PPO block copolymers to PEO-
poly(styrene oxide) (PSO) block copolymers. The time needed
To decouple the relative contributions of the block copolymer to complete the metal salt reduction was much longer in the
overall molecular weight and the PEO and PPO block lengths case of the PEO-PSO block copolymers (in the range of
on the reduction of gold ions and the formation of gold nano- 6–96 h) compared to that (less than 2 h) of PEO-PPO block
particles, Sakai and Alexandridis [52] considered the absor- copolymers. This has been attributed to the greater hydropho-
bances at 240 nm (due to AuCl4– concentration) and at 540 nm bicity of PEO-PSO block copolymers: The micelles formed
(due to nanoparticle concentration) recorded at 2 h after mix- promote polymer entanglements which decrease the concen-
ing of aqueous AuCl4H solution with aqueous solutions of sev- tration of crown ether-like structures, where the initial AuCl4H
eral PEO-PPO-PEO block copolymers. For block copolymers reduction takes place [52], so that nucleation becomes more
having shorter PEO block lengths, the absorbance at 240 nm
decreased linearly, and that at 540 nm increased, with increas-
ing block copolymer PPO length, indicating that PPO also
plays a role in the AuCl4H reduction and nanoparticle forma-
tion [52]. In colloidal systems, it is common that the adsorp-
tion process or micelle formation significantly affects the parti-
cle size. The number-average diameters of gold nanoparticles
produced in Pluronic P103, P105, F127, and F108 solutions
are plotted in Fig. 3 as a function of (a) block copolymer molar
concentration, (b) PEO concentration, (c) PPO concentration,
and (d) block copolymer concentration relative to the cmc of
the PEO-PPO-PEO block copolymers. In the plot of diameter
against PEO concentration (Fig. 3b), an increase in size in the
order F108 < F127 < P105 < P103 (at a given PEO concentra-
tion) was observed. On the other hand, when plotted against
the PPO concentration (Fig. 3c), the diameter values were
close to each other for different polymers. This indicates that
the PPO concentration also contributes to the particle size de-
termination. When plotted against the block copolymer con-
centration relative to the cmc at 25 °C, the diameter plots were
spread in the order of P103 < P105 < F127 < F108 (see
Fig. 3d). The order of particle size (P103 < P105 < F127 <
F108) in Fig. 3d is the same below and above the cmc, indicat-
ing no major contribution of block copolymer micelles to the
particle size determination. The contribution of PPO concen-
tration to size determination is most likely due to adsorption
of PPO blocks on the surface of gold clusters. If the block co-
polymer covers the surface of a gold nanoparticle, the effect
would be to restrict the final particle size. Namely, competition
between (i) the reaction activity enhanced by block copolymer
concentration or PEO block length and (ii) the block copoly-
mer adsorption favored by PPO block (hydrophobicity) deter-
mines the particle size. It is assumed that the reaction activity
enhancement due to block copolymer concentration and PEO
block length affects the particle growth (size) more than the
block copolymer adsorption does, because the particle size in-
creased with increasing block copolymer concentration and
PEO block length when block copolymers with similar PPO
molecular weight (3500) were used (Pluronic P103, P105,
F127, and F108) [52]. In the context of data in Fig. 3, we note
that the nanoparticle size distribution is not narrow. Given our
current, improved understanding of the synthesis mechanism Figure 3. Average diameters of gold nanoparticles produced in
aqueous PEO-PPO-PEO block copolymer solutions, plotted as a
in functional polymers, there are opportunities for improve-
function of the (a) block copolymer molar concentration, (b)
ment. Some other techniques for gold nanoparticle synthesis
PEO (wt/v) concentration, (c) PPO (wt/v) concentration, and
lead to narrower particle size distribution, but lack several of (d) block copolymer concentration relative to the cmc: Pluronic
the benefits of the reviewed methodology. P103 (䊊), P105 (䊉), F127 (䊐), and F108 (䊏). The bars repre-
The role of the hydrophobic block in the mechanism of gold sent 1 standard deviation [52]. (Reprinted with permission from
nanoparticle spontaneous synthesis mediated by PEO-contain- [52]. Copyright 2005 American Chemical Society)

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
20 P. Alexandridis

difficult to occur. In addition, PEO-PSO block copolymers are gold nanoparticles prepared by the Sakai and Alexandridis
tightly packed in aqueous solution, even when not inside mi- [24] method. With good stabilization, gold particles were
celles, and this conformation disfavors the contact with AuCl4– spherical and uniform in size with a diameter in the range of
ions and their subsequent reduction [58]. The hydrophobic 5–10 nm. The presence of 0.7 M of NaF, an electrolyte that is
PSO block also affected steps 2 and 3 of the synthesis mecha- known to decrease the solvent quality of water and to promote
nism (Fig. 1), by means of the preferential adsorption of the the formation of PEO-PPO-PEO block copolymer micelles
block copolymer on certain crystallographic planes (see related [62], significantly increased the stabilization capacity of the
discussion in Section 3). micelles and favored spherical gold particles [54]. Khullar et al.
further explored the role of temperature and hydrophobic ef-
fects on the synthesis of gold nanoparticles in aqueous PEO-
2.4 Role of Solvent Quality on Nanoparticle PPO-PEO block copolymer solutions [63]. Significant differ-
Synthesis ences were observed when polymers of different hydrophobic/
hydrophilic character were used. In the case of the relatively
The complexation of metal ions with PEO-PPO-PEO block hydrophilic Pluronic F68, extensive hydration of the PEO
copolymers (related to step 1 of the synthesis mechanism) blocks that form crown ether-like cavities in the corona of the
should be affected by the temperature and solvent. Further- micelles produced a few small nanoparticles, but their yield
more, the competition between gold ion reduction in the bulk and size increased upon increasing the temperature, as the mi-
solution and on the surface of gold particles could be modu- celles were dehydrated. The relatively hydrophobic Pluronic
lated by the solvent quality since several solution properties of P103 forms well-defined micelles with less hydrated surface
the PEO-PPO-PEO block copolymers (e.g. solubility, interfa- cavities compared to Pluronic F68. It is interesting that Pluro-
cial activity, micelle formation, micelle structure) are strongly nic P103 micelles were found covered with very small nanopar-
affected by the temperature and solvent type [41, 42, 59, 60]. ticles at the (relatively high) temperature and concentration
These features can provide opportunities to control the reac- conditions considered [63].
tivity and resulting particle size.
Sakai and Alexandridis [61] reported on the effects that the
solution properties of PEO-PPO-PEO block copolymers have 3 Morphogenesis of Metal Nanoparticles
on the reduction of AuCl4H and the size of the gold nano- in Aqueous PEO-PPO-PEO Solutions
particles produced. The conformation of the amphiphilic
block copolymers in solution was modulated by varying the In addition to the continuing interest in controlling the size of
temperature and the solvent type (water, formamide, and their nanoparticles, significant efforts are extended nowadays in tai-
mixtures). The solvent quality becomes worse with increasing loring the shape of materials at the nanoscale. This is moti-
temperature, leading to lower cmc [41], higher surface adsorp- vated by the intriguing shape-dependent properties exhibited
tion [42], and denser micelles [60], while it becomes better by nanostructures [1, 2, 12, 64]. For example, while the inter-
when replacing water with formamide [59]. Two main factors action of electromagnetic radiation with spherical gold nano-
were found to be important for controlling the competition particles leads to only one type of polarization, and hence
between the reactivities of AuCl4H reduction in the bulk solu- shows up as a single peak in UV-visible spectra, anisotropic
tion to form gold seeds and on the surface of gold seeds (parti- shapes such as rods, wires, and prisms exhibit more than one
cles), and for the particle size determination: (i) block copoly- resonance in the UV/near-IR region [65]. The number of reso-
mer conformation or structure (e.g. loops vs. entanglements, nances depends on the number of ways in which the electron
non-associated polymers vs. micelles) and (ii) interactions be- density can be polarized and is dictated by the shape of the
tween AuCl4– ions and block copolymers (attractive ion-dipole nanoparticles. The sharp tips and edges found in nanoparticles
interactions vs. repulsive interactions due to hydrophobicity) are regions of high electric field that greatly enhance the opti-
[61]. More specifically, a particle size increase was observed in cal effects [64]. In the case of catalysis, nanoparticles with dif-
aqueous solutions with increased temperature, which has been ferent faces have different densities of adsorption sites, and
attributed to (a) a decrease in the number of gold seeds (reac- thus catalysts of the same material but with different shapes
tion sites) due to a decrease in the number of unassociated can exhibit very different performance [5]. In what follows, it
polymers and an increase in repulsive interactions between the is discussed how PEO-PPO-PEO block copolymers can direct
AuCl4– ions and the more hydrophobic PEO-PPO-PEO block the synthesis of non-spherical gold particles.
copolymers present in solution, combined with (b) an en- In a study of the effects of PEO-PPO-PEO block copolymer
hanced AuCl4– reduction on the surface of seeds where the concentration and PEO and PPO block lengths on the size of
block copolymer predominantly resided due to their increased gold nanoparticles synthesized from HAuCl4 in aqueous solu-
hydrophobicity. In formamide solutions, a lower reactivity and tions, Sakai and Alexandridis [66] found that an increase of
a higher particle size were observed compared to water, which the HAuCl4 concentration caused a change in the particle
were attributed to the shielding by formamide of ion-dipole shape from spherical to triangular or hexagonal nanoplates
interactions between AuCl4– ions and block copolymers, which (Fig. 4). In a paper published in the same period, Wang et al.
overcomes the beneficial effects of formamide on the block co- [67] reported the synthesis of crystalline gold nano- and mi-
polymer conformation (lower micelle concentration) [61]. croplates with triangular or hexagonal shapes by reduction of
Chen et al. [54] considered the effect of PEO-PPO-PEO HAuCl4 in lyotropic liquid crystals (LLC) [44, 49] mainly
block copolymer micelle hydrophobicity on the stabilization of made of PEO-PPO-PEO block copolymers and water after

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 21

rather compact in solution

a b c d and does not facilitate pseudo-
crown ether cavity formation
for metal nuclei reduction. In-
stead, block copolymer ad-
sorption onto metal clusters/
nanoparticles, and subsequent
surface reduction in the vicini-
ty, emerged as the dominant
process: The rate of creation of
new metal nuclei in solution
100 nm
decreased, and the polymer se-
Figure 4. Transmission electron micrographs of gold nanoparticles produced in 5.0 mM Pluronic lectively adsorbed on the low-
P105 block copolymer aqueous solutions at different HAuCl4 concentrations: (a) 0.2, (b) 0.4, (c) 0.6, est energy {111} planes of the
and (d) 0.8 mM L–1. The scale bar represents 100 nm. Note the transition from spherical nanoparti- nanocrystals, inhibiting their
cles to triangular or hexahedral nanoplates occurring with an increase in the HAuCl4 concentration growth. This promoted aniso-
[66]. Also note the hexagonal symmetry spots in the electron diffraction pattern shown in the insets. tropic growth along the {100}
orientation and the formation
of {111}-bounded structures as
adding a small amount of cetyltrimethylammonium bromide thin nanoplates [58]. The reaction temperature was very im-
(CTAB) or tetrabutylammonium bromide (TBAB). The for- portant for nanoplate formation. At room temperature, the re-
mation of microplates occurred at an optimal value of CTAB action was faster, growth occurred in all crystallographic direc-
or TBAB concentration, and was attributed to the selective ad- tions and spherical nanoparticles with mean sizes of 70–20 nm
sorption of CTAB or TBAB on certain crystallographic facets were formed. At higher temperatures (above 70 °C), only poly-
[67]. Although the LLC structure does not really act as a tem- disperse, irregular particles were produced from a rather slow
plate, Wang et al. [67] hypothesized that it provided a certain reduction [58].
ordering that confined CTAB as well as the metal nuclei and The synthesis of icosahedral (30 sharp edges and 12 corners)
facilitated the consequent growth of single-crystal plates. To gold particles using HAuCl4 as a precursor and PEO-PPO-
test this hypothesis, Sakai and Alexandridis [68] considered PEO block copolymers as both reductant and directing agent
the synthesis of gold microplates through autoreduction of has been reported by Zhang et al. (Fig. 5) [70]. It was demon-
HAuCl4·in aqueous solutions of the PEO-PPO-PEO block co- strated that icosahedral gold nanoparticles can be formed un-
polymer Pluronic L64 under ambient conditions, in the ab- der a wide range of experimental conditions, and the size of
sence of added energy, reductant, or other surfactants. Pluro- the obtained icosahedral particles can be tuned from 100 nm
nic L64 forms both cylindrical/hexagonal and lamellar to 1 mm by varying experimental conditions. For example, the
lyotropic liquid crystals as well as micellar solutions [44]. It size of the gold icosahedral particles decreased with increasing
turns out that crystalline microplates can form across a wide concentration of Pluronic F88. Under these conditions, more
Pluronic L64 composition range. The plate morphology has block copolymer molecules attached to the gold facets, which
been attributed to gold ion reduction on the {100} facets (pro- inhibited their further growth and resulted in a smaller particle
moted by the lower reduction activity of the relatively short size. Icosahedral gold nanoparticles with sizes of about 100–
PEO length Pluronic L64 block copolymers that adsorb there), 250 nm formed in the presence of Pluronic P105. More regular
rather than the shape-directing action of LLC as templates icosahedral gold nanoparticles were formed when a high-mo-
[68]. Triangle and hexagonal gold nanoparticles have also been lecular-weight copolymer was used. This could result from the
obtained by AuCl4– reduction in mixed micelles of Pluronic fact that a polymer with a larger molecular weight is more flex-
P103 + P84 and P103 + P123 (but, interestingly, not in the mi- ible and can be absorbed more efficiently on the surface of
celles of the individual Pluronic block copolymers, under the gold clusters, which is favorable for forming regular icosahe-
same conditions) [69]. dral gold nanoparticles. The results suggested that the icosahe-
In their aqueous solution synthesis of gold nanoparticles dral gold particles were formed at an early stage in the reaction
mediated by PEO-PSO block copolymers as both reductants [70].
and stabilizers, Goy-Lopez et al. [58] observed the formation Gold icosahedra with an average diameter of about 600 nm
of single-crystalline gold nanoplates in good yields (up to have been prepared by heating an aqueous solution of the
70 %) in a certain temperature range (30–65 °C). These nano- PEO-PPO-PEO block copolymer Pluronic P123 and HAuCl4
plates were of mostly truncated or rounded triangular shape, at 60 °C for 25 min [71]. The authors hypothesized that Pluro-
with {111} planes as the basal surfaces and lateral mean sizes in nic P123 selectively adsorbs on gold crystal faces to promote
the range of 0.1–1.2 lm (depending on polymer concentration the anisotropic growth toward the formation of gold icosahe-
and reaction temperature). The authors point out that the sur- dra. The authors pointed out that an icosahedron, which is a
face energy of nanoplates is much higher compared to cubooc- type of multiple-twinned particle (MTP), tends to achieve a
tahedra and multiply twinned particles; thus, the nanoplate low total free energy by assuming a twinned structure with the
formation would require kinetic control. This was accom- lower energy {111} facets. Because of lattice distortions and
plished by the hydrophobic functional polymer used, which is surface defects, however, this twinned structure exhibits strong

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
22 P. Alexandridis

reactivity toward oxidative etching [72]. Furthermore, the bromide or iodide ion adlayer has a large mismatch with the
strain energy emanating from the twin defects increases as the Au (111) surface and generates interfacial strain [75]. This
MTP size increases [73]. Thus, it is generally thought that strain prevents the gold crystals from growing with extended
MTP are not stable when they grow to a large size. The authors (111) faces. NaBr and NaI thus favor gold particles with irregu-
stipulated that the surface capping ability of Pluronic P123 re- lar shapes [71].
duced the surface energy, so as to offset the strain energy of the
twinned structure, and protected the gold icosahedra from oxi-
dative etching [71]. Hence, Pluronic P123 was able to stabilize 4 Efficient Stabilization of Metal
the growth of large multiple-twinned icosahedra. Nanoparticles in Aqueous PEO-PPO-
Single-crystalline gold nanoplates were produced when so- PEO Solutions
dium chloride was added to the aqueous Pluronic P123 solu-
tion (at a molar ratio NaCl/HAuCl4 = 10:1) [71]. The chloride The role of PEO-PPO-PEO block copolymers in the synthesis
ion is thought to act by facilitating the growth of {111}-orient- of gold nanoparticles and in guiding their morphology has
ed hexagonal/triangular gold nanoplates. It is well known that been established following a number of studies, as discussed in
Cl– ions chemisorb on the surface of gold to form a hexagonal the previous two sections. The same polymers serve an impor-
closed packed adlayer on the Au (111) surface, and inhibit the tant function as colloidal stabilizers for the gold nanoparticle
growth along the <111> direction [74]. Thus, Cl– ions pro- dispersions. In an attempt to uncouple the nanoparticle for-
mote the crystal growth perpendicular to the <111> direction mation and colloidal stabilization processes that take place in
required for the formation of the flat gold nanoplates. The tandem in the PEO-PPO-PEO block copolymer media dis-
authors hypothesized that the crystal growth mechanism in- cussed previously (Fig. 1), Rahme et al. [21] examined the sta-
volves a competition between the chemisorption ability of Cl– bilization function of PEO-PPO-PEO block copolymers in
ions to produce nanoplates and the capping ability of Pluronic aqueous dispersions of well-defined gold nanoparticles
P123 that favors icosahedra. The experimental results sug- (∼12 nm diameter) that had previously been synthesized
gested that the degree of formation of the gold nanoplates was through a standard citrate reduction procedure. The stabilizing
proportional to the concentration of Cl– ions. It has been re- effects of block copolymer concentration and molecular struc-
ported that a combination of Cl– ions and oxygen from the air ture (PEO block length, PPO block length) have been system-
promotes the etching and dissolution of twinned seeds [72, atically compared for the same nanoparticle type. Aggregation
73]. Single-crystal seeds, free of twin boundary defects on their and precipitation processes were assessed separately using em-
surface, are more stable than twinned seeds in this oxidative pirical parameters calculated from optical absorbance spectra.
environment. On the basis of this, the authors proposed that The authors found the stabilization of the gold nanoparticles
the increase of the Cl– concentration, caused by adding a large by the PEO-PPO-PEO block copolymers to occur below the
NaCl amount, enhanced the oxidative dissolution selectively, cmc. Increasing the polymer concentration, PEO and PPO
so that more single-crystal seeds were produced than twinned block lengths, or the overall length enhanced the nanoparticle
seeds and, consequently, more single crystalline nanoplates colloidal stability. The most important parameter appeared to
formed than multiple-twinned icosahedra [71]. be the length of the hydrophobic PPO block. Among the var-
Gold nanoplates were also produced when LiCl or KCl was ious PEO-PPO-PEO block copolymers considered (Pluronics
added to the aqueous solution instead of NaCl. However, gold P123, P104, P84, F88, L62, L64, F108, P85, and P65), Pluronic
nanocrystals with irregular shapes were produced when NaBr F127 emerged as the most efficient toward colloidal stabiliza-
or NaI was added [71]. While the hexagonal packed adlayer of tion. Different aggregation states were observed and character-
chloride ions is well aligned with the Au (111) surface, the ized by the displacement of the plasmon resonance band. A

Figure 5. Characterization of gold icosahedra synthesized at 40 °C from 0.84 mM and 5.8 mM Pluronic F88 and HAuCl4, respectively, fol-
lowing reaction for 1 day: (a) SEM image; (b) higher-magnification SEM image; (c, d) SEM images of a single gold particle observed from
different angles of view; (e) geometrical model of the obtained icosahedron particles; (f) representative TEM image [70]. (Reproduced
from [70], DOI: 10.1039/b805392h, by permission of the Royal Society of Chemistry.)

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 23

correlation between the displacement of this band and precipi- 0.04 mM/L (approximately ten times lower than the cmc)
tation of the nanoparticles was established [21]. Rahme et al. [77]. In most cases, gold occupied a central position inside the
[76] also considered diblock PEO-PPO block copolymers as polymer core. The thickness of the polymer corona was esti-
stabilizers for gold nanoparticles. These polymers were found mated by measuring the brightness profile to about 3 nm, and
to provide long-term colloidal stability; however, this was re- the diameter of the gold nanoparticles to about 20 nm. A small
lated to the formation of micelles, whereas triblock copolymers fraction of gold nanoparticles were not surrounded by poly-
could provide good stability even at concentrations at which mer and, conversely, several polymer globules were not asso-
micelles do not form [76]. It was pointed out that the excep- ciated with gold nanoparticles. The same features were ob-
tional colloidal stability conferred by the PEO-PPO block co- served in cryo-TEM images taken while the polymer
polymers, which interact in a noncovalent, reversible manner aggregates remained in a fully hydrated state [77].
with the gold nanoparticles, should be readily translated to In a modeling study that nicely complements the aforemen-
other types of nanoparticles and/or amphiphilic polymers. tioned experiments, the dissipative particle dynamics (DPD)
In a subsequent study, the same group characterized the method was used to simulate the formation and stabilization
structure of preformed gold particles that had been stabilized of gold nanoparticles in PEO-PPO-PEO block copolymer mi-
by PEO-PPO-PEO block copolymers, using a range of tech- celles [78]. DPD treats simulated elements in a coarse-grained
niques: transmission electron microscopy (TEM), dynamic level by grouping atoms together up to a single bead. The
light scattering (DLS), and small-angle neutron scattering beads interact through a simple soft pairwise potential that al-
(SANS) with contrast variation that matched the scattering lows large time-scale simulations. The solution of Newton’s
length density of gold [77]. Gold nanoparticles were found in- equations of motion generates the time evolution of the sys-
dividually embedded within globules of polymer, consistent tem. In the DPD simulation, the primary gold clusters that
with the colloidal stability of these systems, even under condi- were experimentally observed in the early stage of gold nano-
tions for which block copolymer micelles would not form in particle formation were modeled as gold beads. The results
solution. The TEM, DLS, and SANS data demonstrated that showed these gold beads to be aggregated into spherical parti-
Pluronic F127 was adsorbed on the surface of gold nanoparti- cles inside the micelles and to form stable PEO-PPO-PEO
cles to form non-micellar aggregates that can be much larger block copolymer-gold colloids with two-layer structure: The
than the typical size of F127 micelles. The DLS and TEM ex- hydrophobic PO segments were adsorbed on the surface of the
periments both reveal a large polydispersity of the aggregate gold particles whereas the hydrophilic EO segments were ex-
sizes, and most probably a variety of structures. The results ob- posed to water [78]. Increasing the polymer concentration,
tained from the different techniques used are illuminating as molecular weight, and PPO block length led to the formation
to the interactions of the nanoparticle with the functional of more uniform and more stable gold nanoparticles, in agree-
polymer [77]. ment with the picture emerging from experiments. Density
The aforementioned core-shell morphology, with gold parti- profiles of water beads suggested that the micelles, and espe-
cles surrounded by a polymer shell, is shown in Fig. 6 in TEM cially the hydrophobicity of the micellar cores, played an im-
images obtained from a dispersion of preformed gold nano- portant role in the entrapment of primary gold clusters and in
particle prepared with a Pluronic F127 concentration of stabilizing the gold nanoparticles [78].

5 Spontaneous Synthesis of Metal

Nanoparticles in Functional Polymer
Solutions
The principle of having a single functional polymer that can
serve as a reductant, morphogenic agent, and also colloidal sta-
bilizer for metal nanoparticles, as exemplified by the PEO-
PPO-PEO block copolymers discussed above, can be readily
extended to other polymers. In this section, cases of sponta-
neous gold nanoparticle formation in solutions of polymers
containing PEO and/or amines are highlighted. These func-
tional polymers can be linear, branched, or dendrimers, and
produced by simple or sophisticated chemistry.
Figure 6. TEM images of preformed gold nanoparticles coated
with Pluronic F127. Following negative staining with uranyl ace-
tate, the gold particle core appears as dark contrast, while the 5.1 PEO-PPO Block Copolymers with Added Amine
polymer has lighter contrast. The indications sps, lps, fAu, and fp
stand for small polymer shell, large polymer shell, free gold par- Functionality
ticle, and free polymer nodule, respectively [77]. Scale bars are
50 nm. (Copyright Wiley-VCH Verlag GmbH & Co. KGaA. Repro- A family of polymers that resemble the PEO-PPO-PEO tri-
duced with permission from: Rahme et al., ChemPhysChem block copolymers (Pluronics), but contain an additional func-
2008, 9, 2230–2236.) tionality, are the Tetronics, which consist of four PEO-PPO

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
24 P. Alexandridis

block copolymer arms linked at the center with a tertiary ent modes of binding of alkylamines with the gold surface were
amine group. A representative member of this family, Tetronic identified: a weak binding due to the formation of an electro-
T904, has been shown to act as both reductant and stabilizer static complex between protonated amine molecules and sur-
in the one-pot aqueous solution synthesis of gold nanoparti- face-bound AuCl4–/AuCl2– ions, and a stronger binding due to
cles [79]. The synthesis mechanism remains the same as in a complex of the form [AuCl(NH2R)] [81]. In 2004, the same
PEO-PPO-PEO block copolymers. Low polymer/AuCl4– molar year when the spontaneous synthesis of gold nanoparticles in
ratios led to a low reduction rate that favored the formation of aqueous PEO-PPO block copolymer solutions was reported
triangular or hexagonal nanoplates. Upon increasing the poly- [24], Aslam et al. [82] recognized that amines, in addition to
mer/AuCl4– ratio, the reduction became faster, the number of modifying the surface of the nanoparticles, can also function
crystal seeds increased and, in turn, the particle size decreased; as reductants. They reported the preparation of gold nanopar-
a spherical shape is favored under these conditions. The pres- ticles in water directly by oleyl amine, which can electrostati-
ence of the amine group in the polymer molecule conferred cally complex with AuCl4– ions, reduce them and cap the
sensitivity to the solution pH. In particular, the particle size in- resulting gold particles to colloidally stabilize them. The reduc-
creased when the synthesis was carried out in acidic condi- tion could take place under ambient conditions, but was con-
tions. This has been attributed by the authors to a decreasing siderably enhanced at 50 °C; hence, the reported data were for
number of nuclei, as the protons inhibit the PEO blocks of the synthesis that was carried out at that temperature [82]. We
polymer from interacting and reducing the metal ions [79], note that the ability of amines to reduce gold ions and to bind
but could also reflect a change due to pH in the block copoly- to metallic gold needs to be combined with a dispersion stabi-
mer conformation and/or structure of the micelles. lization function, in order for the synthesis methodology to be
In comparing the gold nanoparticle synthesis in aqueous effective. In what follows, several studies aimed at this target
solutions containing Tetronic T904 with that in Pluronic P105 are reviewed.
(which has a comparable number of EO and PO units with
Tetronic T904), the authors noted that the reduction reaction
is also more efficient and faster in the presence of T904 [79].
This has been attributed to the more open conformation of the 5.2 Amine-Containing Amphiphiles, Block
star-shaped Tetronic block copolymer that facilitates the Copolymers, and Dendrimers
formation of crown ether-like cavities by the PEO blocks,
but also by the presence of reducing amino groups (as Ishii et al. [83] achieved autoreduction of HAuCl4 by a diblock
discussed below). The authors also pointed out that, while the copolymer consisting of a-biotinyl-PEO and poly[2-(N,N-di-
gold nanoparticle size decreased from 64 to 6–8 nm in methylamino) ethyl methacrylate] (PDMA) in aqueous solu-
Pluronic P105 media [54], it decreased from 40 to 5 nm in tion at room temperature, which resulted in PEO-modified
Tetronic T904 media, which indicates a better stabilization gold nanoparticles with biotin recognition moieties installed at
capacity of T904. The star architecture of T904 could the distal end of the PEO-tethered chains. The nanoparticles
presumably provide a better coverage of the nanoparticle sur- had a size in the range of 6–13 nm, depending on the initial
face [79]. AuCl4–/polymer ratio, and exhibited high dispersion stability
Members of a related family of block copolymers, amino- in water. A related diblock copolymer, consisting of the bio-
terminated PEO-PPO block copolymers (Surfonamine), were compatible poly(2-(methacryloyloxy) ethyl phosphorylcho-
recently reported to reduce AuCl4– and form gold nanoparti- line) (PMPC) block and PDMA, mediated the aqueous solu-
cles under some heating and at sufficiently long PEO blocks tion synthesis of sterically stabilized gold nanoparticles at
[80]. The Surfonamine polymers could bind to the surface of ambient temperature without any additional reducing agent
the gold nanoparticles, resulting in an enhanced activity for [84]. The authors indicate that the PDMA block becomes par-
AuCl4– reduction at that location. The strong binding of these tially protonated upon addition of HAuCl4, and the remaining
block copolymers resulted in nanoparticles with different sur- nonprotonated tertiary amine groups reduce the AuCl4– coun-
face properties, depending on the polymer PEO/PPO ratio. terion to metallic gold. The PDMA block is adsorbed on the
For example, gold nanoparticles synthesized in Surfonamine gold nanoparticle surface while the PMPC chains serve as a
L-207 (EO33PO10NH2) could mix well with water but not with stabilizing block. The size and shape of gold nanoparticles
cyclohexane. On the other hand, gold nanoparticles synthe- could be controlled by tuning synthesis parameters such as the
sized in Surfonamine B-200 (EO6PO29NH2) were miscible block composition and the concentrations of the PMPC-
with cylcohexane but not with water [80]. PDMA polymer and HAuCl4 [84].
In the two studies highlighted above, the presence of amine The assemblies formed by the functional polymer can serve
groups conferred further functionality to the PEO-PPO block to localize the formed nanoparticles. Meristoudi and Pispas
copolymers. Alkylamines have been previously investigated as [85] synthesized gold nanoparticles within a corona of micelles
capping agents for the preparation of gold nanoparticles that formed in aqueous solution through self-assembly of the di-
are dispersible in organic solvents [81]. The reduction of the block copolymer poly[tert-butylstyrene-b-sodium (sulfamate/
gold ions was accomplished with another agent, similar to the carboxylate-isoprene)] (BS-SCI). The metal precursor,
case of the more common alkanethiol capping agents [15], HAuCl4, coordinated with the anionic SCI corona of the mi-
and the capping of the gold nanoparticles with alkylamines celles and was subsequently reduced by the amine groups pres-
was accomplished during phase transfer of the nanoparticles ent there. The polyelectrolyte nature of the hybrid BS-SCI/gold
to chloroform that contained the alkylamines [81]. Two differ- micelles resulted in colloidal stability that depended on the so-

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 25

lution pH and ionic strength [85]. Sakai et al. [86] prepared addition of any other reducing agent [93]. The shape and size
gold nanoparticles (of 30–50 nm in diameter) on the surface of of the particles could be tuned by the PVP/metal salt ratio.
liposomes (with a diameter of 50–200 nm) formed by dis- Various gold nanostructures, decahedral, icosahedral and
tearoyl-N-monomethyoxy PEO-succinyl-phosphatidylethano- plates, were synthesized through heating of a PVP/HAuCl4
lamine (DSPE-PEO) and L-a-dipalmitoylphosphatidylcholine aqueous solution, with the ratio of polymer OH end-groups to
(DPPC). The synthesis proceeded in aqueous solutions under Au ions identified as an important experimental parameter for
ambient conditions in the absence of any reducing agents or varying the shape of the particles formed [94]. Anisotropic
energy input [86]. gold nanostructures with various shapes, produced by reduc-
Sardar et al. [87] used poly(allylamine) (PAAm) as a reduc- ing HAuCl4 with PVP in aqueous solutions without the use of
ing and stabilizing agent for the single-step synthesis of gold any additional capping agent or reductant, were reported by
nanoparticles in aqueous solution. The PAAm adsorbed on the Lim et al. [95]. As the HAuCl4 amount increased, the mor-
surface of these nanoparticles can be exchanged with a variety phology evolved from nanotadpoles to nanokites and then tri-
of omega-functionalized acid-, alcohol-, amine-, and biotin- angular and hexagonal microplates. The authors noted that
terminated alkylthiols [87]. Gold nanocrystals with different the mild reducing power of PVP, resulting in a slow reduction
shapes, wire, sheet, octahedral, and decahedral, were synthe- rate, played an important role in the formation of nanoplates
sized by in situ reduction within gels formed by low-molecu- during nucleation and in their growth into highly anisotropic
lar-weight tryptophan-containing peptide amphiphiles in nanostructures [95]. The same group reported a protocol that
water, without using any external reducing or capping agents generates gold icosahedra of about 18 nm in size in high yields
[88]. The authors noted that the gel morphology at minimum by simply mixing aqueous solutions of HAuCl4 and PVP [96].
gelation concentration is the prime requirement to prepare This protocol was also used to prepare multiply twinned silver
such different nanocrystal shapes [88]. nanoparticles (15–20 nm in size), spherical aggregates
Gold nanoparticles can be synthesized and stabilized within (25–30 nm in size) of Pd nanoparticles, and very small (2 nm)
poly(amidoamine) (PAMAM) dendrimers. For example, hy- Pt nanoparticles [96]. Triblock copolymers with PVP end-
droxyl-functionalized dendrimer-stabilized gold nanoparticles blocks and the biodegradable poly(e-caprolactone) (PCL) as a
can be formed by simply mixing glycidol hydroxyl-terminated middle block have been reported to reduce HAuCl4 and stabi-
PAMAM dendrimers of generation 5 (G5.NGlyOH) with lize the obtained nanoparticles in aqueous solution [97].
HAuCl4, and acetamide-functionalized dendrimer-stabilized Two possible mechanisms were initially proposed for the
gold nanoparticles can be formed by acetylation of amine- PVP-mediated reduction of metal ions: direct hydrogen ab-
terminated G5 PAMAM dendrimers (G5.NH2) complexed with straction induced by the metal ion and/or the reducing action
AuCl4– ions [89]. In both cases, no additional reducing agents of macroradicals formed during degradation of the polymer
were required, and the reactions were completed at room tem- [93]. More recent mechanistic studies revealed that water plays
perature. All of these functionalized nanoparticle-dendrimer an important role in this synthesis: As a nucleophile, it attacks
hybrids are water soluble and stable [89]. Gold nanoparticles the gold-vinyl complex, leading to the production of an alco-
also formed spontaneously by simply mixing generation 4 (G4) hol-based Au–1 intermediate [96]. This intermediate then un-
or 5 (G5) glycidol-modified PAMAM dendrimers with HAuCl4 dergoes a redox reaction in which Au–1 is reduced to Au0,
in either methanol or water at room temperature [90]. The size leading to the formation of gold clusters, together with a car-
of the formed nanoparticles can be varied through a change of boxylic acid in the final product [96].
the dendrimer generation or solvent. The use of 1,2-epoxyhex-
ane-modified G4 PAMAM dendrimers can allow for tuning of
the surface hydrophilicity of the gold nanoparticles [90]. 6 Concluding Remarks
Amine-terminated hyperbranched PAMAM in aqueous solu-
tion served as both reductant and stabilizer for the preparation Gold nanoparticles are attractive in a range of applications,
of silver nanoparticles with sizes in the range of 4–15 nm, ad- e.g. catalysis, photonics, diagnostics, and therapeutics, because
justed by the initial polymer/Ag ratio [91]. PEGylated Percec- of their novel properties, biocompatibility, and low toxicity.
type dendrons in arene-cored dendrimers were found capable The properties, processing, and integration of the nanoparti-
of the spontaneous reduction of HAuCl4 and stabilization of cles into various products are highly dependent upon the
dendrimer-stabilized gold nanoparticles, in the absence of any nanoparticle morphology (size and shape) and their surface
other reductant in water [92]. properties, which dictate both short- and long-range interac-
tions (and possible organization) between particles and be-
tween the particles and the medium into which they are em-
5.3 Poly(vinylpyrrolidone) Polymers bedded.
Here, the synthesis, morphology control, and colloidal stabi-
Poly(N-vinyl-2-pyrrolidone) (PVP) is a water-soluble polymer lization of gold nanoparticles in aqueous media are reviewed,
which, similarly to PEO, can provide multiple functions, as with an emphasis on systems where these distinct functions
homopolymer or part of a copolymer, in the synthesis of gold can be bestowed by the same macromolecule. These multiple
nanomaterials. PVP was initially used a colloidal stabilizer, but functionalities emanate from the polymer intermolecular con-
it was recognized in 2006 that it also served as a reductant of formation (that affords ion-binding and reduction sites) and
metal salts in aqueous solutions to produce gold and silver col- the supramolecular organization (adsorption on the surface of
loids in a one-step process, at low temperatures, without the nanoparticles, formation of micelles).

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
26 P. Alexandridis

Block copolymers based on the water-soluble PEO that is References

covalently attached to a hydrophobic block, such as PPO, can
act as very efficient reductants and stabilizers in the single-step
synthesis and stabilization of gold nanoparticles from tetra- [1] C. J. Murphy, T. K. San, A. M. Gole, C. J. Orendorff, J. X.
chloroaureate(III) (AuCl4–) ions in air-saturated aqueous solu- Gao, L. Gou, S. E. Hunyadi, T. Li, J. Phys. Chem. B 2005, 109
tions, at ambient temperature, in the absence of any additional (29), 13857. DOI: 10.1021/jp0516846
reductants or energy input. These attractive features are com- [2] C. Burda, X. Chen, R. Narayanan, M. A. El-Sayed, Chem.
pounded by the commercial availability of PEO-PPO block co- Rev. 2005, 105, 1025. DOI: 10.1021/cr030063a
polymers and their biocompatibility, to result in a methodolo- [3] T. K. Sau, A. L. Rogach, F. Jackel, T. A. Klar, J. Feldmann,
gy with favorable cost and low impact to the environment. Adv. Mater. 2010, 22 (16), 1805. DOI: 10.1002/
Moreover, the gold nanoparticles emerge coated with physical- adma.200902557
ly adsorbed polymer which can be subsequently removed or [4] D. V. Talapin, J. S. Lee, M. V. Kovalenko, E. V. Shevchenko,
exchanged with other functional ligands, and the nanoparticles Chem. Rev. 2010, 110 (1), 389. DOI: 10.1021/cr900137k
can be readily integrated into diverse products (from compos- [5] B. R. Cuenya, Thin Solid Films 2010, 518 (12), 3127. DOI:
ites to cells). 10.1016/j.tsf.2010.01.018
The multi-scale functionality of PEO-PPO block copolymers [6] M. C. Daniel, D. Astruc, Chem. Rev. 2004, 104 (1), 293. DOI:
emanates from the PEO-rich domains that provide the loci 10.1021/cr030698+
where the initial reduction of AuCl4– takes place, from the hy- [7] S. Eustis, M. A. El-Sayed, Chem. Soc. Rev. 2006, 35, 209.
drophobic PPO domains that assemble the block copolymers [8] R. Sardar, A. M. Funston, P. Mulvaney, R. W. Murray, Lang-
(to increase the local concentration of gold) and make them muir 2009, 25 (24), 13840. DOI: 10.1021/la9019475
adsorb on the surface of nanoparticles (to offer a means of [9] J. F. Zhou, J. Ralston, R. Sedev, D. A. Beattie, J. Colloid Inter-
growth and colloidal stability), and from the combined PEO- face Sci. 2009, 331 (2), 251. DOI: 10.1016/j.jcis.2008.12.002
PPO block copolymers (PEO/PPO block ratio and molecular [10] N. L. Rosi, C. A. Mirkin, Chem. Rev. 2005, 105, 1547. DOI:
weight) that act locally, to modulate the reduction rate and di- 10.1021/cr030067f
rect the growth of certain crystallographic planes, and also in [11] D. A. Giljohann, D. S. Seferos, W. L. Daniel, M. D. Massich,
terms of overall concentration with respect to that of gold ions. P. C. Patel, C. A. Mirkin, Angew. Chem., Int. Ed. 2010, 49
As a result, the polymer chemical composition, architecture, (19), 3280. DOI: 10.1002/anie.200904359
molecular weight, and concentration allow for fine-tuning of [12] Y. Xia, Y. J. Xiong, B. Lim, S. E. Skrabalak, Angew. Chem., Int.
the size and shape of the resulting nanoparticles. Following the Ed. 2009, 48 (1), 60. DOI: 10.1002/anie.200802248
articles published by our group in 2004 and 2005, many of the [13] T. K. Sau, A. L. Rogach, Adv. Mater. 2010, 22 (16), 1781.
issues that we had considered and the questions that we had DOI: 10.1002/adma.200901271
left unanswered (due to lack of funding for continuing this line [14] K. Sohn, F. Kim, K. C. Pradel, J. S. Wu, Y. Peng, F. M. Zhou,
of research) have been properly addressed in the literature: J. X. Huang, ACS Nano 2009, 3 (8), 2191. DOI: 10.1021/
smaller size of spherical nanoparticles, narrower particle size nn900521u
distribution, higher yield, improved understanding of nuclea- [15] M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, R. Whyman,
tion and growth mechanism, location of polymer with respect J. Chem. Soc., Chem. Commun. 1994, 801.
to the metal particles, greater variation of solution conditions [16] M. Mandal, S. K. Ghosh, S. Kundu, K. Esumi, T. Pal, Lang-
(temperature/salt), particles with different sizes and shapes. muir 2002, 18 (21), 7792. DOI: 10.1021/la0118107
The range of the materials obtained and the applications that [17] R. A. Caruso, M. Ashokkumar, F. Grieser, Langmuir 2002, 18
are impacted has thus expanded, and the scope has been gener- (21), 7831. DOI: 10.1021/la020276f
alized to encompass other polymers and other metals. Salient [18] X. Sun, X. Jiang, S. Dong, E. Wang, Macromol. Rapid Com-
findings on the above have been presented in this review. mun. 2003, 24 (17), 1024.
The principle of having a single functional polymer that can [19] T. Ishii, H. Otsuka, K. Kataoka, Y. Nagasaki, Langmuir 2004,
serve as a reductant, structure-directing agent, and also colloi- 20 (3), 561. DOI: 10.1021/la035653i
dal stabilizer for metal nanoparticles, as exemplified by the [20] M. M. Alvarez, J. T. Khoury, T. G. Schaaff, M. N. Shafigullin,
PEO-PPO block copolymers discussed above, can be readily I. Vezmar, R. L. Whetten, J. Phys. Chem. B 1997, 101 (19),
extended to other polymers. In fact, recent advances in macro- 3706. DOI: 10.1021/jp962922n
molecular synthesis, coupled with our current, improved un- [21] K. Rahme, F. Gauffre, J.-D. Marty, B. Payre, C. Mingotaud,
derstanding of how metal nanoparticles form and grow, pro- J. Phys. Chem. C 2007, 111 (20), 7273. DOI: 10.1021/
vide ample opportunities for synergisms between polymer jp070274+
science and nanotechnology toward the design and develop- [22] L. Reijnders, J. Ind. Ecol. 2008, 12 (3), 297. DOI: 10.1111/
ment of novel nanomaterials that can be integrated into var- j.1530-9290.2008.00049.x
ious devices and processes [98–100]. At the same time, it is re- [23] H. Sengul, T. L. Theis, S. Ghosh, J. Ind. Ecol. 2008, 12 (3),
warding to discover new functions for common, commercially 329. DOI: 10.1111/j.1530-9290.2008.00046.x
available polymers such as PEO and PVP. [24] T. Sakai, P. Alexandridis, Langmuir 2004, 20 (20), 8426. DOI:
10.1021/la049514s
The author has declared no conflict of interest. [25] P. Alexandridis, T. Sakai, US Patent 7 718 094, 2010.
[26] M. R. Bockstaller, R. A. Mickiewicz, E. L. Thomas, Adv.
Mater. 2005, 17 (11), 1331. DOI: 10.1002/adma.200500167

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28
 Colloids 27

[27] R. B. Grubbs, J. Polym. Sci., Part A: Polym. Chem. 2005, 43, [54] S. Chen, C. Guo, G. H. Hu, J. Wang, J. H. Ma, X. F. Liang,
4323. L. Zheng, H. Z. Liu, Langmuir 2006, 22 (23), 9704. DOI:
[28] R. A. Vaia, J. F. Maguire, Chem. Mater. 2007, 19 (11), 2736. 10.1021/la061093m
DOI: 10.1021/cm062693+ [55] K.-J. Liu, Macromolecules 1968, 1 (4), 308.
[29] D. C. Pozzo, L. M. Walker, Eur. Phys. J. E: Soft Matter Biol. [56] J. Polte, F. Emmerling, M. Radtke, U. Reinholz, H. Riese-
Phys. 2008, 26 (1/2), 183. DOI: 10.1140/epje/i2007-10303-4 meier, A. F. Thunemann, Langmuir 2010, 26 (8), 5889.
[30] S. K. Kumar, R. Krishnamoorti, Ann. Rev. Chem. Biomol. DOI: 10.1021/la903829q
Eng. 2010, 1, 37. DOI: 10.1146/annurev-chembioeng- [57] D. Ray, V. K. Aswal, J. Macromol. Sci., Part B: Phys. 2010, 49
073009-100856 (4), 810. DOI: 10.1080/00222341003603743
[31] P. Alexandridis, T. A. Hatton, Colloids Surf., A 1995, 96 [58] S. Goy-Lopez, E. Castro, P. Taboada, V. Mosquera, Langmuir
(1/2), 1. 2008, 24 (22), 13186. DOI: 10.1021/la802279j
[32] P. Alexandridis, Curr. Opin. Colloid Interface Sci. 1997, 2 (5), [59] P. Alexandridis, L. Yang, Macromolecules 2000, 33 (9), 3382.
478. [60] P. Alexandridis, L. Yang, Macromolecules 2000, 33 (15), 5574.
[33] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. [61] T. Sakai, P. Alexandridis, Langmuir 2005, 21 (17), 8019.
Chmelka, G. D. Stucky, Science 1998, 279, 548. DOI: 10.1021/la050756h
[34] G. J. de A. A. Soler-Illia, E. L. Crepaldi, D. Grosso, C. San- [62] P. Alexandridis, J. F. Holzwarth, Langmuir 1997, 13 (23),
chez, Curr. Opin. Colloid Interface Sci. 2003, 8, 109. 6074.
[35] Y. Wan, D. Y. Zhao, Chem. Rev. 2007, 107 (7), 2821. DOI: [63] P. Khullar, A. Mahal, V. Singh, T. S. Banipal, G. Kaur, M. S.
10.1021/cr068020s Bakshi, Langmuir 2010, 26 (13), 11363. DOI: 10.1021/
[36] G. N. Karanikolos, P. Alexandridis, G. Itskos, A. Petrou, T. J. la100734p
Mountziaris, Langmuir 2004, 20 (3), 550. DOI: 10.1021/ [64] B. Viswanath, P. Kundu, A. Halder, N. Ravishankar, J. Phys.
la035397+ Chem. C 2009, 113 (39), 16866. DOI: 10.1021/jp903370f
[37] G. N. Karanikolos, P. Alexandridis, R. Mallory, A. Petrou, T. J. [65] X. H. Huang, S. Neretina, M. A. El-Sayed, Adv. Mater. 2009,
Mountziaris, Nanotechnology 2005, 16 (10), 2372. DOI: 21 (48), 4880. DOI: 10.1002/adma.200802789
10.1088/0957-4484/16/10/063 [66] T. Sakai, P. Alexandridis, Nanotechnology 2005, 16 (7), S344.
[38] G. N. Karanikolos, N. L. Law, R. Mallory, A. Petrou, P. Alex- DOI: 10.1088/0957-4484/16/7/006
andridis, T. J. Mountziaris, Nanotechnology 2006, 17 (13), [67] L. Y. Wang, X. Chen, J. Zhan, Y. C. Chai, C. J. Yang, L. M.
3121. DOI: 10.1088/0957-4484/17/13/007 Xu, W. C. Zhuang, B. Jing, J. Phys. Chem. B 2005, 109 (8),
[39] G. N. Karanikolos, P. Alexandridis, T. J. Mountziaris, 3189. DOI: 10.1021/jp0449152
Mater. Sci. Eng., B 2008, 152 (1–3), 66. DOI: 10.1016/ [68] T. Sakai, P. Alexandridis, Macromol. Symp. 2010, 289, 18.
j.mseb.2008.06.028 DOI: 10.1002/masy.200900003
[40] P. Alexandridis, G. N. Karanikolos, T. J. Mountziaris, US Pa- [69] M. S. Bakshi, A. Kaura, P. Bhandari, G. Kaur, K. Torigoe, K.
tent 7 608 237, 2009. Esumi, J. Nanosci. Nanotechnol. 2006, 6 (5), 1405. DOI:
[41] P. Alexandridis, J. F. Holzwarth, T. A. Hatton, Macro- 10.1166/jnn.2006.196
molecules 1994, 27 (9), 2414. [70] C. X. Zhang, J. L. Zhang, B. X. Han, Y. J. Zhao, W. Li, Green
[42] Y. N. Lin, P. Alexandridis, J. Phys. Chem. B 2002, 106 (42), Chem. 2008, 10 (10), 1094. DOI: 10.1039/b805392h
10834. DOI: 10.1021/jp014221i [71] W.-K. Lee, S.-H. Cha, K.-H. Kim, B.-W. Kim, J.-C. Lee, J.
[43] P. Alexandridis, R. J. Spontak, Curr. Opin. Colloid Interface Solid State Chem. 2009, 182 (12), 3243. DOI: 10.1016/
Sci. 1999, 4 (2), 130. j.jssc.2009.09.020
[44] P. Alexandridis, D. L. Zhou, A. Khan, Langmuir 1996, 12 [72] Y. J. Xiong, J. M. McLellan, Y. D. Yin, Y. N. Xia,
(11), 2690. Angew. Chem., Int. Ed. 2007, 46 (5), 790. DOI: 10.1002/
[45] Z. Y. Gu, P. Alexandridis, Macromolecules 2004, 37 (3), 912. anie.200604032
DOI: 10.1021/ma0206218 [73] J. Xu, S. Y. Li, J. Weng, X. F. Wang, Z. M. Zhou, K. Yang,
[46] G. Schmidt, W. Richtering, P. Lindner, P. Alexandridis, M. Litt, X. Chen, Q. Cui, M. Y. Cao, Q. Q. Zhang, Adv. Funct.
Macromolecules 1998, 31 (7), 2293. Mater. 2008, 18 (2), 277. DOI: 10.1002/adfm.200700123
[47] B. Svensson, U. Olsson, P. Alexandridis, Langmuir 2000, 16 [74] S. S. Shankar, S. Bhargava, M. Sastry, J. Nanosci. Nanotechnol.
(17), 6839. 2005, 5 (10), 1721. DOI: 10.1166/jnn.2005.192
[48] R. Ivanova, B. Lindman, P. Alexandridis, Langmuir 2000, 16 [75] O. M. Magnussen, Chem. Rev. 2002, 102 (3), 679. DOI:
(23), 9058. 10.1021/cr000069p
[49] R. Ivanova, B. Lindman, P. Alexandridis, Adv. Colloid Inter- [76] K. Rahme, P. Vicendo, C. Ayela, B. Payre, C. Mingotaud,
face Sci. 2001, 89, 351. F. Gauffre, Chem. Eur. J. 2009, 15 (42), 11151. DOI: 10.1002/
[50] P. Alexandridis, K. Andersson, J. Phys. Chem. B 1997, 101 chem.200901564
(41), 8103. [77] K. Rahme, J. Oberdisse, R. Schweins, C. Gaillard, J.-D. Marty,
[51] B. Svensson, U. Olsson, P. Alexandridis, K. Mortensen, C. Mingotaud, F. Gauffre, ChemPhysChem 2008, 9 (15),
Macromolecules 1999, 32 (20), 6725. 2230. DOI: 10.1002/cphc.200800358
[52] T. Sakai, P. Alexandridis, J. Phys. Chem. B 2005, 109 (16), [78] S. Chen, C. Guo, G.-H. Hu, H.-Z. Liu, X.-F. Liang, J. Wang,
7766. DOI: 10.1021/jp046221z J.-H. Ma, L. Zheng, Colloid Polym. Sci. 2007, 285 (14), 1543.
[53] A. Warshawsky, R. Kalir, A. Deshe, H. Berkovitz, A. Patchor- DOI: 10.1007/s00396-007-1721-x
nik, J. Am. Chem. Soc. 1979, 101 (15), 4249.

Chem. Eng. Technol. 2011, 34, No. 1, 15–28 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
28 P. Alexandridis

[79] S. Goy-Lopez, P. Taboada, A. Cambon, J. Juarez, C. Alvarez- [90] M. W. Shen, K. Sun, X. Y. Shi, Curr. Nanosci. 2010, 6 (3),
Lorenzo, A. Concheiro, V. Mosquera, J. Phys. Chem. B 2010, 307.
114 (1), 66. DOI: 10.1021/jp908569z [91] Y. W. Zhang, H. S. Peng, W. Huang, Y. F. Zhou, X. H. Zhang,
[80] T. Sakai, M. Ishigaki, T. Okada, S. Mishima, J. Nanosci. Na- D. Y. Yan, J. Phys. Chem. C 2008, 112 (7), 2330. DOI:
notechnol. 2010, 10 (2), 919. DOI: 10.1166/jnn.2010.1899 10.1021/jp075436g
[81] A. Kumar, S. Mandal, P. R. Selvakannan, R. Pasricha, A. B. [92] E. Boisselier, A. K. Diallo, L. Salmon, C. Ornelas, J. Ruiz,
Mandale, M. Sastry, Langmuir 2003, 19 (15), 6277. DOI: D. Astruc, J. Am. Chem. Soc. 2010, 132 (8), 2729. DOI:
10.1021/la034209c 10.1021/ja909133f
[82] M. Aslam, L. Fu, M. Su, K. Vijayamohanan, V. P. Dravid, [93] C. E. Hoppe, M. Lazzari, I. Pardinas-Blanco, M. A. Lopez-
J. Mater. Chem. 2004, 14 (12), 1795. DOI: 10.1039/b402823f Quintela, Langmuir 2006, 22 (16), 7027. DOI: 10.1021/
[83] T. Ishii, H. Otsuka, K. Kataoka, Y. Nagasaki, Langmuir 2004, la060885d
20 (3), 561. DOI: 10.1021/la035653i [94] M. Zhou, M. Bron, W. Schuhmann, J. Nanosci. Nanotechnol.
[84] J. J. Yuan, A. Schmid, S. P. Armes, A. L. Lewis, Langmuir 2008, 8 (7), 3465. DOI: 10.1166/jnn.2008.172
2006, 22 (26), 11022. DOI: 10.1021/la0616350 [95] B. Lim, P. H. C. Camargo, Y. N. Xia, Langmuir 2008, 24 (18),
[85] A. Meristoudi, S. Pispas, Polymer 2009, 50 (13), 2743. DOI: 10437. DOI: 10.1021/la801803z
10.1016/j.polymer.2009.04.045 [96] M. S. Yavuz, W. Y. Li, Y. N. Xia, Chem. Eur. J. 2009, 15 (47),
[86] T. Sakai, T. Mukawa, K. Tsuchiya, H. Sakai, M. Abe, 13181. DOI: 10.1002/chem.200901440
J. Nanosci. Nanotechnol. 2009, 9 (1), 461. DOI: 10.1166/ [97] A. Leiva, C. Saldias, C. Quezada, A. Toro-Labbe, F. J. Espi-
jnn.2009.J058 noza-Beltran, M. Urzua, L. Gargallo, D. Radic, Eur. Polym. J.
[87] R. Sardar, J. W. Park, J. S. Shumaker-Parry, Langmuir 2007, 2009, 45 (11), 3035. DOI: 10.1016/j.eurpolymj.2009.08.005
23 (23), 11883. DOI: 10.1021/la702359g [98] J. Shan, H. Tenhu, Chem. Commun. 2007, 4580. DOI:
[88] R. N. Mitra, P. K. Das, J. Phys. Chem. C 2008, 112 (22), 8159. 10.1039/b707740h
DOI: 10.1021/jp712106d [99] B. A. Rozenberg, R. Tenne, Prog. Polym. Sci. 2008, 33 (1), 40.
[89] X. Y. Shi, K. Sun, J. R. Baker, J. Phys. Chem. C 2008, 112 (22), DOI: 10.1016/j.progpolymsci.2007.07.004
8251. DOI: 10.1021/jp801293a [100] Y. Ofir, B. Samanta, V. M. Rotello, Chem. Soc. Rev. 2008, 37
(9), 1814. DOI: 10.1039/b712689c

www.cet-journal.com © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2011, 34, No. 1, 15–28