View Article Online / Journal Homepage / Table of Contents for this issue

HIGHLIGHT www.rsc.org/materials | Journal of Materials Chemistry

Core@shell nanomaterials: gold-coated magnetic

oxide nanoparticles
Lingyan Wang, Hye-Young Park,† Stephanie I-Im Lim, Mark J. Schadt, Derrick Mott, Jin Luo,
Xin Wang‡ and Chuan-Jian Zhong*
DOI: 10.1039/b719096d

The study of core@shell magnetic nanoparticles has a wide range of applications because of
the unique combination of the nanoscale magnetic core and the functional shell. This report
highlights some of the recent findings in the investigation of the synthesis, characterization
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D

and application of one important class of core@shell magnetic nanoparticles, i.e., magnetic
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.

nanoparticles coated with a gold shell (MNP@Au). The gold shell imparts the magnetic
nanoparticles with many intriguing functional properties. Areas specifically highlighted in this
report include strategies for the synthesis of MNP@Au nanoparticles, characterization of the
core@shell nanostructures, and exploration of potential applications of the core@shell
nanomaterials in terms of biological and catalytic interfacial reactivities. Implications of some
of the research findings to address both fundamental and practical issues are also briefly
discussed in an effort to further broaden the rapidly-emerging field of core@shell magnetic
nanoparticles.

The design of the surface chemistry of
magnetic nanoparticles (MNPs) is
increasingly important for exploring a
wide range of technological applications
of MNPs, including micro/nano-
electronics, catalysis, chemical sensing,
information storage, and medical diag-
Department of Chemistry, State University of
New York at Binghamton, Binghamton, New
York 13902, U. S. A. E-mail: cjzhong@
binghamton.edu
† Current address: Institute Pasteur Korea,
Seoul, South Korea.
‡ Current address: School of Material Science
and Engineering, Hebei University of
Technology, Tianjin, China.
nostics.1–13 Examples include magnetic
resonance imaging contrast enhance-
ment, controlled drug delivery, tissue
repair, detoxification of biological fluids,
immunoassay, and biological targeting or
separation.14–19 A key challenge in these
applications is the synthesis of MNPs
with controlled size, composition, and
surface properties, which has been the
subject of research of an increasingly
interdisciplinary nature.20,21 Significant
progress has been made for bottom-up
fabrication of MNPs including transition
metals, alloys and metal oxides, via
chemical processes such as decomposi-
tion, reduction, or oxidation reactions in
both aqueous and organic media.6–12,22–24
In many areas of biological application,
the ability to engineer surface properties is
important because MNPs are desired to
have the desired biocompatibility and
interfacial reactivity. Among many
approaches to the modification or func-
tionalization of the surfaces of MNPs
with materials such as polymers, organic
monolayers, oxides, and metals,25–47 one
of the most promising systems involves
magnetic nanoparticles coated with gold
shells (Scheme 1).
This type of core@shell nanoparticle,
e.g., MNPs@Au, not only provides
enhanced stabilization, but also allows

Dr Lingyan Wang received C. J. Zhong is professor of

a PhD degree in Chemistry in
2007, and is currently a post-
doctoral associate researcher at
the State University of New
York at Binghamton. Working
with C. J. Zhong, her current
research interests include
synthesis, assembly and charac-
terization of nanostructured
materials for applications in
chemical sensors and catalysis.
She was awarded the University
Lingyan Wang Outstanding Graduate Research
Award in 2006.
chemistry at the State Univer-
sity of New York at Bing-
hamton. His current research
interests are the interdisciplinary
fields of analytical, materials,
catalysis, electrochemistry and
nanotechnology, focusing on
developing advanced nano-
materials for applications in fuel
cells, chemical/bio sensors and
biomedical devices.
C: J: Zhong

This journal is ª The Royal Society of Chemistry 2008 J. Mater. Chem., 2008, 18, 2629–2635 | 2629

Scheme 1 An illustration of gold-coated MNPs emphasizing the importance of synthesis, charac-
terization and application.
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
fine-tuning of the surface biocompati-
bility, and importantly imparts the
surfaces with the desired chemical,
biological, or catalytic interfacial reac-
tivities.26–47 However, the synthesis and
characterization of MNPs@Au with the
desired size and composition are chal-
lenging. There have been a number of
examples reporting on the synthesis of
MNPs@Au. For example, gold-coated
iron oxide (Fe2O3 or partially oxidized
Fe3O4) nanoparticles (
60 nm) were
synthesized by depositing Au onto iron
oxide nanoparticles (9 nm) via hydroxyl-
amine seeding in aqueous solution.26
Gold-coated iron27–29 and gold (silver)-
coated magnetite30 nanoparticles have
also been synthesized using a reverse
micelle method. A similar approach has
been demonstrated for the formation of
gold-coated Fe3O4 nanoparticles which
involved the attachment of gold nano-
particles (2–3 nm) via 3-aminopropyl
triethylsilane onto 10 nm sized Fe3O4
nanoparticles.31 Several other approaches
to the synthesis of gold-coated magnetic
core@shell particles have also been
reported, including g-ray radiation,36
laser ablation,37 sonochemical reaction,38
layer-by-layer electrostatic deposition,39
wet chemical reduction,40,41 and photo-
chemical reduction.42 Other types of gold-
coated magnetic nanoparticles include
composite nanoparticles consisting of
a silica core, an Fe3O4 inner shell, and a
gold shell,43 FePt nanoparticles with
a gold shell,44 cobalt nanoparticles with
a gold shell,45 iron oxide core (Fe3O4/g-
Fe2O3) with a thick silica shell and outer
shell of gold,46 and Fe nanoparticles with
an Au shell.47
The success of some of these synthetic
approaches has led to increasing interest
in the exploration of the potential appli-
cations of MNPs@Au. It has also gener-
2630 | J. Mater. Chem., 2008, 18, 2629–2635
View Article Online
of the core@shell nanomaterials in terms
of biological and catalytic interfacial
reactivities.
The first area concerns strategies or
approaches for the synthesis of
MNPs@Au nanoparticles. While there
are a number of strategies reported for the
synthesis and fabrication of MNPs@Au
nanoparticles,26–47 the two strategies
described here highlight the importance
of bottom-up synthesis and processing.
One strategy involves sequential forma-
tion of the Fe-oxide core and Au shell,
which was used for the synthesis of
ated many fundamental and technical highly-monodisperse Fe2O3@Au and
issues related to the control and charac- Fe3O4@Au nanoparticles34 (Fig. 1). The
terization of the core@shell size and strategy starts with the synthesis of Fe3O4
composition. For example, the gold- seeds according to an established
coating of the magnetic cores will depend protocol24 in which Fe(acac)3 is reduced
on their surface state and on the growth using 1,2-hexadecanediol in the presence
orietation of the gold layer. In an effort of capping agents (e.g., oleylamine
to address some of the issues, we have (OAM) and/or oleic acid (OA)).
recently developed several approaches Following the formation of Fe3O4 as
to the synthesis and characterization seeds with the desired sizes, gold is
of MNP@Au nanoparticles.34,35 Some deposited onto the surface of Fe3O4 by
MNP@Au nanoparticles are shown to be reduction of Au(CH3COO)3 using 1,2-
highly-monodisperse in particle size and hexadecanediol in the presence of capping
exhibit interesting interfacial interactions agents at elevated temperature (180–
and reactivities. In this article, we discuss 190  C). A key element of this process
a few examples from our study of involves careful manipulation of the
MNP@Au nanoparticles, including our reaction temperature to control the ther-
latest findings, by highlighting areas mally-activated partial desorption of the
related to strategies for the synthesis of capping layer from the core, the deposi-
MNP@Au nanoparticles, characteriza- tion of Au on the exposed Fe3O4 surface,
tion of the core@shell nanostructures, and the subsequent re-encapsulation of
and exploration of potential applications the Au shell surface by the capping agent.
Fig. 1 Top panel: An illustration of the synthesis of the Fe3O4 (1* ¼ reducing agent, capping agent,
and solvent) and the formation of Fe3O4@Au nanoparticles in the presence of capping agents
(2* ¼gold precursor, reducing agent, capping agent, and temperature manipulation) which involves
capping-shell desorption, deposition of Au on the exposed Fe3O4 surface, and re-encapsulation.
Bottom panel: TEM micrographs (and HRTEM) and size distributions comparing Fe3O4 (5.3 
0.5 nm) (left) and Fe3O4@Au (6.7  0.4 nm) (right).
This journal is ª The Royal Society of Chemistry 2008

The resulting Fe3O4@Au nanoparticles
can be separated by centrifugation from
the uncoated Fe3O4 nanoparticles. This
approach can produce highly-mono-
disperse Fe-oxide@Au nanoparticles in
a core size range of 5–15 nm with a shell
thickness range of 0.5–2.0 nm. By
controlling the reaction time and the
concentration of Au precursor, the
thickness can be effectively controlled in
a wide range. The subtle differences in
comparing the high-resolution TEM
(HRTEM) images (and electron diffrac-
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
tion as well) seemed to support the
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
formation of Fe3O4@Au nanoparticles
from Au and Fe-oxide nanoparticles,
which is however not a conclusive way
due to the lack of a clear contrast between
the core and the shell in the HRTEM
images.
Another strategy involves thermally-
activated processing of Fe-oxide nano-
particles and Au nanoparticles as
precursors in a mixed solution.35 This
strategy expands the method of ther-
mally-induced homo-interparticle coal-
escence of metal nanoparticles, as
demonstrated earlier in our laboratory for
the particle size and monodispersity
evolution at mild temperature elevation
(140–160  C).48 The fundamental basis
stems from the decrease of melting point,
especially the surface melting, for many
nanosized metal particles. In contrast to
the dramatically-decreased melting
temperature of gold nanoparticles, iron
oxide nanoparticles do not exhibit coa-
lescence under such a mild temperature
elevation (140–160  C). The thermal
processing involves molecular desorption,
nanocrystal core coalescence and molec-
ular re-encapsulation processes in the
evolution of nanoparticle precursors,48
which has gained increasing interest for
processing nanoparticle size and mono-
dispersity.49 Fig. 2 illustrates the thermal
processing of Fe2O3 (or Fe3O4) and Au
Fig. 2 Left: an idealized illustration of hetero-interparticle coalescence of molecularly-capped Au
(2 nm) and Fe2O3 (5 nm) nanoparticles in solution leading to core@shell nanoparticles. Right: TEM
micrographs for the resulting Fe2O3@Au nanoparticles of two different sizes 6.2  0.3 nm (a) and
31.4  3.0 nm (b).
This journal is ª The Royal Society of Chemistry 2008
nanoparticles in solution via thermally-
activated hetero-interparticle coalescence
between gold and magnetic nanoparticles
under an encapsulating environment for
creating the core@shell type nano-
particles,35 Fe2O3@Au (or Fe3O4@Au).
The processing environment is important
for the stabilization of the nanoparticles,
which include the presence of organic
ionic materials such as tetraoctylammo-
nium bromide (TOABr) in the solution
and capping molecules such as alka-
nethiols [e.g., decanethiols (DTs)] for
capping Au nanoparticles and those such
as oleylamine and/or oleic acid for
capping Fe-oxide nanoparticles. The
presence of molecularly-capped iron
oxide nanoparticles in the solution
created a unique thermal microenviron-
ment for the core@shell coalescence to
produce monodisperse Fe-oxide@Au
nanoparticles of controlled sizes. The Au
shell thickness can be manipulated
depending on the relative ratio of Au and
Fe-oxide precursors. The competition
between growing Au and Fe-oxide@Au
with single or multiple Fe-oxide cores
(pomegranate-like) nanoparticles
determined by a combination of the
solution temperature, the composition
and the capping structures.
The manipulation of the shell or the
core composition is also part of our study
aimed at tailoring the solubility.
Depending on the specific application, the
ability to tailor the solubility, especially in
aqueous solutions or biological systems,
is important. One of our approaches
involves ligand exchange for making
water-soluble magnetic core@shell nano-
particles. Ligand exchange, a well estab-
lished method for functionalization of the
organic shell,50 involves replacement of
the original capping molecules (e.g., DTs,
OAM, and OA) on Fe-oxide@Au nano-
particles by functionalized thiols. For
example, OAM- and OA-capped
View Article Online
Fe2O3@Au particles (organic soluble)
were converted to water-soluble particles
by a ligand exchange reaction with
mercaptoundecanoic acid (MUA). The
detection of the band at 1709 cm1
corresponding to the carboxylic acid
group of MUA, accompanied by the
disappearance of the band at 3004 cm1
corresponding to the C–H stretching
mode next to the double bond from OA
and OAM capping molecules, confirmed
the successful exchange of the MUA with
the original ligands on the nanoparticles.
This was further evidenced by the fact
that the post-exchanged core@shell
nanoparticles became water-soluble.
Another approach involves the synthesis
of water-soluble magnetic cores with the
desired composition. For example, MnZn
ferrite [(MnxZnyFe2+1xy)Fe3+ 2O4]
nanoparticles represent a technologically-
important class of spinel magnetic mate-
rials with a large and tunable magnetic
polarization.51 In comparison with the
extensive studies of iron oxide (e.g.,
Fe2O3, Fe3O4) nanoparticles, the
synthesis of both MnZn ferrite nano-
is particles and MnZn ferrite@Au nano-
particles in aqueous solutions,51b,c which is
part of our on-going work, may52 present
a useful route towards effective explora-
tion of their applications in biologically-
relevant solutions.
The second area concerns approaches
to the characterization of properties and
reactivities of MNPs@Au nanoparticles
for understanding the core@shell nano-
structure. As stated earlier, HRTEM is
a powerful tool, but sometimes inclusive
in the case of lacking enough contrast of
the core and shell materials. Crystallo-
graphic and composition analyses can
provide information for the structural
assessment. For example, the comparison
of the XRD spectra for Fe3O4, Au, and
Fe3O4@Au nanoparticles showed that the
diffraction peaks for Fe3O4@Au nano-
particles are similar to those for Au
nanoparticles, but different from those
for Fe3O4 nanoparticles.34 The absence of
diffraction peaks from magnetite has also
been observed by others.9 This is possibly
due to the heavy atom effect from gold53
as a result of complete coverage of the
oxide core by Au shell. The relative
surface composition of Fe3O4@Au can
also be analyzed using XPS and Direct
Current Plasma-Atomic Emission Spec-
troscopy (DCP-AES) techniques, though
J. Mater. Chem., 2008, 18, 2629–2635 | 2631

XPS analysis is sometimes inconclusive
for small-sized particles because of the
depth sensitivity issue. On the other hand,
the DCP data showed Fe : Au ratios of
34 : 66 and 29 : 71 for Fe3O4@Au particles
of two different core sizes (5.2 and
4.5 nm, respectively), which were quite
close to the results based on calculations
from the TEM-determined size changes
and the density values for Au and Fe3O4
materials.
Despite some inconclusive results
about the detailed core@shell nano-
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
structure from HRTEM, XPS, and XRD
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
data, the characterization of the nano-
materials’ properties (optical and
magnetic) and the interfacial reactivities
have proven very useful for assessing the
core@shell nanostructures. In addition to
FTIR probing of CO adsorption and
electrochemical characterizations of the
surface properties of the core@shell
nanoparticles,54 several examples of the
characterization of the nanomaterials’
properties (optical and magnetic) and the
interfacial reactivities have provided
important insights into the core@shell
nanostructures.
From the measurement of the surface
plasmon (SP) resonance band of gold
nanoparticles, Fe3O4@Au particles
showed an SP band at 535–550 nm
depending on the core size and Au shell
thickness. This band is characteristic of
the optical properties of gold nano-
structures, in contrast to the largely silent
feature in the visible region for Fe3O4
particles. The observed SP band showed
a red shift in comparison with Au nano-
particles. Interestingly, the core@shell
nanoparticles with a thicker Au shell
displayed a smaller red shift than those
with thinner Au shells. This finding is in
fact consistent with theoretical calcula-
tion of the Fe3O4@Au core@shell
morphology based on Mie theory,55
suggesting that the optical properties are
affected by the chemical nature of the
oxide core.
The measurement of the magnetic
properties of the Fe3O4@Au nano-
particles in comparison with Fe3O4 using
SQUID technique, on the other hand,
allows us to assess the saturation magne-
tization, coercivity, susceptibility, and
blocking temperature. The temperature
dependence of the magnetic susceptibility
[0.30 emu Oe1 g1 (Fe3O4) at 17 K for
Fe3O4 and 0.037 emu Oe1 g1 (Fe3O4) at
2632 | J. Mater. Chem., 2008, 18, 2629–2635
13 K for Fe3O4@Au] showed a significant
decrease for Fe3O4@Au in comparison
with Fe3O4.34b From this measurement,
a clear decrease in blocking temperature
was also found for Fe3O4@Au (13 K) in
comparison with 17 K for Fe3O4 nano-
particles, which is believed to reflect the
decreased coupling of the magnetic
moments as a result of the increased
interparticle spacing of the magnetic
cores56 by gold and organic capping-
shells. The magnitude of the magnetiza-
tion for Fe3O4@Au [66 emu g1 (Fe3O4)]
is much smaller than that of Fe3O4 [15
emu g1 (Fe3O4)]34b (Fig. 3). On the basis
of the data near zero magnetization, the
coercivity showed (Fig. 3 insert) a clear
increase for Fe3O4@Au nanoparticles (40
Oe for Fe3O4 and 160 Oe for Fe3O4@Au),
reflecting the fact that coercivity of a
superparamagnetic nanoparticle is related
to a change in dipolar coupling or a
change in the magnetic core size.56 The
increase in coercivity can be attributed to
the larger size of Au-coated Fe3O4 which
leads to a less-effective coupling of the
magnetic dipole moments.
The characterization of the interfacial
reactivity characteristics of the gold shell
provides an important platform for
assessing the core@shell nanostructures.
This approach is based on our early work
for the assembly of gold nanoparticles via
interparticle covalent or hydrogen-
bonding linkages.57 The thiol-mediated
binding chemistry for the assembly of
Fe3O4@Au nanoparticles was examined
using 1,9-nonanedithiol (NDT) and
mercaptoundecanoic acid (MUA). As
illustrated in Fig. 4, the basic chemistry
Fig. 3 Magnetic susceptibility hysterisis at 5 K for Fe3O4 (a) and Fe3O4@Au (b) nanoparticles.
Insert: a magnified view of the 600 to 600 Oe region.
This journal is ª The Royal Society of Chemistry 2008
View Article Online
involved an initial thiolate–oleylamine
exchange reaction followed by cross-
linking via the alkyl chain for the case of
dithiol as a linker or hydrogen-bonding
for the case of carboxylic acid function-
alized thiol as a linker. This assembly
chemistry is expected to operate for
Au-coated iron oxide nanoparticles, but
not for iron oxide nanoparticles because
the thiolate binding is highly specific
to Au.
The characterization of the gold based
interfacial binding chemistry and thin film
assembly has revealed several important
pieces of information for assessing the
core@shell nanostructure. Note that the
color of the film formed ranged from
brown to blue depending on the particle
size, linker molecule and film thickness,
similar to thin film assemblies of gold
nanoparticles.57 In comparison with the
SP band for Fe3O4@Au nanoparticles in
solution and thin film assemblies of gold
nanoparticles, the SP band is shifted to
a longer wavelength for NDT- or MUA-
mediated thin film assemblies of
Fe3O4@Au nanoparticles. The shift of the
SP band is characteristic of the changes in
interparticle spacing and dielectric prop-
erties as a result of the thin film assembly.
The Au–thiolate binding chemistry is
responsible for the formation of
Fe3O4@Au thin films, in contrast to the
absence of any assembly of Fe3O4 nano-
particles under the same conditions. The
DCP analysis of the metal composition
(Au and Fe) in the thin film assemblies
which were dissolved in aqua regia solu-
tion detected both Au and Fe. The Au : Fe
ratios for both NDT- and MUA-linked

Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
Fig. 4 Schematic illustrations of the thiol-mediated thin film assembly of Au (middle), Fe3O4
(bottom) and Fe3O4@Au (top) nanoparticles on a substrate. The insert illustrates the thiol-mediated
interparticle binding chemistry involving exchange, cross-linking and thin film precipitation.
thin film assemblies of Fe3O4@Au nano-
particles were slightly higher than that for
the particles before assembly. Since the
uncoated Fe3O4 nanoparticles were not
able to form any thin films, the detected
Au : Fe ratio was therefore a measure of
Au and Fe in Fe3O4@Au nanoparticles
which were actually assembled into the
thin film. Based on a spherical core@shell
model, the average thickness of the Au
shell calculated from the DCP data yiel-
ded 0.6 nm and 0.8 nm for Fe3O4@Au
nanoparticles derived from Fe3O4 core
sizes of 5.2 nm and 4.5 nm, respectively.
The remarkable closeness between the
average particle sizes estimated from the
DCP analysis of the core@shell nano-
particle composition and those deter-
mined from TEM support the nature of
the core@shell nanostructure for the
Fe3O4@Au nanoparticles in the thin film
assemblies. In addition to confirming the
core@shell morphology, this finding
demonstrated the utility of the interfacial
reactivity of the core@shell nanoparticles
for thin film assembly.
The synthesis and characterization of
MNPs@Au nanoparticles have aimed at
many areas of potential applications. Our
studies have focused on biological sepa-
ration and catalytic reaction. The study of
MNP@Au based biological separation
stems from the established protocol for
protein or DNA separations using labeled
magnetic beads.14–19 The immobilization
This journal is ª The Royal Society of Chemistry 2008
View Article Online
nanoparticles were reacted with Au
particles capped with protein A. The latter
was labeled with a Raman-active label,
e.g., mercaptobenzoic acid (MBA). For
the product separation of the antibody-
labeled Fe2O3@Au nanoparticles after
reaction with protein A capped gold
nanoparticles, a magnetic field was
applied to collect the magnetically-active
products for SERS analysis. Fig. 5 shows
one example to illustrate the viability of
this potential,35 along with representative
SERS spectrum for the products collected.
In comparison with the spectrum from
the control experiment in which the Au
nanoparticles capped with BSA protein
and MBA label were used to react with
MNP@Au nanoparticles capped with
anti-rabbit IgG (Immunoglobulin G)
under the same conditions (not shown),
the product from the reaction between
Au/Protein-A/L and MNP@Au/Ab
collected by a magnet showed the expec-
ted SERS signature of MBA, at 1081 and
of biological recognition sites on gold- 1591 cm1, corresponding to n(CC) ring-
coated magnetic nanoparticles and the breathing modes of MBA. This finding
subsequent recognition to the targeted demonstrates the viability of exploiting
proteins provide an effective means for the magnetic core and gold shell of the
the separation of biological molecules via MNP@Au nanoparticles for interfacial
application of a magnetic field.19 For bio-assay and magnetic bio-separation,
example, the MUA-capped Fe2O3@Au the study of which is part of our on-going
nanoparticles in water underwent further work.
exchange reactions with a protein- Another area of our study of the
coupling agent, dithiobis(succinimidyl MNPs@Au concerns catalysis, especially
propionate) (DSP), forming a DSP- fuel cell catalysts.58–67 Many of the MNPs
derived monolayer on the gold surface. function as unique support materials of
Antibody (Ab, e.g., anti-rabbit IgG) was metal catalysts in catalytic reactions.
then immobilized onto the nanoparticles Examples include nanosized gold on an
via coupling with the surface DSP. The oxide support for CO oxidation,59–61 and
resulting Ab-immobilized MNP@Au many other metal or oxide core@shell
Fig. 5 (Left) Illustrations of the product separation of antibody-labeled MNP@Au nanoparticles
in reaction with protein A capped gold nanoparticles. (Right) SERS spectra of the products magnet-
ically collected from the reaction between Au/Protein-A/L and MNP@Au/Ab. SERS label (L):
mercaptobenzoic acid (MBA); antibody (Ab): anti-rabbit-IgG (MNPs ¼ MnZnFerrite).
J. Mater. Chem., 2008, 18, 2629–2635 | 2633

nanoparticles.62–65 We have recently
developed methods for synthesizing
bimetallic alloys54,66,67 and Fe-oxide@Au
nanoparticles.34,35 The on-going studies
focus on the correlation between the
synergistic catalytic properties and the
composition and spatial arrangement for
metal–metal and metal–oxide core@shell
nanoparticles.
In summary, the examples highlighted
in this article represent a small fraction
of a variety of magnetic core@shell
nanoparticles being studied in the litera-
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
ture.26–47 These examples show promising
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
approaches to the synthesis, character-
ization and applications of MNPs@Au
nanoparticles. It is important to empha-
size that while increasing applications
explore the unique properties of nano-
scale MNPs–Au combinations, there are
many challenging issues for the precise
control of size and composition and the
characterization of the detailed core@
shell nanostructures. In addition to
biological and catalytic applications,
there are many other potential applica-
tions which are part of our on-going work
and the results will be discussed in our
future reports. The coupling of the inter-
facial reactivity and the magnetic activity
of core@shell nanoparticles has impor-
tant implications for further broadening
the emerging fields of nanotechnology,
biotechnology and catalysis.
Acknowledgements
This work is supported by the National
Science Foundation (CHE 0349040,
CBET-0709113), and in part by
NYSTAR (C060057). Help from Dr
Richard Naslund in DCP-AES measure-
ment is also acknowledged.
References
1 C. B. Murray, C. R. Kagan and
M. G. Bawendi, Annu. Rev. Mater. Res.,
2000, 30, 545.
2 C. Ross, Annu. Rev. Mater. Res., 2001, 31,
203.
3 P. Tartaj, M. D. Morales, S. Veintemillas-
Verdaguer, T. Gonzalez-Carreno and
C. J. Serna, J. Phys. D, 2003, 36, 182.
4 B. Bonnemain, J. Drug Targeting, 1998, 6,
167.
5 (a) P. Li, D. E. Miser, S. Rabiei,
R. T. Yadav and M. R. Hajaligol, Appl.
Catal., B, 2003, 43, 151; (b) D. Cameron,
R. Holliday and D. Thompson, J. Power
Sources, 2003, 118, 298.
6 S. Sun, C. B. Murray, D. Weller, L. Folks
and A. Moser, Science, 2000, 287, 1989.
2634 | J. Mater. Chem., 2008, 18, 2629–2635
7 A. K. Boal, K. Das, M. Gray and V. M.
Rotello, Chem. Mater., 2002, 14, 2628.
8 K. Woo, J. Hong, S. Choi, H. W. Lee,
J. P. Ahn, C. S. Kim and S. W. Lee,
Chem. Mater., 2004, 16, 2814.
9 M. Mikhaylova, D. K. Kim,
N. Bobrysheva, M. Osmolowsky,
V. Semenov, T. Tsakalakos and
M. Muhammed, Langmuir, 2004, 20, 2472.
10 K. V. P. M. Shafi, A. Ulman, X. Z. Yan,
N. L. Yang, C. Estournes, H. White and
M. Rafailovich, Langmuir, 2001, 17, 5093.
11 C. Wilhelm, F. Gazeau, J. Roger, J. N. Pons
and J. C. Bacri, Langmuir, 2002, 18, 8148.
12 X. W. Teng and H. Yang, J. Mater. Chem.,
2004, 14, 774.
13 D. Wang, J. He, N. Rosenzweig and
Z. Rosenzweig, Nano Lett., 2004, 4, 409.
14 M.-C. Daniel and D. Astruc, Chem. Rev.,
2004, 104, 293.
15 Y. Xia, B. Gates, Y. Yin and Y. Lu, Adv.
Mater., 2000, 12, 693.
16 D. S. Grubisha, R. J. Lipert, H. Y. Park,
J. Driskell and M. D. Porter, Anal. Chem.,
2003, 75, 5936.
17 M. J. Kogan, I. Olmedo, L. Hosta,
A. R. Guerrero, L. J. Cruz and
F. Albericio, Nanomedicine, 2007, 2, 287.
18 J. Wang, Electroanalysis, 2007, 19, 769.
19 P. Fortina, L. J. Kricka, D. J. Graves,
J. Park, T. Hyslop, F. Tam, N. Halas,
S. Surrey and S. A. Waldman, Trends
Biochem. Sci., 2007, 25, 145.
20 Y. Kobayashi, S. C. Gu, D. Nagao and
M. Konno, Curr. Nanosci., 2007, 3, 222.
21 J. Park, J. Joo, S. G. Kwon, Y. Jang and
T. Hyeon, Angew. Chem., Int. Ed., 2007,
46, 4630.
22 C. J. O’Connor, C. T. Seip, E. E. Carpenter,
S. C. Li and V. T. John, Nanostruct. Mater.,
1999, 12, 65.
23 T. Hyeon, S. S. Lee, J. Park, Y. Chung and
H. B. Na, J. Am. Chem. Soc., 2001, 123,
12798.
24 (a) S. H. Sun and H. Zeng, J. Am. Chem.
Soc., 2002, 124, 8204; (b) S. H. Sun,
H. Zeng, D. B. Robinson, S. Raoux,
P. M. Rice, S. X. Wang and G. X. Li,
J. Am. Chem. Soc., 2004, 126, 273.
25 C. C. Berry, J. Phys. D: Appl. Phys., 2003,
36, 198.
26 J. L. Lyon, D. A. Fleming, M. B. Stone,
P. Schiffer and M. E. Williams, Nano
Lett., 2004, 4, 719.
27 E. E. Carpenter, C. Sangregorio and
C. J. O’Connor, IEEE Trans. Magn.,
1999, 35, 3496.
28 J. Lin, W. Zhou, A. Kumbhar, J. Wiemann,
J. Fang, E. E. Carpenter and
C. J. O’Connor, J. Solid State Chem.,
2001, 159, 26.
29 S.-J. Cho, J.-C. Idrobo, J. Olamit, K. Liu,
N. D. Browning and S. M. Kauzlarich,
Chem. Mater., 2005, 17, 3181.
30 (a) M. Mikhaylova, D. K. Kim,
N. Bobrysheva, M. Osmolowsky,
V. Semenov, T. Tsakalatos and
M. Muhammed, Langmuir, 2004, 20, 2472;
(b) M. Mandal, S. Kundu, S. K. Ghosh,
S. Panigrahi, T. K. Sau, S. M. Yusuf and
T. Pal, J. Colloid Interface Sci., 2005, 286,
187.
31 D. Caruntu, B. L. Cushing, G. Carunt and
C. J. O’Connor, Chem. Mater., 2005, 17,
3398.
This journal is ª The Royal Society of Chemistry 2008
View Article Online
32 S. Sun, S. Anders, T. Thomson,
J. E. E. Baglin, M. F. Toney, H. Hamann,
C. B. Murray and B. D. Terris, J. Phys.
Chem. B, 2003, 107, 5419.
33 M. P. Pileni, Y. Lalatonne, D. Ingert,
I. Lisiecki and A. Courty, Faraday
Discuss., 2004, 125, 251.
34 (a) L. Y. Wang, J. Luo, M. M. Maye,
Q. Fan, Q. Rendeng, M. H. Engelhard,
C. M. Wang, Y. H. Lin and C. J. Zhong,
J. Mater. Chem., 2005, 15, 1821; (b)
L. Y. Wang, J. Luo, Q. Fan, M. Suzuki,
I. S. Suzuki, M. H. Engelhard, Y. Lin,
N. Kim, J. Q. Wang and C. J. Zhong,
J. Phys. Chem. B, 2005, 109, 21593.
35 H.-P. Park, M. J. Schadt, L. Y. Wang,
I. S. Lim, P. N. Njoki, S. H. Kim,
M. Jang, J. Luo and C. J. Zhong,
Langmuir, 2007, 23, 9050.
36 T. Kinoshita, S. Seino, Y. Mizukoshi,
Y. Otome, T. Nakagawa, K. Okitsu and
T. A. Yamamoto, J. Magn. Magn. Mater.,
2005, 293, 106.
37 K. Kawaguchi, J. Jaworski, Y. Ishikawa,
T. Sasaki and N. Koshizaki, J. Magn.
Magn. Mater., 2007, 310, 2369.
38 W. Wu, Q.-G. He, H. Chen, J.-X. Tang and
L.-B. Nie, Acta Chim. Sin., 2007, 65, 1273.
39 M. Spasova, V. Salgueirino-Maceira,
A. Schlachter, M. Hilgendorff, M. Giersig,
L. M. Liz-Marzan and M. Farle, J. Mater.
Chem., 2005, 15, 2095.
40 C. K. Lo, D. Xiao and M. M. F. Choi,
J. Mater. Chem., 2007, 17, 2418.
41 Z. Xu, Y. L. Hou and S. Sun, J. Am. Chem.
Soc., 2007, 129, 8698.
42 B. L. Oliva, A. Pradhan, D. Caruntu,
C. J. O’Connor and M. A. Tarr, J. Mater.
Res., 2006, 21, 1312.
43 S. I. Stoeva, F. W. Huo, J. S. Lee and
C. A. Mirkin, J. Am. Chem. Soc., 2005,
127, 15362.
44 P. de la Presa, M. Multigner,
M. P. Morales, T. Rueda, E. Fernandez-
Pinel and A. Hernando, J. Magn. Magn.
Mater., 2007, 316, E753.
45 S. Mandal and K. M. Krishnan, J. Mater.
Chem., 2007, 17, 372.
46 (a) V. Salgueirino-Maceira, M. A. Correa-
Duarte, M. Farle, A. Lopez-Quintela,
K. Sieradzki and R. Diaz, Chem. Mater.,
2006, 18, 2701; (b) M. A. Correa-Duarte,
V. Salgueirino-Maceira, B. Rodriguez-
Gonzalez, L. M. Liz-Marzan,
A. Kosiorek, W. Kandulski and
M. Giersig, Adv. Mater., 2005, 17, 2014.
47 J. Zhang, M. Post, T. Veres, Z. J. Jakubek,
J. W. Guan, D. S. Wang, F. Normandin,
Y. Deslandes and B. Simard, J. Phys.
Chem. B, 2006, 110, 7122.
48 (a) M. J. Schadt, W. Cheung, J. Luo and
C. J. Zhong, Chem. Mater., 2006, 18,
5147; (b) M. M. Maye, W. Zheng,
F. L. Leibowitz, N. K. Ly and
C. J. Zhong, Langmuir, 2000, 16, 490; (c)
C. J. Zhong, W. X. Zheng,
F. L. Leibowitz and H. H. Eichelberger,
Chem. Commun., 1999, 13, 1211.
49 (a) N. Z. Clarke, C. Waters, K. A.
Johnson, J. Satherley and D. J.
Schiffrin, Langmuir, 2001, 17, 6048; (b)
T. Teranishi, S. Hasegawa, T. Shimizu
and M. Miyake, Adv. Mater., 2001, 13,
1699; (c) H. Fan, J. Gabaldon, C. J.
Brinker and Y. B. Jiang, Chem. Commun.,

2006, 2323; (d) F. Terzi, R. Seeber,
L. Pigani, C. Zanardi, L. Pasquali,
S. Nannarone, M. Fabrizio and S. Daolio,
J. Phys. Chem. B, 2005, 109, 19397; (e)
A. W. Shaffer, J. G. Worden and Q. Huo,
Langmuir, 2004, 20, 8343; (f) S. W. Chen
and J. M. Sommers, J. Phys. Chem. B,
2001, 105, 8816.
50 R. Guo, Y. Song, G. L. Wang and
R. W. Murray, J. Am. Chem. Soc., 2005,
127, 2725.
51 (a) V. Zaspalis, V. Tsakaloudi,
E. Papazoglou, M. Kolenbrander,
R. Guenther and P. Van Der Valk,
J. Electroceram., 2004, 13, 585; (b)
Y. F. Cui, X. Wang, Y. Wei, S. L. Hao
and M. Wang, J. Synth. Cryst., 2005, 34,
Published on 28 February 2008 on http://pubs.rsc.org | doi:10.1039/B719096D
1096; (c) S. L. Hao, X. Wang, Y. Wei,
Downloaded by Ryerson Polytechnic University on 06/05/2013 08:39:16.
Y. M. Wang and C. J. Liu, Rare Metals,
2006, 25, 466.
52 X. Wang, L. Y. Wang, H. Park,
P. N. Njoki, S. Lim and C. J. Zhong,
presented at the American Chemical
Society 234 th National Meeting, Boston,
USA, August 19–23, 2007, INOR 636.
53 X. W. Teng, D. Black, N. J. Watkins,
Y. Gao and H. Yang, Nano Lett., 2003,
3, 261.
This journal is ª The Royal Society of Chemistry 2008
54 (a) D. Mott, J. Luo, P. Njoki, Y. Lin,
L. Y. Wang and C. J. Zhong, Catal.
Today, 2007, 122, 378; (b) D. Mott,
J. Luo, A. Smith, L. Y Wang, P. N. Njoki
and C. J. Zhong, Nanoscale Res. Lett.,
2007, 2, 12.
55 G. Mie, Ann. Phys., 1908, 25, 377.
56 A. K. Boal, B. L. Frankamp, O. Uzun,
M. Tuominen and V. M. Rotello, Chem.
Mater., 2004, 16, 3252.
57 (a) F. L. Leibowitz, W. X. Zheng,
M. M. Maye and C. J. Zhong, Anal.
Chem., 1999, 71, 5076; (b) L. Han,
M. M. Maye, F. L. Leibowitz, N. K. Ly
and C. J. Zhong, J. Mater. Chem., 2001,
11, 1259; (c) W. X. Zheng, M. M. Maye,
F. L. Leibowitz and C. J. Zhong, Anal.
Chem., 2000, 72, 2190; (d) L. Han, J. Luo,
N. N. Kariuki, M. M. Maye, V. W. Jones
and C. J. Zhong, Chem. Mater., 2003,
15, 29.
58 D. Andreeva, Gold Bull., 2002, 35, 82.
59 M. Haruta and M. Date, Appl. Catal., A,
2001, 222, 427.
60 C. T. Campbell, Science, 2004, 306, 234.
61 (a) G. C. Bond and D. T. Thompson, Catal.
Rev., 1999, 41, 319; (b) D. R. Rolison,
Science, 2003, 299, 1698.
J. Mater. Chem., 2008, 18, 2629–2635 | 2635
View Article Online
62 D. I. Garcia-Gutierrez, C. E. Gutierrez-
Wing, L. Giovanetti, J. M
Ramallo-Lopez, F. G. Requejo and
M. Jose-Yacaman, J. Phys. Chem. B,
2005, 109, 3813.
63 C. Damle, K. Biswas and M. Sastry,
Langmuir, 2001, 17, 7156.
64 (a) N. Toshima, Y. Shiraishi, A. Shiotsuki,
D. Ikenaga and Y. Wang, Eur. Phys. J. D,
2001, 16, 209; (b) J. I. Park, M. G. Kim,
Y. W. Jun, J. S. Lee, W. R. Lee and
J. Cheon, J. Am. Chem. Soc., 2004, 126,
9072.
65 N. Toshima, M. Kanemaru, Y. Shiraishi
and Y. Koga, J. Phys. Chem. B, 2005, 109,
16326.
66 (a) J. Luo, P. Njoki, Y. Lin, D. Mott,
L. Y Wang and C. J. Zhong, Langmuir,
2006, 22, 2892; (b) J. Luo, P. Njoki,
Y. Lin, L. Y Wang, D. Mott and
C. J. Zhong, Electrochem. Commun., 2006,
8, 581.
67 (a) J. Luo, M. M. Maye, V. Petkov,
N. N. Kariuki, L. Y Wang, P. Njoki,
D. Mott, Y. Lin and C. J. Zhong, Chem.
Mater., 2005, 17, 3086; (b) P. N. Njoki,
J. Luo, M. M. Maye, L. Y. Wang and
C. J. Zhong, Langmuir, 2005, 21, 1623.