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
scientists because of their superior optical,1 electronic,2 cata-
lytic,3 and magnetic4 properties compared to their monometallic
counterparts. These interesting physicochemical properties result
from the combination of two kinds of metals and their fine
structures, evolving new surface characteristics.5 Thus, bimetallic
nanoparticles, composed of two different metal elements, are
of greater interest than monometallic nanoparticles, from both
the scientific and technological points of view.6-10 The structure
of bimetallic nanoparticles is defined by the distribution modes
of the two elements and can be oriented in random alloy, alloy
with an intermetallic compound, cluster-in-cluster, and core-
shell structures. A variety of synthetic strategies (chemical,
radiolytic, and photolytic) have been adopted during the past
few years to prepare stable bimetallic particles in both
aqueous11-13 and nonaqueous14 media. In addition, different
capping agents have been used to stabilize the resulting
particles.15,16 Methods for the preparation of bimetallic nano-
particles from metal salts can be divided into two groups: co-
reduction and successive reduction of two metal salts. Co-
reduction is the simplest preparative method whereby the
simultaneous reduction of two metal precursors is achieved.
Successive reduction is usually carried out for the preparation
of core-shell or structured bimetallic nanoparticles. Therefore,
synthesis of stable bimetallic particles with sizes in the
nanometer range requires a great deal of control over the
synthetic technique.
Colloidal solutions of noble metals, especially those of gold
and silver, have been studied extensively because of their intense
absorption band in the visible region, often called surface
* To whom correspondence should be addressed. E-mail: tpal@chem.
iitkgp.ernet.in.
† Department of Civil Engineering, Indian Institute of Technology.
‡ Institute for Molecular Science (IMS).
§ Department of Chemistry, Indian Institute of Technology.
10.1021/jp0702393 CCC: $37.00 © 2007 American Chemical Society
Published on Web 07/04/2007
oscillation of the electron gas in the particles with a change in
the electron density at the surface.17 Because of these attractive
plasmon absorption features, the optical properties of bimetallic
nanoparticles composed of gold and silver are the subject of
considerable interest in the fields of nanoscience and nanotech-
nology. The comparison of calculated and measured surface
plasmon (SP) extinction spectra has frequently been employed
as one of the criteria for distinguishing between alloyed and
layered core-shell structures of bimetallic Au-Ag/Ag-Au
nanoparticles. Since its discovery in 1974, the single-molecule
sensitivity of Raman scattering enhanced by resonantly excited
metal nanoparticles has caused a renewed interest in surface-
enhanced Raman scattering (SERS).18 However, the mechanism
for SERS has been a matter of considerable debate.19-24 The
two phenomena responsible for SERS are a large increase in
the electric field near the surface (electromagnetic effect) and
specific adsorbate-surface interactions (chemical effect). Modi-
fied surfaces of silver and gold nanoparticles have attracted wide
interest because of their potential applications in sensors,25
catalysis,26 nonlinear optical materials,27 etc.
Modification of silver and gold nanoparticle surfaces with
different organic receptors is important for the development of
biological tracers as well as optoelectronic nanodevices. Cy-
clodextrin (CD), a soluble nontoxic molecule, is an important
receptor and becomes a unique choice as it can form both
channel and cage complexes incorporating nanosize metal guests
with its cyclic oligosaccharide containing internal cavities. The
host molecules are made up of six, seven, or eight glucose units
connected in a large ring, called R-, β-, or γ-CD, respectively.
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
of fit” between host and guest and the hydrophobic effect are
probably the most important. The use of β-CD as a complexing
agent represents a useful strategy for minimizing the photoin-
duced biological damage associated with many nonsteroidal anti-
Gold-Silver Core-Shell Architectures in β-Cyclodextrin
inflammatory drugs (NSAIDs) as well as a tool for increasing
drug photostability. Moreover, the weak binding forces respon-
sible for association with the β-CD cavity provide a useful model
for mimicking the interactions of drugs with hydrophobic
pockets of biological substrates. To exploit the host-guest
interactions of β-CD, different modified29 and unmodified β-CD
molecules have been chemisorbed onto gold films, gold
electrodes, and gold electrodes of a quartz microbalance.30-32
Recently, perthiolated β-CD, i.e., per-6-thio-β-CD and mono-
6-lipoyl-amido-2,3,6-O-permethyl-β-CD, has been used to
modify gold nanoparticle surfaces upon direct addition to
HAuCl4 solution. Unmodified β-CD has also been used to
prepare gold and silver nanoparticles in the presence of different
reducing agents such as dimethyl formamide, ethanol, methanol,
ethylene glycol, and sodium citrate.33-35 We recently reported
the reducing and capping properties of glucose for preparing
size- and shape-selective metal nanoparticles in alkaline me-
dium.36 As β-CD is the higher homologue of glucose, we tried
to examine its glucose-like properties for the reduction of
metallic precursor salts to well stabilize metal nanoparticles.
With this idea in mind, for the first time, we have employed
unmodified β-CD in aqueous solution, which acts as both a
reducing and stabilizing agent in alkaline medium.
In this article, we report a general method for the synthesis
of gold and silver nanoparticles and their bimetallic conjugates,
i.e., Aucore-Agshell and Agcore-Aushell, using unmodified β-CD
in alkaline medium. The structure and composition of the
bimetallic particles were characterized by UV-visible spec-
troscopy, transmission electron microscopy (TEM), high-
resolution transmission electron microscopy (HRTEM), electron
dispersive spectroscopy (EDS), and X-ray photoelectron spec-
troscopy (XPS). Here, β-CD plays a dual role: it acts as both
a reducing and capping agent. β-CD becomes kinetically capable
of reducing Au(III) ions on silver seed particles to obtain an
inverted core-shell architecture. Finally, we used 1,10-phenan-
throline as a molecular probe to compare the SERS activity of
the core-shell bimetallic nanoparticles with that of the corre-
sponding monometallic nanoparticles and found that the core-
shell structured bimetallic nanoclusters exhibit a higher SERS
activity than the corresponding monometallic nanoclusters.
2. Experimental Section
2.1. Reagents and Instruments. All reagents were of
analytical reagent grade. Chloroauric acid (HAuCl4), silver
nitrate (AgNO3), β-CD, and 1,10-phenanthroline were obtained
from Sigma-Aldrich and were used as received. Pyrene, mercuric
chloride (HgCl2), sodium hydroxide (NaOH), and potassium
cyanide (KCN) were obtained from S. D. Fine Chemicals.
Dopamine, aminopyrene, crystal violet, and rhodamine 6G were
obtained from Sigma-Aldrich. Doubly distilled water was used
throughout the course of this investigation.
All absorption spectra were recorded on a Shimadzu UV-
160 spectrophotometer (Kyoto, Japan) using solutions in a 1-cm
quartz cuvette. TEM, HRTEM, and EDS measurements of the
metal sols were performed with a Hitachi H-9000 NAR
instrument on samples prepared by placing a drop of fresh metal
sols on copper grids precoated with carbon films and then
evaporating the solvent under a vacuum. XPS analysis was
performed on an ESCA LAB MK II instrument using Mg as
the exciting source. The samples were prepared by placing one
drop of the prepared mono- and bimetallic nanoparticles on a
clean glass slide and then allowing them to dry in air. SERS
spectra of 1,10-phenanthroline were obtained with a Renishaw
Raman microscope, equipped with a He-Ne laser excitation
J. Phys. Chem. C, Vol. 111, No. 29, 2007 10807
source emitting at a wavelength of 633 nm and a Peltier cooled
(-70 °C) charge coupled device (CCD) camera. A Leica
microscope was attached and was fitted with three objectives
(5×, 20×, 50×). For these experiments, the 20× objective was
used. Laser power at the sample was 20 mW, and the data
acquisition time was usually 30 s. The holographic grating (1800
grooves/mm) and the slit provided a spectral resolution of
1 cm-1.
2.2. Synthesis of Monometallic Gold and Silver Colloids.
The metal nanoparticles (gold and silver) were synthesized by
dissolving 0.0396 g of β-CD in 4.93 mL of water and shaken
well. After dissolving the β-CD, 0.02 mL of the corresponding
metal salt solution HAuCl4 (10 mM) and AgNO3 (10 mM) were
added to it. After 2 min, 0.05 mL of NaOH (1.0 M) was added
to the solution so that the pH of the solution became ∼10-12.
Then, the reaction mixtures were shaken well and heated on a
water bath. After ∼20 min, the solution turned pink for gold
and yellow for silver, indicating the formation of the corre-
sponding metal nanoparticles in the solution.
2.3. Synthesis of Aucore-Agshell and Agcore-Aushell Bimetal-
lic Nanoparticles. Aucore-Agshell nanoparticles were synthesized
using the following procedure: An aliquot of 0.04 mL of AgNO3
(10 mM) was added dropwise to 5 mL of the preformed gold
colloidal solution. The solution was allowed to incubate for
5 min and then heated on a water bath. After about 30 min, the
pink color of the solution turned to reddish yellow, indicating
the formation of a silver shell on the gold particles, i.e., the
formation of Aucore-Agshell particles. During the formation of
the particles, the initial pink color of the solution gradually
deceased, and a yellow color developed. The final concentrations
of the gold and silver colloids in the bimetallic nanoparticles
were adjusted to 0.05 and 0.1 mM, respectively. No extra β-CD
or NaOH was added to induce the chemical reduction of silver
ions and their deposition on the gold seed particles. The
alkalinity of the gold colloidal solution helps to induce the
chemical reduction of Ag(I) ions and their deposition on the
gold particles.
For the synthesis of inverted core-shell nanoparticles, an
aliquot of 0.04 mL HAuCl4 (10 mM) was added dropwise to
5 mL of preformed silver colloids with vigorous stirring. During
the progress of the reaction, the yellow color of the silver colloid
gradually diminished, and the pink color of the gold colloid
evolved; after ∼20 min, the pink color of the solution was found
to be persistent, indicating the formation of Agcore-Aushell
nanoparticles. Here, also, no extra β-CD or NaOH was added
to induce the formation of core-shell particles.
3. Results and Discussion
3.1. Evolution of Normal and Inverted Core-Shell Bi-
metallic Nanoparticles. The interaction of small metal particles
with an external electromagnetic field induced by light results
in coherent oscillations of the conduction (free) electrons (mainly
within the surface), called surface plasmon oscillations. This
surface plasmon resonance largely depends on the particle size
and shape and, of course, on the metallic material and its
surrounding environment. The optical absorption spectra of gold
and silver colloids have been a subject of study for decades.
Because of the different plasmonic excitation resonances of the
two metals, these colloids exhibit absorption maxima at about
520 and 402 nm for gold and silver, respectively. Figure 1 shows
UV-visible spectra of gold and silver colloids in their final
stage of preparation using β-CD at an alkaline pH of ∼10-12
by reduction of HAuCl4 and AgNO3, respectively. Interestingly,
it was seen that the absorption profile shows a high degree of
10808 J. Phys. Chem. C, Vol. 111, No. 29, 2007
Figure 1. Absorption spectra of (a) Au(0) and (b) Ag(0) seed particles.
Figure 2. Time-dependent absorption spectra of (A) Aucore-Agshell and
(B) Agcore-Aushell bimetallic nanoparticles prepared from β-CD (7 mM)
capped Au and Ag seed at pH ∼ 10-12.
well-imposed absorption profiles, indicating the reproducibility
of nanoparticle synthesis during β-CD-mediated reduction for
the metal salts.
During the evolution of the bimetallic nanoparticles from the
monometallic particles, we recorded their UV-visible spectra
at different stages. The modification of the plasmon absorption
band in successive stages of formation of the core-shell
structure from gold seeds is shown in Figure 2A. Initially, gold
particles were synthesized separately by the β-CD reduction
method and were used as seed for the evolution of Aucore-
Agshell bimetallic nanoparticles. The colloidal solution of the
seed particles shows a pink color with an absorption band at
520 nm. Upon addition of Ag(I) ions to the gold seed particles,
silver ions are adsorbed onto the surface of the gold seed
particles and thereby reduced37,38 in successive stages to form
a shell layer over the gold particles, as seen from the absorbance
measurements. At the intermediate stages of particle evolution,
two plasmon bands can be observed at 508 and 438 nm, which
indicates the partial coverage of gold by silver nanoparticles.
With progressive heating, the absorption band of the gold
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
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-
515 nm) because of the partial coverage of the seed particles.
The peak maximum shifts to longer wavelength compared to
that of silver nanoparticles. Moreover, there is no separate
plasmon resonance of silver in the gold colloids, which indicates
that the nanoparticles are not a simple physical mixture of two
different kinds of metal particles. Finally, the peak becomes
shifted to 523 nm, which can be attributed to the complete
encapsulation of silver nanoparticles by gold, i.e., Agcore-Aushell
particles are formed. The changes in the surface plasmon
absorption of the Agcore-Aushell particles can be explained by
considering the polarizability in eq i in a fashion similar to that
used for the Aucore-Agshell particles.
From these surface plasmon resonance spectra, we conclude
that the monometallic gold and silver colloids and bimetallic
Aucore-Agshell and Agcore-Aushell particles are formed by using
β-CD at alkaline pH of ∼10-12. Thus, this phenomenon
indicates that β-CD acts as a reducing agent under alkaline
conditions.
3.2. Characterization of the Bimetallic Nanoparticles.
3.2.1. Transmission Electron Microscopy (TEM) Study. Clear
confirmation of the formation of normal and inverted core-
shell structures emerged from TEM, HRTEM, EDS, and XPS
studies. The TEM images of the mono- (gold and silver) and
Gold-Silver Core-Shell Architectures in β-Cyclodextrin
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
in Figure 3A-D. From the TEM images, it can be seen that
the monometallic particles are ∼10 nm, which is consistent with
the results obtained by UV-visible spectroscopy. From TEM
images of bimetallic particles, it can be observed that the particle
sizes are 13 ( 2 and 11 ( 3 nm for the Aucore-Agshell and
Agcore-Aushell particles, respectively.
To examine whether a core-shell structure was obtained in
the β-CD reduction reaction, HRTEM images of the as-prepared
materials were obtained. The HRTEM images support the
formation of normal and inverted core-shell structures rather
than hollow-core structure. Figure 4A,B shows HRTEM images
of Aucore-Agshell and Agcore-Aushell nanoparticles, respectively.
The inverted core-shell structure shows a less dense interior
core of silver surrounded by a thicker shell. Here, the less dense
interior core and thicker shell were produced because of presence
of silver in the core and gold in the shell.
EDS measurements indicate the organization of the particles
or the presence of the metals employed in the preparation
procedure. Here, the EDS spectra of the Agcore-Aushell structure
show the presence of silver and gold atoms (see Supporting
Information). HRTEM observations together with the EDS
measurements, conducted with electron beam irradiation clearly
indicate the formation of the Agcore-Aushell structure. Prolonged
electron beam irradiation (∼10 min) during EDS studies not
only destroys the core-shell morphology but also brings the
core material, Ag(0), to the surface (see Supporting Information).
Thus, both silver and gold become obvious surface atoms, and
the bimetallic particles take on a new shape. From this
J. Phys. Chem. C, Vol. 111, No. 29, 2007 10809
observation, we conclude that, in the case of Agcore-Aushell
nanoparticles, silver remains in the core as Ag(0).
3.2.2. X-ray Photoelectron Spectroscopy (XPS). XPS was
employed as a surface monitoring technique to further support
the above results. In the case of the Aucore-Agshell nanoparticles
(Figure 5A,B), XPS clearly shows that the shell is composed
of silver. The binding energies of Ag 3d5/2 and Ag 3d3/2
measured for the two peaks are 373 and 379 eV, respectively.
The binding energies of Au 4f7/2 and Au 4f5/2 were measured
at approximately 88.2 and 92 eV, respectively. Similarly, in
the case of the Agcore-Aushell nanoparticles (Figure 6A,B), the
shell is encapsulated with gold. The binding energies of Au
4f7/2 and Au 4f5/2 measured for the two peaks are 88.2 and
92 eV, and those for Ag 3d5/2 and Ag 3d3/2 are 373 and
379 eV, respectively. The energies for gold and silver are in
good agreement with the literature values for the binding
energies of gold and silver.40 These data confirm the formation
of an inverted core-shell structure rather than formation of a
hollow core inside the gold shell.
3.2.3. Cyanide Dissolution Reaction. To confirm the forma-
tion of the core-shell architectures, i.e., Aucore-Agshell and
Agcore-Aushell structures, typical complexation reactions with
cyanide were carried out under ambient conditions.12,36 The
successive changes of the surface plasmon absorption of the
bimetallic colloids upon dissolution with cyanide clearly support
the formation of core-shell structures. An aliquot of KCN
(10 mM) was added to 5 mL of bimetallic colloids separately,
and the changes in absorbance values were measured spectro-
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
conditions facilitate the deprotonation of the alcohol function-
alities of β-CD molecules (the stretching frequency due to -OH
shifts from 3368 to 3390 cm-1), which promotes the kinetic
evolution and stabilization of nanoparticles.
Interestingly enough, the evolution of mono- or bimetallic
nanoparticles of gold and silver from the corresponding precur-
sor salt solutions was not observed when individual PACs
(polyaromatic compounds) such as pyrene or 1,10-phenanthro-
line or HgCl2-saturated β-CD were employed in lieu of
unsaturated β-CD. These guest molecules individually can
saturate the cavity of β-CD, forming host-guest-type inclusion
complexes.45 In such cases, β-CD binds the guest, the alcohol
functionalities of β-CD remain completely engaged with sto-
ichiometric amounts of individual guest molecules, and cavity
saturation takes place through hydrogen bonding. Under these
circumstances, β-CD fails to reduce metallic precursor salts
because its reducing functionalities (-OH groups) remain
occupied by the formation of inclusion complexes with the guest.
However, conventional reducing agents can produce metallic
particles from HAuCl4 or AgNO3 solution in the presence of
guest-saturated β-CD, but the metallic particles precipitate from
alkaline β-CD solutions. This precipitation is observed because
the guest-saturated β-CD cannot offer stability to the otherwise
produced metal particles.
During the reduction of metal salts to the corresponding metal
nanoparticles, the β-CD molecules are oxidized. The presence
of oxidized and unoxidized β-CD was confirmed by ESI mass
spectra measured in anionic mode. From the ESI mass spectra,
the peaks are obtained in the 1134 and 1232 mass regions due
to unoxidized β-CD and the oxidized primary alcohol func-
tionality of β-CD, i.e., the -COOH group, respectively. It has
been reported that, at pH ∼10-12, the secondary alcoholic
group of β-CD is not oxidized and also no dioxirane formation
is formed.46,47 To offset the van der Waals forces responsible
for particle coalescence, carboxylic acids (produced as the
oxidation products of β-CD molecules) bearing a negative
surface charge provide a dense coating on the surfaces of the
metal particles and provide stabilization.
3.3.2. Probing Normal and InVerted Core-Shell Structures
Obtained by a Similar Synthetic Strategy: Extraordinary Role
of β-CD. It is now well-established in the literature that one
can easily obtain a normal core-shell structure from the
constituents where the more noble metal constitutes the core
while the less noble metal forms the shell of the bimetallic
cluster.37 However, the synthesis of an inverted core-shell
architecture is unfamiliar without the use of any extra reagent.
It is almost impossible because of the inevitable redox reaction,
i.e., Ag(0) oxidation by Au(III) ions.39,48-50 The successful
synthesis of inverted core-shell architectures thus addresses
several challenges. In the present experiments, the preformed
Au(0) or Ag(0) nanoparticles act as seeds and β-CD becomes
kinetically capable of reducing the incoming Ag(I) or Au(III)
ions onto the seed particles to create the core-shell morphology
as represented in the following reaction
Aucore + Ag(I) 9
β-CD
8 Aucore-Agshell (1)
pH ∼ 10-12
β-CD
Agcore + Au(III) 9
pH ∼ 10-12
8 Agcore-Aushell (2)
Reaction 1 is favorable, as the standard reduction potential of
Ag(I)/Ag(0) is lower than that of Au(III)/Au(0). In the case of
reaction 2, however, β-CD helps to produce the inverted core-
shell architecture through the reduction of Au(III) ions in the
presence of preformed Ag(0). Here, the Au(III) reduction rate
J. Phys. Chem. C, Vol. 111, No. 29, 2007 10811
is possibly higher than the galvanic replacement reaction rate
under the experimental conditions. Mechanistically, it can be
specified that the oxidation resistance of silver presumably
increases and this inhibits the normal oxidation of Ag(0) in the
presence of Au(III) ions. The diffusion resistance (DR) and
charge-transfer resistance (CTR) should also have a bearing on
the oxidation of Ag(0), as has been described only recently.13
Presumably, both the DR and CTR of Au(III) are increased in
β-CD, so that the electron transfer from Ag(0) to Au(III) ions
is inhibited. Furthermore, it can also be suggested that the self-
organization and hydrophobic interaction of β-CD with Ag(0)
makes the latter nobler than Au(0). This results in the formation
of the Agcore-Aushell structure instead of the formation of a
hollow core inside the gold shell.
3.4. Application of Normal and Inverted Core-Shell
Bimetallic Nanoparticles in SERS Spectroscopy: Electronic
Ligand Effect. SERS spectroscopy has been producing en-
lightening results since its discovery in 1974.18 Noble-metal
nanoparticles, usually silver and gold, are well-known for their
strong interactions with visible light through the resonant
excitations of the collective oscillations of the conduction
electrons within the particles. Creighton et al.51 and Jeanmaire
and Van Duyne52 independently confirmed the findings on the
enhancement aspect of Raman signals, and silver is the best-
suited choice for such studies.45,49,50 However, the mechanism
of SERS has been a matter of considerable debate.19,53-55 It
has been widely accepted that there are two mechanisms for
the observed and, at times, huge enhancement in SERS:
electromagnetic and chemical. The electromagnetic mechanism
is based on the interaction of the electric field of the surface
plasmons with the transition moment of the adsorbed molecule,
whereas the chemical mechanism is based on the idea that
mixing of molecular and metal states occurs. The chemical
mechanism might arise from the mixing of metal orbitals with
orbitals on a molecule, providing charge transfer that results in
a resonant Raman mechanism at much lower energies than those
available in the free molecule. Both mechanisms and even others
can contribute simultaneously to the SERS enhancement to a
certain extent, which is dependent on the experimental condi-
tions, the nature and morphology of the metallic nanoparticles,
and other factors.
The present report of SERS measurements probes the
influence of the shell material of the as-prepared particles in
solution using 1,10-phenanthroline as a molecular probe. The
molecule 1,10-phenanthroline has been used in SERS as a probe
by Li et al. and Miranda in the cases of gold electrode and silver
sols.56,57 However, there have been no reports of SERS studies
in a particular dielectric medium involving individual gold,
silver, and their bimetallic conjugates as substrates for examining
the electromagnetic (EM) mechanism. This has not been
possible, and it has remained a challenge to produce all of these
particles in the same dielectric environment. Here, the probe
molecules induce particle aggregation without the need of any
extra electrolyte for generating a “hot junction”. The junction
can therefore function as an electromagnetic “hot spot” analo-
gous to those predicted to exist in large fractal aggregates. Thus,
absolute EM effects can be confirmed from the SERS signal
enhancement. In the present experiments, bimetallic nanopar-
ticles were employeing the d at the same concentration as
monometallic particles of silver and gold of the same size range
(∼12 nm) to investigate the electronic ligand effect4,5,8,9 (the
so-called electronic ligand effect in the case of core-shell
particles) on the SERS spectra of 1,10-phenanthroline. It can
be seen that the probe molecules show distinctly different SERS
10812 J. Phys. Chem. C, Vol. 111, No. 29, 2007
Figure 7. SERS spectra of 1,10-phenanthroline (0.5 mM) using (a)
Aucore-Agshell nanoparticles, (b) Agcore-Aushell nanoparticles, (c) Ag-
(0), and (d) Au(0) (0.15 mM).
SCHEME 1: Schematic Representation of the
Formation of Mono- and Bimetallic Nanoparticles and
their Corresponding SERS Spectra
signals in the presence of different sets of colloidal solutions.
The salient feature of physical significance is that we observe
better enhancement of the SERS signal of the probe molecule
with Aucore-Agshell particles than with bimetallic Agcore-Aushell
or monometallic gold or even silver particles, as shown in
Figure 7 (Scheme 1). Similar results were also obtained with
other probe molecules, e.g., dopamine, aminopyrene, crystal
violet, rhodamine 6G, etc.
It is known that, in general, silver monometallic nanoclusters
are good SERS-active substrates, whereas gold monometallic
nanoclusters are less active. Thus, one can conclusively
characterize the constituents of a metallic substrate. The
enhancement of Raman signals with Aucore-Agshell nanoparticles
in comparison to monometallic silver particles can be explained
in light of the electronic ligand effect in bimetallic nanoparticles.
The gold atoms in the core can have a strong electronic effect
on the surface silver atoms by charge transfer, and thus, the
surface silver atoms neighboring the gold core become more
active than the silver atoms in monometallic silver nanoclusters.8-11
Charge-transfer interactions in Aucore-Agshell bimetallic nano-
particles can be explained in terms of the electronegativity values
of the constituents. Given that gold is more electronegative than
silver, gold will withdraw electron density from the silver shell
in the case of the Aucore-Agshell nanostructure. As a result, the
silver shell will experience the effect of electrophiles, and the
core will experience the effect of nucleophiles.58,59 Again, this
can be explained on the basis of the concept of the Fermi level
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
higher SERS activities than the corresponding monometallic
structures. Hence, one can probe the shell material beyond
doubt.
4. Conclusion
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.
Supporting Information Available: EDS of spectra of
Agcore-Aushell bimetallic nanoparticles and HRTEM images of
Agcore-Aushell bimetallic nanoparticles (a) before and (b) after
prolonged (∼10 min) electron beam irradiation. This material
is available free of charge via the Internet at http://pubs.acs.org.
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