10806 J. Phys. Chem.

C 2007, 111, 10806-10813

Synthesis of Normal and Inverted Gold-Silver Core-Shell Architectures in β-Cyclodextrin

and Their Applications in SERS

Surojit Pande,† Sujit Kumar Ghosh,† Snigdhamayee Praharaj,† Sudipa Panigrahi,†

Soumen Basu,† Subhra Jana,† Anjali Pal,† Tatsuya Tsukuda,‡ and Tarasankar Pal*,§
Departments of CiVil Engineering and Chemistry, Indian Institute of Technology, Kharagpur 721302, India,
and Institute for Molecular Science (IMS), Myodaiji, Okazaki 444-8585, Japan
ReceiVed: January 11, 2007; In Final Form: May 21, 2007

Beta-cyclodextrin (β-CD) in alkaline solution has been observed to produce mono- and bimetallic nanoparticles
of silver and gold and to provide in-house stability to both types of particles. Thus, the weak reducing capability
of the β-CD molecule (oxidation occurs at +1.33 V vs Ag/AgCl) and its unique kinetic control over the
evolution of both normal and inverted core-shell bimetallic architectures have been established. The structure
and composition of the bimetallic particles were characterized by UV-visible spectroscopy, transmission
electron microscopy, high-resolution transmission electron microscopy, electron dispersive spectroscopy, and
X-ray photoelectron spectroscopy. Bimetallic core-shell particles containing silver shells have been shown
to provide an elegant SERS-active substrate compared to the corresponding monometallic nanoparticles, and
therefore, they highlight the importance of electronic ligand effects on the enhancement of the Raman signals
of molecular probes on nanostructured metallic surfaces.

1. Introduction plasmon absorption. This band is attributed to the collective

In recent years, bimetallic nanoparticles have fascinated oscillation of the electron gas in the particles with a change in
scientists because of their superior optical,1 electronic,2 cata- the electron density at the surface.17 Because of these attractive
lytic,3 and magnetic4 properties compared to their monometallic plasmon absorption features, the optical properties of bimetallic
counterparts. These interesting physicochemical properties result nanoparticles composed of gold and silver are the subject of
from the combination of two kinds of metals and their fine considerable interest in the fields of nanoscience and nanotech-
structures, evolving new surface characteristics.5 Thus, bimetallic nology. The comparison of calculated and measured surface
nanoparticles, composed of two different metal elements, are plasmon (SP) extinction spectra has frequently been employed
of greater interest than monometallic nanoparticles, from both as one of the criteria for distinguishing between alloyed and
the scientific and technological points of view.6-10 The structure layered core-shell structures of bimetallic Au-Ag/Ag-Au
of bimetallic nanoparticles is defined by the distribution modes nanoparticles. Since its discovery in 1974, the single-molecule
of the two elements and can be oriented in random alloy, alloy sensitivity of Raman scattering enhanced by resonantly excited
with an intermetallic compound, cluster-in-cluster, and core- metal nanoparticles has caused a renewed interest in surface-
shell structures. A variety of synthetic strategies (chemical, enhanced Raman scattering (SERS).18 However, the mechanism
radiolytic, and photolytic) have been adopted during the past for SERS has been a matter of considerable debate.19-24 The
few years to prepare stable bimetallic particles in both two phenomena responsible for SERS are a large increase in
aqueous11-13 and nonaqueous14 media. In addition, different the electric field near the surface (electromagnetic effect) and
capping agents have been used to stabilize the resulting specific adsorbate-surface interactions (chemical effect). Modi-
particles.15,16 Methods for the preparation of bimetallic nano- fied surfaces of silver and gold nanoparticles have attracted wide
particles from metal salts can be divided into two groups: co- interest because of their potential applications in sensors,25
reduction and successive reduction of two metal salts. Co- catalysis,26 nonlinear optical materials,27 etc.
reduction is the simplest preparative method whereby the Modification of silver and gold nanoparticle surfaces with
simultaneous reduction of two metal precursors is achieved. different organic receptors is important for the development of
Successive reduction is usually carried out for the preparation biological tracers as well as optoelectronic nanodevices. Cy-
of core-shell or structured bimetallic nanoparticles. Therefore, clodextrin (CD), a soluble nontoxic molecule, is an important
synthesis of stable bimetallic particles with sizes in the receptor and becomes a unique choice as it can form both
nanometer range requires a great deal of control over the channel and cage complexes incorporating nanosize metal guests
synthetic technique. with its cyclic oligosaccharide containing internal cavities. The
Colloidal solutions of noble metals, especially those of gold host molecules are made up of six, seven, or eight glucose units
and silver, have been studied extensively because of their intense connected in a large ring, called R-, β-, or γ-CD, respectively.
absorption band in the visible region, often called surface Among the three CDs, β-CD is the most widely used because
its internal cavity diameter ranges from 6 to 6.5 Å.28 The “mod
* To whom correspondence should be addressed. E-mail: tpal@chem. of fit” between host and guest and the hydrophobic effect are
iitkgp.ernet.in. probably the most important. The use of β-CD as a complexing
† Department of Civil Engineering, Indian Institute of Technology.
‡ Institute for Molecular Science (IMS). agent represents a useful strategy for minimizing the photoin-
§ Department of Chemistry, Indian Institute of Technology. duced biological damage associated with many nonsteroidal anti-
10.1021/jp0702393 CCC: $37.00 © 2007 American Chemical Society
Published on Web 07/04/2007
Gold-Silver Core-Shell Architectures in β-Cyclodextrin J. Phys. Chem. C, Vol. 111, No. 29, 2007 10807

inflammatory drugs (NSAIDs) as well as a tool for increasing source emitting at a wavelength of 633 nm and a Peltier cooled
drug photostability. Moreover, the weak binding forces respon- (-70 °C) charge coupled device (CCD) camera. A Leica
sible for association with the β-CD cavity provide a useful model microscope was attached and was fitted with three objectives
for mimicking the interactions of drugs with hydrophobic (5×, 20×, 50×). For these experiments, the 20× objective was
pockets of biological substrates. To exploit the host-guest used. Laser power at the sample was 20 mW, and the data
interactions of β-CD, different modified29 and unmodified β-CD acquisition time was usually 30 s. The holographic grating (1800
molecules have been chemisorbed onto gold films, gold grooves/mm) and the slit provided a spectral resolution of
electrodes, and gold electrodes of a quartz microbalance.30-32 1 cm-1.
Recently, perthiolated β-CD, i.e., per-6-thio-β-CD and mono- 2.2. Synthesis of Monometallic Gold and Silver Colloids.
6-lipoyl-amido-2,3,6-O-permethyl-β-CD, has been used to The metal nanoparticles (gold and silver) were synthesized by
modify gold nanoparticle surfaces upon direct addition to dissolving 0.0396 g of β-CD in 4.93 mL of water and shaken
HAuCl4 solution. Unmodified β-CD has also been used to well. After dissolving the β-CD, 0.02 mL of the corresponding
prepare gold and silver nanoparticles in the presence of different metal salt solution HAuCl4 (10 mM) and AgNO3 (10 mM) were
reducing agents such as dimethyl formamide, ethanol, methanol, added to it. After 2 min, 0.05 mL of NaOH (1.0 M) was added
ethylene glycol, and sodium citrate.33-35 We recently reported to the solution so that the pH of the solution became ∼10-12.
the reducing and capping properties of glucose for preparing Then, the reaction mixtures were shaken well and heated on a
size- and shape-selective metal nanoparticles in alkaline me- water bath. After ∼20 min, the solution turned pink for gold
dium.36 As β-CD is the higher homologue of glucose, we tried and yellow for silver, indicating the formation of the corre-
to examine its glucose-like properties for the reduction of sponding metal nanoparticles in the solution.
metallic precursor salts to well stabilize metal nanoparticles. 2.3. Synthesis of Aucore-Agshell and Agcore-Aushell Bimetal-
With this idea in mind, for the first time, we have employed lic Nanoparticles. Aucore-Agshell nanoparticles were synthesized
unmodified β-CD in aqueous solution, which acts as both a using the following procedure: An aliquot of 0.04 mL of AgNO3
reducing and stabilizing agent in alkaline medium. (10 mM) was added dropwise to 5 mL of the preformed gold
In this article, we report a general method for the synthesis colloidal solution. The solution was allowed to incubate for
of gold and silver nanoparticles and their bimetallic conjugates, 5 min and then heated on a water bath. After about 30 min, the
i.e., Aucore-Agshell and Agcore-Aushell, using unmodified β-CD pink color of the solution turned to reddish yellow, indicating
in alkaline medium. The structure and composition of the the formation of a silver shell on the gold particles, i.e., the
bimetallic particles were characterized by UV-visible spec- formation of Aucore-Agshell particles. During the formation of
troscopy, transmission electron microscopy (TEM), high- the particles, the initial pink color of the solution gradually
resolution transmission electron microscopy (HRTEM), electron deceased, and a yellow color developed. The final concentrations
dispersive spectroscopy (EDS), and X-ray photoelectron spec- of the gold and silver colloids in the bimetallic nanoparticles
troscopy (XPS). Here, β-CD plays a dual role: it acts as both were adjusted to 0.05 and 0.1 mM, respectively. No extra β-CD
a reducing and capping agent. β-CD becomes kinetically capable or NaOH was added to induce the chemical reduction of silver
of reducing Au(III) ions on silver seed particles to obtain an ions and their deposition on the gold seed particles. The
inverted core-shell architecture. Finally, we used 1,10-phenan- alkalinity of the gold colloidal solution helps to induce the
throline as a molecular probe to compare the SERS activity of chemical reduction of Ag(I) ions and their deposition on the
the core-shell bimetallic nanoparticles with that of the corre- gold particles.
sponding monometallic nanoparticles and found that the core- For the synthesis of inverted core-shell nanoparticles, an
shell structured bimetallic nanoclusters exhibit a higher SERS aliquot of 0.04 mL HAuCl4 (10 mM) was added dropwise to
activity than the corresponding monometallic nanoclusters. 5 mL of preformed silver colloids with vigorous stirring. During
the progress of the reaction, the yellow color of the silver colloid
2. Experimental Section gradually diminished, and the pink color of the gold colloid
evolved; after ∼20 min, the pink color of the solution was found
2.1. Reagents and Instruments. All reagents were of
to be persistent, indicating the formation of Agcore-Aushell
analytical reagent grade. Chloroauric acid (HAuCl4), silver
nanoparticles. Here, also, no extra β-CD or NaOH was added
nitrate (AgNO3), β-CD, and 1,10-phenanthroline were obtained
to induce the formation of core-shell particles.
from Sigma-Aldrich and were used as received. Pyrene, mercuric
chloride (HgCl2), sodium hydroxide (NaOH), and potassium
3. Results and Discussion
cyanide (KCN) were obtained from S. D. Fine Chemicals.
Dopamine, aminopyrene, crystal violet, and rhodamine 6G were 3.1. Evolution of Normal and Inverted Core-Shell Bi-
obtained from Sigma-Aldrich. Doubly distilled water was used metallic Nanoparticles. The interaction of small metal particles
throughout the course of this investigation. with an external electromagnetic field induced by light results
All absorption spectra were recorded on a Shimadzu UV- in coherent oscillations of the conduction (free) electrons (mainly
160 spectrophotometer (Kyoto, Japan) using solutions in a 1-cm within the surface), called surface plasmon oscillations. This
quartz cuvette. TEM, HRTEM, and EDS measurements of the surface plasmon resonance largely depends on the particle size
metal sols were performed with a Hitachi H-9000 NAR and shape and, of course, on the metallic material and its
instrument on samples prepared by placing a drop of fresh metal surrounding environment. The optical absorption spectra of gold
sols on copper grids precoated with carbon films and then and silver colloids have been a subject of study for decades.
evaporating the solvent under a vacuum. XPS analysis was Because of the different plasmonic excitation resonances of the
performed on an ESCA LAB MK II instrument using Mg as two metals, these colloids exhibit absorption maxima at about
the exciting source. The samples were prepared by placing one 520 and 402 nm for gold and silver, respectively. Figure 1 shows
drop of the prepared mono- and bimetallic nanoparticles on a UV-visible spectra of gold and silver colloids in their final
clean glass slide and then allowing them to dry in air. SERS stage of preparation using β-CD at an alkaline pH of ∼10-12
spectra of 1,10-phenanthroline were obtained with a Renishaw by reduction of HAuCl4 and AgNO3, respectively. Interestingly,
Raman microscope, equipped with a He-Ne laser excitation it was seen that the absorption profile shows a high degree of
10808 J. Phys. Chem. C, Vol. 111, No. 29, 2007 Pande et al.

particles gradually becomes blue-shifted, and the absorption

spectrum of silver emerges. Within ∼20 min, the two bands
merge together into a single band at 402 nm. Finally, the Aucore-
Agshell bimetallic colloids show only one plasmon resonance at
402 nm, which can be attributed to the plasmon resonance of
silver particles alone. The appearance of only one absorption
band corresponding to silver indicates that homogeneous mixed
colloidal particles of the two metals are formed without
significant formation of independent particles. The presence of
only one plasmon band indicates the core-shell structure of
the particles that reflects the true silver plasmon band as if there
were no monometallic gold in the medium. Therefore, it is
presumed that the gold nanoparticles are now completely
Figure 1. Absorption spectra of (a) Au(0) and (b) Ag(0) seed particles. covered by silver.
The evolution of the surface plasmon band for the core-
shell bimetallic nanoparticles can be described by considering
the polarizability of a core-shell particle of radius R as follows39

(s - m)(c + 2s) + (1 - g)(c - s)(m + 2s)

R ) R3 (i)
(s + 2m)(c + 2s) + (1 - g)(2s - 2m)(c - s)

where m is the dielectric constant of the ambient; c and s are

the dielectric functions of the core and shell materials, respec-
tively; and g is the volume fraction of the shell layer (i.e., if
the outer radii of the composite particle and its core are R2 and
R1, respectively, then g ) 1 - R13/R23). This equation indicates
that, in the absorption spectrum, which initially looks like that
of gold, the surface plasmon peak observed for silver colloidal
particles progressively gets more intense as the silver shell
increases in thickness. Thus, it can be concluded that the optical
properties differ from those of both silver and gold and the Au-
Ag composition varies smoothly from Ag-lean to Ag-rich
material as the concentration of silver allowed to react with the
colloidal gold seed particles increases.
Figure 2B shows the emergence in the absorption spectra of
gold-coated silver colloids, i.e., Agcore-Aushell bimetallic nano-
particles from silver seeds. When HAuCl4 is added, the color
of the silver colloids changes to reddish pink through orange
within a few minutes. In the colloid having a lower amount of
gold deposited on silver, a unique, broad absorption band
appears in an intermediate wavelength region (within 405-
Figure 2. Time-dependent absorption spectra of (A) Aucore-Agshell and 515 nm) because of the partial coverage of the seed particles.
(B) Agcore-Aushell bimetallic nanoparticles prepared from β-CD (7 mM)
capped Au and Ag seed at pH ∼ 10-12.
The peak maximum shifts to longer wavelength compared to
that of silver nanoparticles. Moreover, there is no separate
well-imposed absorption profiles, indicating the reproducibility plasmon resonance of silver in the gold colloids, which indicates
of nanoparticle synthesis during β-CD-mediated reduction for that the nanoparticles are not a simple physical mixture of two
the metal salts. different kinds of metal particles. Finally, the peak becomes
During the evolution of the bimetallic nanoparticles from the shifted to 523 nm, which can be attributed to the complete
monometallic particles, we recorded their UV-visible spectra encapsulation of silver nanoparticles by gold, i.e., Agcore-Aushell
at different stages. The modification of the plasmon absorption particles are formed. The changes in the surface plasmon
band in successive stages of formation of the core-shell absorption of the Agcore-Aushell particles can be explained by
structure from gold seeds is shown in Figure 2A. Initially, gold considering the polarizability in eq i in a fashion similar to that
particles were synthesized separately by the β-CD reduction used for the Aucore-Agshell particles.
method and were used as seed for the evolution of Aucore- From these surface plasmon resonance spectra, we conclude
Agshell bimetallic nanoparticles. The colloidal solution of the that the monometallic gold and silver colloids and bimetallic
seed particles shows a pink color with an absorption band at Aucore-Agshell and Agcore-Aushell particles are formed by using
520 nm. Upon addition of Ag(I) ions to the gold seed particles, β-CD at alkaline pH of ∼10-12. Thus, this phenomenon
silver ions are adsorbed onto the surface of the gold seed indicates that β-CD acts as a reducing agent under alkaline
particles and thereby reduced37,38 in successive stages to form conditions.
a shell layer over the gold particles, as seen from the absorbance 3.2. Characterization of the Bimetallic Nanoparticles.
measurements. At the intermediate stages of particle evolution, 3.2.1. Transmission Electron Microscopy (TEM) Study. Clear
two plasmon bands can be observed at 508 and 438 nm, which confirmation of the formation of normal and inverted core-
indicates the partial coverage of gold by silver nanoparticles. shell structures emerged from TEM, HRTEM, EDS, and XPS
With progressive heating, the absorption band of the gold studies. The TEM images of the mono- (gold and silver) and
Gold-Silver Core-Shell Architectures in β-Cyclodextrin J. Phys. Chem. C, Vol. 111, No. 29, 2007 10809

Figure 3. TEM images of (A) Au(0), (B) Ag(0), (C) Aucore-Agshell, and (D) Agcore-Aushell nanoparticles.

bimetallic particles (Aucore-Agshell and Agcore-Aushell) are shown observation, we conclude that, in the case of Agcore-Aushell
in Figure 3A-D. From the TEM images, it can be seen that nanoparticles, silver remains in the core as Ag(0).
the monometallic particles are ∼10 nm, which is consistent with 3.2.2. X-ray Photoelectron Spectroscopy (XPS). XPS was
the results obtained by UV-visible spectroscopy. From TEM employed as a surface monitoring technique to further support
images of bimetallic particles, it can be observed that the particle the above results. In the case of the Aucore-Agshell nanoparticles
sizes are 13 ( 2 and 11 ( 3 nm for the Aucore-Agshell and (Figure 5A,B), XPS clearly shows that the shell is composed
Agcore-Aushell particles, respectively. of silver. The binding energies of Ag 3d5/2 and Ag 3d3/2
To examine whether a core-shell structure was obtained in measured for the two peaks are 373 and 379 eV, respectively.
the β-CD reduction reaction, HRTEM images of the as-prepared The binding energies of Au 4f7/2 and Au 4f5/2 were measured
materials were obtained. The HRTEM images support the at approximately 88.2 and 92 eV, respectively. Similarly, in
formation of normal and inverted core-shell structures rather the case of the Agcore-Aushell nanoparticles (Figure 6A,B), the
than hollow-core structure. Figure 4A,B shows HRTEM images shell is encapsulated with gold. The binding energies of Au
of Aucore-Agshell and Agcore-Aushell nanoparticles, respectively. 4f7/2 and Au 4f5/2 measured for the two peaks are 88.2 and
The inverted core-shell structure shows a less dense interior 92 eV, and those for Ag 3d5/2 and Ag 3d3/2 are 373 and
core of silver surrounded by a thicker shell. Here, the less dense 379 eV, respectively. The energies for gold and silver are in
interior core and thicker shell were produced because of presence good agreement with the literature values for the binding
of silver in the core and gold in the shell. energies of gold and silver.40 These data confirm the formation
EDS measurements indicate the organization of the particles of an inverted core-shell structure rather than formation of a
or the presence of the metals employed in the preparation hollow core inside the gold shell.
procedure. Here, the EDS spectra of the Agcore-Aushell structure 3.2.3. Cyanide Dissolution Reaction. To confirm the forma-
show the presence of silver and gold atoms (see Supporting tion of the core-shell architectures, i.e., Aucore-Agshell and
Information). HRTEM observations together with the EDS Agcore-Aushell structures, typical complexation reactions with
measurements, conducted with electron beam irradiation clearly cyanide were carried out under ambient conditions.12,36 The
indicate the formation of the Agcore-Aushell structure. Prolonged successive changes of the surface plasmon absorption of the
electron beam irradiation (∼10 min) during EDS studies not bimetallic colloids upon dissolution with cyanide clearly support
only destroys the core-shell morphology but also brings the the formation of core-shell structures. An aliquot of KCN
core material, Ag(0), to the surface (see Supporting Information). (10 mM) was added to 5 mL of bimetallic colloids separately,
Thus, both silver and gold become obvious surface atoms, and and the changes in absorbance values were measured spectro-
the bimetallic particles take on a new shape. From this photometrically. In the case of Aucore-Agshell particles, it was
10810 J. Phys. Chem. C, Vol. 111, No. 29, 2007 Pande et al.

Figure 5. XPS spectra of (A) Aucore and (B) Agshell in Aucore-Agshell

bimetallic nanoparticles.

Figure 4. HRTEM images of (A) Aucore-Agshell and (B) Agcore-Aushell

bimetallic nanoparticles.

found that the shell first dissolves slowly and the peak due to
the Aucore-Agshell nanoparticles gradually red shifts. On con-
tinuous shaking in the presence of oxygen, the yellow-colored
solution (Aucore-Agshell nanoparticles) turned pink because of
the stepwise removal of silver layers. Finally, bare gold
nanoparticles, i.e., seeds, reappeared with the plasmon peak for
gold nanoparticles at 526 nm via a double-hump curve. Addition
of excess cyanide ions then dissolved the gold nanoparticles,
and finally, the solution became colorless. This study confirms
that the gold layer was completely covered by silver nanopar-
ticles, i.e., Aucore-Agshell bimetallic nanoparticles formed in
solution. Similarly, in the case of Agcore-Aushell nanoparticles,
the Au shell first dissolved, and the color changed from pink
to yellow. Because of the dissolution of the Au shell, the peak
was blue-shifted to 412 nm for silver, and finally, the yellow
color vanished because of the dissolution of the Ag core. The
kinetics of the dissolution reaction has been described else-
where.41 Thus, the stepwise vanishing of the surface plasmon
oscillation demonstrates that the core-shell structures are
dissolved in the presence of cyanide ions under ambient
conditions.
3.3. Role of β-CD. 3.3.1. Kinetic EVolution and Stabilization Figure 6. XPS spectra of (A) Agcore and (B) Aushell in Agcore-Aushell
of the Particles: Ordinary Role of β-CD. Through the manipu- bimetallic nanoparticles.
lation of the kinetics of particle growth, β-CD is introduced to
the reaction medium at a particular concentration that prefer- nanostructured core-shell structures of both normal and inverted
entially allows the adsorption, reduction, and growth of a metal architectures are generated. As these metallic particles shrink
on preformed gold or silver particles, resulting in bimetallic into the nanoscale regime, either electrostatic43 or steric
structures. The layer-by-layer wrapping of one metallic constitu- stabilization44 for the particles must occur to account for the
ent onto the surface of the other is observed because of the very high surface energies of the particles in the nanometer size
similar lattice parameters of the constituents.42 Thus, hierarchical range. β-CD molecules serve this purpose well. Alkaline
Gold-Silver Core-Shell Architectures in β-Cyclodextrin J. Phys. Chem. C, Vol. 111, No. 29, 2007 10811

conditions facilitate the deprotonation of the alcohol function- is possibly higher than the galvanic replacement reaction rate
alities of β-CD molecules (the stretching frequency due to -OH under the experimental conditions. Mechanistically, it can be
shifts from 3368 to 3390 cm-1), which promotes the kinetic specified that the oxidation resistance of silver presumably
evolution and stabilization of nanoparticles. increases and this inhibits the normal oxidation of Ag(0) in the
Interestingly enough, the evolution of mono- or bimetallic presence of Au(III) ions. The diffusion resistance (DR) and
nanoparticles of gold and silver from the corresponding precur- charge-transfer resistance (CTR) should also have a bearing on
sor salt solutions was not observed when individual PACs the oxidation of Ag(0), as has been described only recently.13
(polyaromatic compounds) such as pyrene or 1,10-phenanthro- Presumably, both the DR and CTR of Au(III) are increased in
line or HgCl2-saturated β-CD were employed in lieu of β-CD, so that the electron transfer from Ag(0) to Au(III) ions
unsaturated β-CD. These guest molecules individually can is inhibited. Furthermore, it can also be suggested that the self-
saturate the cavity of β-CD, forming host-guest-type inclusion organization and hydrophobic interaction of β-CD with Ag(0)
complexes.45 In such cases, β-CD binds the guest, the alcohol makes the latter nobler than Au(0). This results in the formation
functionalities of β-CD remain completely engaged with sto- of the Agcore-Aushell structure instead of the formation of a
ichiometric amounts of individual guest molecules, and cavity hollow core inside the gold shell.
saturation takes place through hydrogen bonding. Under these 3.4. Application of Normal and Inverted Core-Shell
circumstances, β-CD fails to reduce metallic precursor salts Bimetallic Nanoparticles in SERS Spectroscopy: Electronic
because its reducing functionalities (-OH groups) remain Ligand Effect. SERS spectroscopy has been producing en-
occupied by the formation of inclusion complexes with the guest. lightening results since its discovery in 1974.18 Noble-metal
However, conventional reducing agents can produce metallic nanoparticles, usually silver and gold, are well-known for their
particles from HAuCl4 or AgNO3 solution in the presence of strong interactions with visible light through the resonant
guest-saturated β-CD, but the metallic particles precipitate from excitations of the collective oscillations of the conduction
alkaline β-CD solutions. This precipitation is observed because electrons within the particles. Creighton et al.51 and Jeanmaire
the guest-saturated β-CD cannot offer stability to the otherwise and Van Duyne52 independently confirmed the findings on the
produced metal particles. enhancement aspect of Raman signals, and silver is the best-
During the reduction of metal salts to the corresponding metal suited choice for such studies.45,49,50 However, the mechanism
nanoparticles, the β-CD molecules are oxidized. The presence of SERS has been a matter of considerable debate.19,53-55 It
of oxidized and unoxidized β-CD was confirmed by ESI mass has been widely accepted that there are two mechanisms for
spectra measured in anionic mode. From the ESI mass spectra, the observed and, at times, huge enhancement in SERS:
the peaks are obtained in the 1134 and 1232 mass regions due electromagnetic and chemical. The electromagnetic mechanism
to unoxidized β-CD and the oxidized primary alcohol func- is based on the interaction of the electric field of the surface
tionality of β-CD, i.e., the -COOH group, respectively. It has plasmons with the transition moment of the adsorbed molecule,
been reported that, at pH ∼10-12, the secondary alcoholic
whereas the chemical mechanism is based on the idea that
group of β-CD is not oxidized and also no dioxirane formation
mixing of molecular and metal states occurs. The chemical
is formed.46,47 To offset the van der Waals forces responsible
mechanism might arise from the mixing of metal orbitals with
for particle coalescence, carboxylic acids (produced as the
orbitals on a molecule, providing charge transfer that results in
oxidation products of β-CD molecules) bearing a negative
a resonant Raman mechanism at much lower energies than those
surface charge provide a dense coating on the surfaces of the
available in the free molecule. Both mechanisms and even others
metal particles and provide stabilization.
can contribute simultaneously to the SERS enhancement to a
3.3.2. Probing Normal and InVerted Core-Shell Structures
certain extent, which is dependent on the experimental condi-
Obtained by a Similar Synthetic Strategy: Extraordinary Role
tions, the nature and morphology of the metallic nanoparticles,
of β-CD. It is now well-established in the literature that one
and other factors.
can easily obtain a normal core-shell structure from the
constituents where the more noble metal constitutes the core The present report of SERS measurements probes the
while the less noble metal forms the shell of the bimetallic influence of the shell material of the as-prepared particles in
cluster.37 However, the synthesis of an inverted core-shell solution using 1,10-phenanthroline as a molecular probe. The
architecture is unfamiliar without the use of any extra reagent. molecule 1,10-phenanthroline has been used in SERS as a probe
It is almost impossible because of the inevitable redox reaction, by Li et al. and Miranda in the cases of gold electrode and silver
i.e., Ag(0) oxidation by Au(III) ions.39,48-50 The successful sols.56,57 However, there have been no reports of SERS studies
synthesis of inverted core-shell architectures thus addresses in a particular dielectric medium involving individual gold,
several challenges. In the present experiments, the preformed silver, and their bimetallic conjugates as substrates for examining
Au(0) or Ag(0) nanoparticles act as seeds and β-CD becomes the electromagnetic (EM) mechanism. This has not been
kinetically capable of reducing the incoming Ag(I) or Au(III) possible, and it has remained a challenge to produce all of these
ions onto the seed particles to create the core-shell morphology particles in the same dielectric environment. Here, the probe
as represented in the following reaction molecules induce particle aggregation without the need of any
extra electrolyte for generating a “hot junction”. The junction
Aucore + Ag(I) 9
β-CD
8 Aucore-Agshell (1) can therefore function as an electromagnetic “hot spot” analo-
pH ∼ 10-12 gous to those predicted to exist in large fractal aggregates. Thus,
β-CD absolute EM effects can be confirmed from the SERS signal
Agcore + Au(III) 9
pH ∼ 10-12
8 Agcore-Aushell (2) enhancement. In the present experiments, bimetallic nanopar-
ticles were employeing the d at the same concentration as
Reaction 1 is favorable, as the standard reduction potential of monometallic particles of silver and gold of the same size range
Ag(I)/Ag(0) is lower than that of Au(III)/Au(0). In the case of (∼12 nm) to investigate the electronic ligand effect4,5,8,9 (the
reaction 2, however, β-CD helps to produce the inverted core- so-called electronic ligand effect in the case of core-shell
shell architecture through the reduction of Au(III) ions in the particles) on the SERS spectra of 1,10-phenanthroline. It can
presence of preformed Ag(0). Here, the Au(III) reduction rate be seen that the probe molecules show distinctly different SERS
10812 J. Phys. Chem. C, Vol. 111, No. 29, 2007 Pande et al.

or the work function. Because the Fermi level is lower for gold
(about -5.0 eV) than for silver (about -4.6 eV), charge transfer
occurs along a direction from silver to gold. Thus, the plasmon
band of silver will be red-shifted, and blue shifting will be
observed when the gold core is taken into consideration. The
spectra of Aucore-Agshell bimetallic nanoparticles with higher
proportions of Ag are the same as those of monometallic silver
particles (Figure 2A). On the other hand, in the case of Agcore-
Aushell nanoparticles, the gold shell will show the opposite effect.
Thus, Aucore-Agshell nanoparticles should welcome probes such
as 1,10-phenanthroline, dopamine, aminopyrene, crystal violet,
and rhodamine 6G for attachment to show a marked SERS
effect. Therefore, the core-shell bimetallic architectures show
Figure 7. SERS spectra of 1,10-phenanthroline (0.5 mM) using (a) higher SERS activities than the corresponding monometallic
Aucore-Agshell nanoparticles, (b) Agcore-Aushell nanoparticles, (c) Ag- structures. Hence, one can probe the shell material beyond
(0), and (d) Au(0) (0.15 mM). doubt.
SCHEME 1: Schematic Representation of the
Formation of Mono- and Bimetallic Nanoparticles and 4. Conclusion
their Corresponding SERS Spectra In summary, the present synthetic method is of three-fold
interest. First, the results reported herein describe particle
evolution in alkaline β-CD solution without the need of any
other reducing agent. Second, this “green chemistry” approach
has the potential to produce both normal and inverted core-
shell morphologies in bimetallic counterparts without changing
the medium. Third, leaving aside the usual redox reaction, β-CD
supports the kinetic evolution of a desired shell on preformed
seed particles. Finally, the present work substantiates the fact
that Aucore-Agshell nanoparticles provide an elegant substrate
for SERS studies and offers the possibility of examining probe
molecules down to the single-molecule level. Thus, the practical
application of unmodified β-CD under alkaline conditions
should gain further momentum in nanoparticle chemistry.

Acknowledgment. The authors are thankful to the UGC,

DST, NST, and CSIR, New Delhi, India, and the IIT Kharagpur
for financial assistance. We are also thankful to IMS, Japan,
for the ESI mass spectroscopy.
signals in the presence of different sets of colloidal solutions.
Supporting Information Available: EDS of spectra of
The salient feature of physical significance is that we observe
Agcore-Aushell bimetallic nanoparticles and HRTEM images of
better enhancement of the SERS signal of the probe molecule
Agcore-Aushell bimetallic nanoparticles (a) before and (b) after
with Aucore-Agshell particles than with bimetallic Agcore-Aushell
prolonged (∼10 min) electron beam irradiation. This material
or monometallic gold or even silver particles, as shown in
is available free of charge via the Internet at http://pubs.acs.org.
Figure 7 (Scheme 1). Similar results were also obtained with
other probe molecules, e.g., dopamine, aminopyrene, crystal References and Notes
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