Journal of Colloid and Interface Science 310 (2007) 144–150

www.elsevier.com/locate/jcis

Fluorescent organosilica micro- and nanoparticles with controllable size

Robert Vogel a,∗ , Peter P.T. Surawski a , Bradley N. Littleton b , Chris R. Miller a ,
Gwendolyn A. Lawrie a , Bronwyn J. Battersby a , Matt Trau a
a Nanotechnology and Biomaterials Centre, Australian Institute for Bioengineering and Nanotechnology, University of Queensland,
Brisbane, QLD 4072, Australia
b Department of Physics, University of Queensland, Brisbane, QLD 4072, Australia

Received 17 August 2006; accepted 18 January 2007

Available online 7 February 2007

Abstract
This paper reports on the synthesis of uniformly dye-doped organosilica particles with narrow size distribution. The particle size can be con-
trolled from tenths of nanometers up to several micrometers, whilst still maintaining monodispersity. Microparticles were observed to swell in
various solvents up to ∼2.5 times their original volume, suggesting the presence of a gel-like internal structure. As shown by confocal microscopy,
this morphological control of particle swelling has important implications for the encoding of the nano/micro particles with organic dyes, such as
rhodamine B isothiocyanate. Swelling allows the dye to penetrate the organosilica matrix and produce uniformly dye-doped nano- and micropar-
ticles. Finally, we suggest a coagulation model for the particle formation which significantly differs from conventional Stöber synthesis.
© 2007 Elsevier Inc. All rights reserved.

Keywords: Colloids; Ormosil; Organosilica; Nanoparticles; Microspheres; Dyes; Biomolecules

1. Introduction ica microspheres are based on aerospraying [9], micron-sized

Optically-encoded silica particles can be utilised in bioan-
alytical applications such as screening of biomolecules [1],
intracellular sensing [2], colloidal encoding [3,4], or signal
amplification [5–7]. The usefulness of silica-based materials
stems from the variety of surface modification and immobilisa-
tion procedures available for the coupling of biomolecules [6].
Key criteria that particles should satisfy in order to be suitable
for these applications are monodispersity, control over parti-
cle size, uniform surface loading and uniform distribution of
internal encoding elements such as organic dyes or quantum
dots.
Stöber et al. achieved the controlled growth of monodis-
perse nonporous silica particles with diameters ranging from
20 nm up to approximately 2 µm [8]. This technique utilised
silicon alkoxide precursors dissolved in short chain alcohols in
the presence of ammonia. Other approaches to synthesising sil-
* Corresponding author.
E-mail address: r.vogel1@uq.edu.au (R. Vogel).
0021-9797/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.01.092
injection nozzles [10], and ultrasonic oscillation [11]. How-
ever, these methods result in a high degree of polydispersity
in size distribution. In comparison, Barbe et al. produced spher-
ical silica particles with narrow size distribution over an exten-
sive size range of 10 nm–50 µm, combining sol–gel synthesis
with surfactant-stabilised water-in-oil emulsion polymerisation
chemistry [12].
Thiol- and amine-based organosilanes can be incorporated
into the silica network by a seeded growth technique [13,14],
to allow for the covalent attachment of thiol- and amine-
reactive organic dyes and the conjugation of biomolecules. We
recently developed an alternative surfactant-free two-step ap-
proach to synthesise thiol-functionalised organosilica micropar-
ticles, based on acid-catalysed hydrolysis and condensation
followed by base-catalysed condensation [1,15]. By carefully
controlling the base-catalysis, these organosilica microparticles
proved to be monodisperse with mean particle diameters rang-
ing from 2 to 5 µm.
Recent approaches in diagnostic bead-based assays have
required the implementation of optical encoding strategies,
whereby the uniform incorporation of encoding elements into
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150
nano- and microparticles is of major importance [7,16]. Tra-
ditional silica microsphere production has utilised the well-
known Stöber synthesis method, as mentioned above. How-
ever, the structure of the internal network of these silica par-
ticles does not allow the access of large organic molecules
such as fluorescent dyes [8,17]. In order to internalise en-
coding elements such as fluorescent dyes, several possibil-
ities are available. These include the generation of poros-
ity within the silica network using surfactant template strate-
gies [18–21], template-free strategies [1] and the incorporation
of encoding elements during synthesis of the silica material
[13,22–24].
Incorporation of encoding dyes into common polymeric
particles is easily achieved by controlled swelling in suitable
solvents. While Stöber silica does possess branched, micro-
porous internal structure, incorporation of dyes is negligi-
ble as any swelling is of a very small scale [25]. In com-
parison, some organically-modified silicate (ORMOSIL) bulk
materials possess enough structural flexibility to allow sol-
vation, resulting in material swelling not unlike a polymer
gel [26]. Research by Rao et al. investigated the swelling
properties of ORMOSIL gels in aqueous solutions and their
applications for microdevices [27,28]. These bulk materials
were touted as environmental sensors and shown to swell
in response to changes of pH, temperature, and an applied
field. However, these ORMOSIL gels were not adopted for
particle synthesis. In comparison, Goller et al. investigated
the swelling of organosilica microparticles in the nonpo-
lar solvent n-heptane [29]. These microparticles were pre-
pared using a combination of bi- and trifunctional silanes
and resulted in relatively small particles with diameters below
1.5 µm. Overall, the organic components of these ORMOSIL
materials have consisted primarily of alkyl chains. In con-
trast to these materials, Walcarius et al. produced mercapto-
functionalised organosilica particles using the co-condensation
of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxy-
silane (MPTMS) [30–32]. The resulting particles were highly
functionalised and successfully removed large amounts of mer-
cury from aqueous solutions. However, the high polydispersity
of these particles renders them unsuitable for most bioanalytical
applications.
It is evident from the research to date that there has not been
a successful synthetic route developed which brings together
all four desirable elements required in a particle designed for
biomolecular synthesis and screening namely: monodispersity,
selective functionality, controlled size and robust dye incorpo-
ration.
In this report we describe a method which achieves all of
these objectives. The modified synthetic route demonstrates
the size control of novel organosilica micro- and nanoparticles
and an aggregation based model for the formation of emulsion
droplets which condense to form solid particles is proposed.
Control of particle size (50 nm–3 µm) is achieved by varying
the total monomer concentration. In addition, dye molecules are
shown to be covalently bound throughout the interior of both
organosilica nano- and microparticles, enabled by solvent as-
sisted swelling of the organosilica matrix.
145
2. Materials and methods
2.1. Materials
3-Mercaptopropyltrimethoxysilane (MPTMS, 95%) was ob-
tained from Lancaster and used as supplied. Triethylamine
(TEA, 99%), hydrochloric acid (37%), dimethylformamide
(DMF), and rhodamine B isothiocyanate (RBITC) were ob-
tained from Sigma–Aldrich and used as received. Commercial
silica particles with a diameter of 5.17 µm (standard deviation
unspecified) were purchased from Bangs labs.
2.1.1. Synthesis
Organosilicate particles were produced using a two step
process. The initial acid catalysis step is described in detail by
Miller et al. [15]. The resulting emulsion was centrifuged and
the supernatant was separated from the oil. The supernatant
phase was then diluted with pH 3.5 water, to obtain various
concentrations (0.1, 1, 5, 10, 50, and 100%) of the supernatant
phase. These supernatant solutions are referred to as “0.1%, . . . ,
100% solutions.” Finally in the base-catalysed step, 70–100 µl
of TEA was rapidly added to 100 ml of the supernatant–water
mixtures under continuous stirring.
Approximately 30 min after the addition of TEA, the formed
particles were separated from solution by centrifugation and
then washed in ethanol. This procedure was applied for samples
with supernatant concentrations >3%. Due to a slower particle
formation process at lower concentrations the samples with su-
pernatant concentrations of 0.1 and 1% were left under basic
conditions for 24 h before being centrifuged and washed.
2.1.2. Dye incorporation
For investigations into dye localisation, the organosilica par-
ticles were covalently labeled with rhodamine B isothiocyanate
(RBITC) in DMF. Once dye incorporation was complete, bead
pellets were washed from DMF into ethanol for confocal mi-
croscopy analysis.
2.2. Methods
2.2.1. Electron microscopy
Scanning electron microscopy (SEM) images of platinum
coated samples were collected on a JEOL JSM 6400F, us-
ing an accelerating voltage of 5–10 kV. Images were analysed
with Image-Pro software to determine size distributions, using
a minimum of 200 particles.
Transmission electron microscopy (TEM) studies on organo-
silica particles were carried out on a JEOL 2010 microscope at
an operating voltage of 200 kV.
2.2.2. Optical transmission microscopy
The swelling of organosilica and silica microparticles (Bangs
Labs) in different solvents (water, ethanol, DMF) was inves-
tigated by suspending dried microparticles in approximately
1 ml of solution and left for at least 48 h. A Nikon Eclipse
TE2000-E with a Photometrics CoolSnap HQ camera attach-
ment was used to image microparticles at 100× magnification
146 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150
Fig. 1. Flow chart of the particle synthesis process.
in the various solvents. The average sphere diameters were de-
termined by measuring over 200 particles.
2.2.3. Confocal microscopy
Confocal images were taken with a Zeiss 510 Meta confocal
microscope. Each support was imaged at 100× magnification
using 543 nm excitation and automatic brightness/contrast cal-
ibration.
Fluorescence intensity measurements were carried out on a
custom confocal microscope. Samples were illuminated with
a 532 nm diode pumped solid state laser and imaged with a
100 × free space objective with a nominal numerical aperture of
0.8. Images were formed by raster scanning the stage (Physik
Instrumente P-517.2CL) and photon flux was measured with
an avalanche photo diode (Perkin–Elmer SPCM-AQR-14FC).
The microscope’s point spread function (spot size) was altered
by decreasing the numerical aperture of the illumination and
increasing the pinhole size, in order to make it significantly
larger than the bead diameter. Also note that in general the axial
spot size is larger than lateral spot size for a standard confocal
microscope [33]. For these reasons we could compare the fluo-
rescence emission from each entire bead by simply comparing
the peak intensities of the images created by raster scanning the
stage.
3. Results and discussion
Monodisperse organosilica particles were produced via a
two step process: acid catalysed hydrolysis and condensa-
tion of 3-mercaptopropyltrimethoxysilane (MPTMS), followed
by base catalysed condensation (see the experimental section
and Fig. 1). Acid catalysed condensation leads to the forma-
tion of emulsion droplets consisting of insoluble organosil-
ica oligomers [1,15]. The supernatant, separated by centrifu-
gation and used as a precursor solution for base catalysed
condensation, was diluted to obtain various concentrations
(0.1, 1, 5, 10, 50, and 100%). These supernatant solutions
are referred to as “0.1, . . . , 100% solutions.” The supernatant
phase predominantly consists of fully hydrolysed organosilica
monomer, dimer and trimer species [15]. The concentration of
these species is referred to as “total monomer” concentration
(Ctotal = Cmonomer + 2Cdimer + 3Ctrimer ). The calculation of the
“total monomer concentration” in 0.1, 1, 5, 10, 50, and 100%
solutions (Fig. 2d) is based on a volumetric approximation.
Knowing the initial volume of added MPTMS precursor and
measuring the volume of the separated oil (consisting of hy-
drolysed organosilane species) after centrifugation, the residual
amount of MPTMS in the supernatant has been estimated. Size
control of organosilica particles was achieved by varying the
total monomer concentration.
In Fig. 2, TEM (a) and SEM (b and c) images of particles
with diameters ranging from approximately 150 nm up to 3 µm
are shown. The various populations of organosilica particles
(using 1, 10, and 100% solutions) all possess very narrow size
distributions with coefficients of variance (CV) 0.1, validat-
ing monodispersity.
Fig. 2d displays the size dependence of the organosilica
spheres on the total monomer concentration (MPTMS concen-
tration). The condensation rate will be proportional to the con-
centration of hydrolysed monomer, dimer, and trimer species.
However, each of these species will contribute to the rate dif-
ferently, dependent upon diffusion rate and number of free hy-
droxyl groups [34]. As shown in Fig. 2d a higher concentration
of hydrolysed species will result in larger particle sizes.
The internal structures of these particles were investigated
to elucidate the accessibility of the organosilica network for or-
ganic molecules. Fig. 3 shows a typical high-resolution bright-
field TEM image of an organosilica particle. Particles with
diameters ranging from 50–200 nm were imaged. No obvi-
ous internal structures, indicating mesoporosity were observed.
These results are supported by N2 adsorption/desorption analy-
sis, resulting in Brunauer–Emmett–Teller (BET) surface areas
which correlate well with the geometric surface areas of solid
particles (1–2 m2 /g). The low surface area is likely to be a
result of shrinkage upon drying. Similar results of low BET
surface areas have been observed for analogous organosilica
nanoparticles [30–32]. The organosilica particles appear to be
comprised of an amorphous organosilica network with no dis-
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150
Fig. 2. TEM (a) and SEM (b and c) images of monodisperse organosilica nano-
and microspheres. Particle size dependence on total monomer concentration is
displayed in (d).
tinguishing features. Diffuse ring electron diffraction patterns
(not displayed) support the existence of an amorphous structure.
Confocal microscopy was used to confirm the ability of the
functionalised particles to bind thiol-reactive dye molecules.
Fig. 4 shows thin slices (<0.5 µm) through representative mi-
croparticles of (a) 10, (b) 50, and (c) 100% solutions after be-
147
Fig. 3. High-resolution TEM micrograph of an organosilica sphere.
ing labeled with rhodamine B isothiocyanate (RBITC), which
covalently reacts with thiol groups to form a dithiocarbamate
throughout the interior of the particles. Dithiocarbamate bonds
are stable in acidic and neutral conditions, but easily cleaved
in basic aqueous solution [35]. It is worth noting that for im-
proved chemical stability maleimides can be used instead [36],
which form a thioether bond that is not easily cleaved to yield
free thiol [35]. Background fluorescence caused by free RBTIC
dye was not detected, suggesting that the RBTIC-molecules are
covalently coupled to the thiol groups and the washing steps
were effective in removing excess dye. The uniform fluores-
cence intensity across the microparticles indicates that the dye
molecules are distributed evenly throughout the interior of the
microparticles.
Confocal microscopy was also applied to measure the to-
tal fluorescence intensities of dye-doped beads with various
sizes (Fig. 4d). Assuming the fluorescence intensity scales as a
power of the particle diameter, d, the intensity is given by I =
C ∗ d n (C is a constant). Hence it follows: log I = log(C ∗ d n ) =
log C + n∗ log d. If fluorescence were to scale with the parti-
cle volume, plotting log I against log d should give a straight
line with a slope equal to 3. In fact, the recorded data is best fit-
ted by a linear regression with n = 2.79 ± 0.1. This shows that
fluorescence scales very well with particle volume. The linear
dye uptake with particle volume indicates that different sized
particles have comparable internal structures suggesting the for-
mation process is independent of particle size.
Based on the BET and TEM studies mentioned above, dye
is expected to bind preferentially onto the particle surface. This
apparent contradiction to the results obtained by confocal mi-
croscopy can be explained by significant swelling of the parti-
cles in certain solvents, which is commonly seen in resin par-
ticles and is absent in Stöber particles. Hydrogel and resin ma-
terials display different volume increases depending upon the
solvent and degree of cross-linking [37]. Optical microscopy
148 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150
Fig. 4. Confocal microscope images of particles synthesised using different
silica precursor concentrations: [(a) 10, (b) 50, and (c) 100%] and dyed with
RBITC. A plot of fluorescence intensity versus particle diameter measured with
a confocal microscope is displayed in (d).
was applied to investigate the effect of various relevant solvents
(e.g., water, ethanol, and dimethylformamide (DMF)) on the di-
ameter and volume of organosilica microparticles. Fig. 5 shows
the volume increase of microparticles in several solvents, used
for synthesis (water), storage (ethanol), and dyeing procedure
(DMF). The microparticles were observed to swell by up to
∼2.5 times the dry volume in DMF. This swelling will cause the
organosilica network porosity to increase, allowing the incorpo-
ration of large molecules such as organic dyes which covalently
bind to the thiol functionalities of the organosilica. As shown
in previous work, these organosilica particles retain their fluo-
rescence when objected to various reagents involved in a mul-
tistep phosphoramidite oligonucleotide synthesis, whilst com-
mercially available encoded polystyrene–divinylbenzene parti-
cles are unstable in most synthesis steps and lose most of their
fluorescence [36]. These findings suggest that dye is covalently
Fig. 5. Swelling of organosilica microspheres and commercial TEOS derived
silica microspheres in different solvents.
linked to the organosilica matrix, stopping the leaching of dye
molecules during various oligonucleotide synthesis and wash-
ing steps.
It is worth mentioning that organosilica microparticles that
have been post-treated with ammonia do not swell to the same
degree. This reduction in swelling potential is attributed to an
increase in the condensation of the organosilica particles yield-
ing a more rigid network. As a negative control, nonporous sil-
ica microparticles of comparable diameter were dispersed in the
same solvents. These microparticles showed no substantial vol-
ume change, highlighting the inability of these TEOS derived
microparticles to become solvated and swell to any observable
degree.
Taking the size control and dye uptake studies as well as
previous investigations [15,36] into consideration we propose a
model for the particle formation process, as illustrated in Fig. 6.
As mentioned earlier, after completion of acid-catalysed
hydrolysis and condensation, the supernatant solution predom-
inantly consists of fully hydrolysed organosilica monomer,
dimer, and trimer species (Fig. 6a). The addition of base
(triethylamine, TEA) initiates the rapid crosslinking of these
fully hydrolysed organosilica species to form larger branched
oligomer assemblies. This rapid condensation triggers self-
emulsification by inducing a change in hydrophobicity of the
organosilica species, which become insoluble in water and
thus form an emulsion. We suggest that the emulsion droplets
(Fig. 6c) form by a coagulation process of precipitated oligomer
assemblies, which act as nuclei (Fig. 6b). This coagulation
process is controlled by the charge of the oligomer assem-
blies which rapidly coalesce to form emulsion droplets with
amounting charge, finally leading to the formation of a sta-
bilised emulsion. Further growth of the droplets is suggested
to be controlled and directed by Ostwald ripening [38] and
monomer addition.
As shown in previous studies, the condensation inside the
emulsion droplets continues and finally yields solid organosil-
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150
Fig. 6. Formation of organosilica particles: (a) hydrolysed monomer, dimer,
and trimer species; (b) hydrolysed species and nuclei; (c) hydrolysed species,
nuclei, and emulsion droplets (optical microscopy image is shown in inset), and
(d) solid particles, residual hydrolysed species and nuclei.
ica particles (Fig. 6d) with comparable size and size distribu-
tion [15]. The condensed particles are stabilised by Coulombic
repulsion, as proven by zeta-potential measurements [15].
Monomer-addition as an alternative growth mechanism to
the suggested coagulation process requires a slow hydrolysis
step [39], typically applied in Stöber synthesis, to enable the
formation of micron-sized particles [39,40]. However under the
synthesis conditions described in this paper, the base catalyst
is added to fully hydrolysed monomeric and small oligomeric
species (dimers and trimers) and hence all species are immedi-
ately available for condensation. In this scenario the monomer
addition growth would result only in a population of very small
particles [40], as opposed to micron sized particles. Instead, the
suggested particle formation process is based on a rapid co-
agulation process preceded by a short nucleation period. This
could also explain the narrow size distribution of the MPTMS
organosilica particles [41,42].
Since all species are initially hydrolysed before addition of
base, the organosilica particle formation process is likely to
be diffusion limited as opposed to reaction limited [39,43].
A lower concentration of hydrolysed species will slow down
nucleation and coagulation processes, and result in an increase
of polydispersity [44], as reflected by CV’s of 0.06, 0.06, 0.10,
and 0.40 for 100, 10, 1, and 0.1 solutions, respectively.
4. Conclusion
A new method for controlling the size of organosilica parti-
cles has been introduced and a coagulation model for their for-
mation has been proposed. Size control of particles with diam-
eters ranging from 50 nm to 3 µm was achieved by varying the
total monomer concentration. Confocal studies on dye-doped
particles showed that dye was uniformly distributed within the
149
interior of these particles enabled by solvent induced swelling
of the particles. The linear dye uptake with particle volume in-
dicates that different sized particles have comparable internal
structures, suggesting the formation process to be independent
of particle size. From these and other findings, we expect that
these organosilica particles will be useful for a wide range of
applications, such as biomolecular screening, colloidal encod-
ing or labelling.
Acknowledgments
We wish to acknowledge the support of OzNano2Life, which
is a project supported by the International Science Linkages
program (CG060027). This work was also supported by the
Australian Research Council (FF0455861) and the NHMRC
through an industry fellowship for B.J.B. (301267). We further
acknowledge Nanomics BioSystems Pty Ltd. and the Centre for
Microanalysis and Microscopy (CMM).
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