Generalized fabrication of multifunctional nanoparticle assemblies on silica spheres

Article abstract of DOI:10.1002/anie.200504107

Sequential decoration of silica spheres by covalent bonding of magnetite nanoparticles (blue) and attachment of functional nanoparticles of Au, CdSe/ZnS, or Pd (red) afforded multifunctional assemblies exhibiting combinations of magnetism with surface pla

Full text of DOI:10.1002/anie.200504107

Angewandte
Chemie
catalysts, contrast-enhancement agents for magnetic reso-
nance imaging (MRI), magnetic carriers for drug-delivery
systems, biosensors, and bioseparation.[6]
Controlled assembly of magnetic nanoparticles on the
desired supports is important for these applications. There
have been several reports on the assembly of magnetic
nanoparticles on spherical templates by the LbL techni-
que.[2d–g] For example, alternating layers of polyelectrolytes
and magnetite nanoparticles, synthesized in an aqueous
phase, were assembled on polystyrene latex spheres. Nano-
particles synthesized in an organic phase are generally more
crystalline and uniform than those prepared in the aqueous
phase. Recently, FePt alloy nanoparticles[7] and magnetite
nanoparticles,[8] synthesized in an organic phase, were assem-
bled on silica spheres by electrostatic interaction. However, it
was necessary for these nanoparticles, initially synthesized in
an organic phase, to be transformed into water-dispersible
nanoparticles, because the assembly procedures were per-
formed in the aqueous phase. Herein we report on a new
procedure to assemble hydrophobic magnetite (Fe3O4) nano-
particles through covalent bonding on silica spheres by means
of a nucleophilic substitution reaction in organic media. We
also fabricated multifunctional nanoparticle/silica sphere
assemblies by subsequent assembly of nanoparticles of Au,
CdSe/ZnS, or Pd on the magnetite nanoparticle-bearing silica
spheres. The synthesized multifunctional silica spheres exhib-
ited a combination of magnetism and surface plasmon
resonance (Au), luminescence (CdSe/ZnS), or catalysis (Pd).
The general synthetic procedure for multifunctional
nanoparticle/silica sphere assemblies is shown in Scheme 1
(see also the Experimental Section). Uniformly sized silica
spheres were prepared by the Stöber method.[9] For the
assembly of the nanoparticles, the surfaces of the silica
spheres were functionalized with amino groups by treatment
with (3-aminopropyl)trimethoxysilane (APS). Monodisperse
nanoparticles of Fe3O4,[5h] Au,[10] CdSe/ZnS,[11] and Pd[12] were
synthesized by procedures described previously. To assemble
Fe3O4 nanoparticles on the silica spheres, the capping oleic
Nanoparticle Assemblies
DOI: 10.1002/anie.200504107
Generalized Fabrication of Multifunctional
Nanoparticle Assemblies on Silica Spheres**
Jaeyun Kim, Ji Eun Lee, Jinwoo Lee, Youngjin Jang,
Sang-Wook Kim, Kwangjin An, Jung Ho Yu, and
Taeghwan Hyeon*
Uniformly sized colloidal nanoparticles have attracted a great
deal of attention, not only for their fundamental scientific
interest, which is derived from their size-dependent proper-
ties, but also for their many technological applications, which
include biomedical imaging and functional building blocks for
nanoscale devices.[1] Many types of nanoparticles have been
assembled on the surfaces of various spherical supports, such
as Stöber silica and polymer latex spheres, by various methods
including layer-by-layer (LbL) techniques using oppositely
charged polyelectrolytes,[2] methods based on direct electro-
static interactions between nanoparticles and supports,[3] and
techniques based on the coordination of the nanoparticles on
amino- or thiol-functionalized silica spheres.[4] Magnetic
nanoparticles[5] have been applied as magnetically separable
[*] J. Kim, J. E. Lee, Dr. J. Lee, Y. Jang, K. An, J. H. Yu, Prof. Dr. T. Hyeon
National Creative Research Initiative Center for Oxide Nano-
crystalline Materials and
School of Chemical and Biological Engineering
Seoul National University
Seoul 151-744 (Korea)
Fax: (+82)2-886-8457
E-mail: thyeon@snu.ac.kr
Prof. Dr. S.-W. Kim
Department of Molecular Science and Technology
Ajou University, Suwon 443-749 (Korea)
[**] T.H. is thankful for financial support by the Korean Ministry of
Science and Technology through the National Creative Research
Initiative Program.
Scheme 1. Synthetic procedure to obtain multifunctional nanoparticle/
silica sphere assemblies.
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acid ligands of the Fe3O4 nanoparticles were exchanged with
unmodified silica spheres, the number of Pd nanoparticles
assembled on the former was much higher than that on the
latter. Figure 2a shows a TEM image of Mag-SiO2-Au, in
which gold nanoparticles 1–3 nm in size and 7-nm Fe3O4
2-bromo-2-methylpropionic acid (BMPA).[13] The BMPA-
stabilized Fe3O4 nanoparticles were assembled on the surfaces
of the amino-functionalized silica spheres. The resulting
Fe3O4 nanoparticle/silica sphere assemblies were designated
as Mag-SiO2. Subsequently, functional nanoparticles of Au,
CdSe/ZnS, or Pd were additionally assembled on Mag-SiO2 to
give multifunctional assemblies designated as Mag-SiO2-Au,
Mag-SiO2-CdSe/ZnS, and Mag-SiO2-Pd, respectively.
A field-emission scanning electron microscopy (FE-SEM)
image of Mag-SiO2 (Figure 1a) showes that uniform 14-nm
Figure 1. SEM and TEM images of Mag-SiO2. a) FE-SEM image of 500-
nm silica spheres assembled with 14-nm Fe3O4 nanoparticles (inset:
high-magnification FE-SEM image). b) TEM image of 300-nm silica
spheres assembled with 7-nm Fe3O4 nanoparticles. c) TEM image of
100-nm silica spheres assembled with 7-nm Fe3O4 nanoparticles.
Figure 2. a) TEM image of Mag-SiO2-Au, in which gold nanoparticles
1–3 nm in size and 7-nm Fe3O4 nanoparticles were assembled on 100-
nm silica spheres. b) TEM image of Mag-SiO2-Au, in which 13-nm Au
nanoparticles and 7-nm Fe3O4 nanoparticles were assembled on 300-
nm silica spheres. c) TEM image of Mag-SiO2-CdSe/ZnS, in which 4.5-
nm CdSe/ZnS quantum dots and 14-nm Fe3O4 nanoparticles were
assembled on 100-nm silica spheres. d) TEM image of Mag-SiO2-Pd,
in which 5-nm Pd nanoparticles and 14-nm Fe3O4 nanoparticles were
simultaneously assembled on 100-nm silica spheres.
Fe3O4 nanoparticles were well assembled on the surfaces of
the 500-nm silica spheres. Figure 1b and c shows transmission
electron microscopy (TEM) images of 7-nm Fe3O4 nano-
particles assembled on 300- and 100-nm silica spheres,
respectively. The BMPA-stabilized Fe3O4 nanoparticles were
covalently bonded onto the surfaces of the amino-function-
alized silica spheres by a direct nucleophilic substitution
reaction between the terminal Br groups of the ligands and
NH2 groups on the silica spheres in THF.[14] This constitutes a
new and simple method of assembling magnetite nanoparti-
cles synthesized in organic media on silica spheres by direct
covalent bonding, as opposed to the more complicated LbL
method, which is conducted in the aqueous phase by using the
electrostatic interaction between magnetic nanoparticles and
polyelectrolytes. When the original oleic acid stabilized Fe3O4
nanoparticles were used instead of BMPA-stabilized ones in
assembling Fe3O4 nanoparticles on the silica spheres, the
number of magnetite nanoparticles attached to the silica
spheres was substantially reduced.
By using Mag-SiO2 as support, various multifunctional
composite nanoparticle assemblies were fabricated by coor-
dinating functional nanoparticles of Au, CdSe/ZnS, or Pd to
the residual surface amino groups. It is well known that alkyl
amines such as hexadecylamine and oleylamine, which are
often used as stabilizing ligands for nanoparticles of noble
metals and semiconductors, bind to the metal atoms on the
surfaces of the nanoparticles through the lone-pair electrons
on the nitrogen atom.[11,12] Similarly, the lone-pair electrons in
the amino groups of the amino-modified silica spheres seem
to bind to the metal atoms (Au in Au nanoparticles, Zn in the
case of CdSe/ZnS core/shell nanoparticles, and Pd in Pd
nanoparticles). For example, when we assembled Pd nano-
particles on both amino-modified silica spheres and pristine
nanoparticles were assembled on 100-nm silica spheres.
Larger Au nanoparticles (13 nm) were also assembled on
300-nm silica spheres with 7-nm magnetite nanoparticles
(Figure 2b). The TEM and high-resolution TEM (HRTEM)
images of Mag-SiO2-CdSe/ZnS showed that these composite
nanoparticle assemblies consist of highly crystalline 4.5-nm
CdSe/ZnS quantum dots coexisting with 14-nm Fe3O4 nano-
particles on the surfaces of 100-nm silica spheres (Figure 2c).
Assembly of 14-nm Fe3O4 nanoparticles and 5-nm Pd nano-
particles on 100-nm silica spheres produced Mag-SiO2-Pd
(Figure 2d).
The properties of these multifunctional nanoparticle
assemblies are depicted in Figure 3. For applications involving
magnetic delivery or separation, superparamagnetic proper-
ties are more desirable than ferromagnetism, because there
should be no residual magnetism after the magnetic field is
removed. The field-dependent magnetization curve of the
Mag-SiO2 sample of Figure 1a at 300 K showes no hysteresis
(Figure 3a), that is, Mag-SiO2 exhibits superparamagnetic
behavior derived from the well-assembled magnetite nano-
particles on the silica spheres. The UV/Vis spectrum of the
Mag-SiO2-Au of Figure 2b showes the characteristic surface
plasmon band at 530 nm (solid line in Figure 3b). On the
other hand, the supernatant solution after removal of Mag-
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Figure 4. Photographs of reaction mixtures a) before and b) after
magnetic separation of Mag-SiO2-Pd used in reaction (1).
iodides and aryl bromides were shown by Mag-SiO2-Pd
(Table 1). To investigate the stability of the silica spheres
during the catalytic reactions, we performed recycling experi-
ments.
Figure 3. a) Field-dependent magnetization at 300 K of the Mag-SiO2
sample of Figure 1a. b) UV/Vis absorption spectra of a suspension of
the Mag-SiO2-Au sample of Figure 2b before (solid line) and after
(dotted line) removal of Mag-SiO2-Au by magnetic separation. c) Pho-
toluminescence spectra (lex =450 nm) of pristine CdSe/ZnS nano-
particles (blue line) and the Mag-SiO2-CdSe/ZnS sample of Figure 2c
(red line). d,e) Confocal micrographs obtained from a mixed suspen-
sion of red-emitting Mag-SiO2-CdSe/ZnS and green-emitting SiO2-
CdSe/ZnS before and after removal of red-emitting Mag-SiO2-CdSe/
ZnS by using a magnet, respectively.
Table 1: Test of catalytic activity of Mag-SiO2-Pd in the Sonogashira
coupling reaction (1).[a]
Entry
X
Ar
Catalyst (mol %)[b]
Yield [%][c]
1
2
3
4
5
6
7
8
9
I
I
I
I
4-acetylphenyl Mag-SiO2-Pd (3)
95.0
99.3
98.1
100
99.5
98.2
88.1
75.7
16.9
2-thienyl
2-thienyl
phenyl
Mag-SiO2-Pd (3)
recovered from entry 2 (3)
Mag-SiO2-Pd (3)
Br 2-thienyl
Br 2-thienyl
Br 2-thienyl
Br 2-thienyl
Br 2-thienyl
Mag-SiO2-Pd (5)
SiO2-Au with a magnet showed no absorption peak (dotted
line in Figure 3b) and thus demonstrated the magnetic-
separation characteristics of the silica spheres. The Mag-SiO2-
CdSe/ZnS spheres of Figure 2c exhibited an emission peak at
a position slightly red-shifted from that of the pristine CdSe/
ZnSnanoparticles (Figure 3c).
recovered from entry 5 (5)
recovered from entry 6 (5)
recovered from entry 7 (5)
recovered from entry 8 (5)
[a] DIA=diisopropylamine; reaction conditions: 858C, 18 h. [b] Catalyst
concentration based on Pd. [c] Yield of isolated product.
To demonstrate the combined magnetic and luminescent
properties of Mag-SiO2-CdSe/ZnS simultaneously, we pre-
pared red-emitting Mag-SiO2-CdSe/ZnS (Fe3O4 nanoparticles
and red-emitting CdSe/ZnS nanoparticles assembled on silica
spheres) and green-emitting SiO2-CdSe/ZnS (green-emitting
CdSe/ZnS nanoparticles assembled on silica spheres without
Fe3O4 nanoparticles). Then, the two samples were mixed in
chloroform and magnetic separation was performed. The
confocal micrograph of the mixed solution (Figure 3d)
showed that red and green dots were coexistent, whereas
only green dots remained after magnetic separation (Fig-
ure 3e), that is, red-emitting Mag-SiO2-CdSe/ZnS was com-
pletely removed from the mixture. This combination of
magnetic and optical properties should enable the Mag-
SiO2-CdSe/ZnS nanoparticle assemblies to be used simulta-
neously for biolabeling and MRI.
To investigate the catalytic activity of Mag-SiO2-Pd, a
Sonogashira coupling reaction was performed. After com-
pletion of the coupling reaction, Mag-SiO2-Pd could easily be
separated from the reaction mixture by using a magnet. The
reaction solution was dark before magnetic separation
(Figure 4a), whereas black Mag-SiO2-Pd was attracted to
the magnet and a yellowish solution remained after magnetic
separation (Figure 4b). High catalytic activities for aryl
As summarized in Table 1 (entries 5–9), Mag-SiO2-Pd was
recycled four times for coupling 2-bromothiophene. Recently,
Nacci et al. reported that the yield of Suzuki and Stille
coupling reactions with Pd nanoparticles gradually decreased
as recycling proceeded.[15] Our recycling experiments showed
a similar trend. The catalytic activity of Mag-SiO2-Pd for the
Sonogashira coupling was maintained above 75% yield until
the third recycling. However, the yield steeply decreased to
17% in the fourth recycling reaction. The TEM image of the
recovered Mag-SiO2-Pd after the first reaction showed that
not only Fe3O4 nanoparticles but also Pd nanoparticles were
firmly attached to the silica spheres. In contrast, the TEM
image after the fourth recycling experiment revealed that
most of Pd nanoparticles were detached from the silica
spheres, whereas many Fe3O4 nanoparticles were still firmly
attached to the silica spheres. These results demonstrate that
the decrease in yield of the catalytic coupling reactions
resulted from detachment of Pd nanoparticles from the silica
spheres.
In summary, we have reported a simple, reproducible, and
general method of preparing multifunctional nanoparticle
assemblies on silica spheres. Magnetite nanoparticles synthe-
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4791

Communications
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sphere assemblies are likely to find many catalytic and
biomedical applications derived from their combination of
magnetic properties with surface plasmon resonance, lumi-
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Experimental Section
Synthesis of amino-functionalized Stöber silica spheres: Uniform
100-, 300-, and 500-nm silica spheres were synthesized by the Stöber
method.[9] The surfaces of the silica spheres were functionalized with
amino groups by treatment with APSin refluxing ethanol.
Ligand exchange of Fe3O4 nanoparticles synthesized in an organic
phase: Monodisperse Fe3O4 nanoparticles (14- and 7-nm) capped with
oleic acid were synthesized in an organic phase by procedures
described previously.[5h] 50 mg of the as-synthesized nanoparticles
were dispersed in 3 mL of chloroform and the resulting solution was
added to 30 mL of BMPA in chloroform (0.1m solution).[13] After
stirring the solution at room temperature for 48 h, the nanoparticles
were precipitated by adding an excess of ethanol. The precipitated
nanoparticles were retrieved by centrifugation.
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Synthesis of Mag-SiO2: The BMPA-stabilized magnetite nano-
particles dispersed in 3 mL of THF were added to a solution
containing 0.1 g of amino-functionalized silica spheres dispersed in
20 mL of THF, and the resulting dispersion was heated to reflux for
3 h. The magnetite nanoparticle/silica sphere assemblies were isolated
by three cycles of centrifugation, redispersion in THF, and magnetic
separation.
Synthesis of Mag-SiO2-Au: Citrate-stabilized gold nanoparticles
with sizes of 1–3 and 13 nm were prepared by procedures described
previously.[10] 10 mg of Mag-SiO2 was dispersed in 30 mL of aqueous
Au nanoparticle solution, and the resulting aqueous dispersion was
stirred for 6 h at room temperature. The Mag-SiO2-Au spheres were
isolated by three cycles of centrifugation, redispersion in water, and
magnetic separation.
Synthesis of Mag-SiO2-CdSe/ZnS: CdSe/ZnS nanoparticles were
prepared by a procedure described previously.[11] A dispersion of
20 mg of CdSe/ZnS nanoparticles in 3 mL of chloroform was mixed
with 10 mg of Mag-SiO2 in 10 mL of chloroform, and the resulting
dispersion was stirred at room temperature for 6 h. The Mag-SiO2-
CdSe/ZnS spheres were isolated by three cycles of centrifugation,
redispersion in chloroform, and magnetic separation.
Synthesis of Mag-SiO2-Pd: 5-nm Pd nanoparticles were prepared
by a procedure described previously.[12] A dispersion of 20 mg of Pd
nanoparticles in 3 mL of chloroform was mixed with 10 mg of Mag-
SiO2 in 10 mL of chloroform, and the resulting dispersion was stirred
at room temperature for 6 h. The Mag-SiO2-Pd spheres were isolated
by three cycles of centrifugation, redispersion in chloroform, and
magnetic separation.
Received: November 18, 2005
Revised: May 12, 2006
Published online: June 27, 2006
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