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

injection nozzles [10], and ultrasonic oscillation [11]. How-
Optically-encoded silica particles can be utilised in bioan- ever, these methods result in a high degree of polydispersity
alytical applications such as screening of biomolecules [1], in size distribution. In comparison, Barbe et al. produced spher-
intracellular sensing [2], colloidal encoding [3,4], or signal ical silica particles with narrow size distribution over an exten-
amplification [5–7]. The usefulness of silica-based materials sive size range of 10 nm–50 µm, combining sol–gel synthesis
stems from the variety of surface modification and immobilisa- with surfactant-stabilised water-in-oil emulsion polymerisation
tion procedures available for the coupling of biomolecules [6]. chemistry [12].
Key criteria that particles should satisfy in order to be suitable Thiol- and amine-based organosilanes can be incorporated
for these applications are monodispersity, control over parti- into the silica network by a seeded growth technique [13,14],
cle size, uniform surface loading and uniform distribution of to allow for the covalent attachment of thiol- and amine-
internal encoding elements such as organic dyes or quantum reactive organic dyes and the conjugation of biomolecules. We
dots. recently developed an alternative surfactant-free two-step ap-
Stöber et al. achieved the controlled growth of monodis- proach to synthesise thiol-functionalised organosilica micropar-
ticles, based on acid-catalysed hydrolysis and condensation
perse nonporous silica particles with diameters ranging from
followed by base-catalysed condensation [1,15]. By carefully
20 nm up to approximately 2 µm [8]. This technique utilised
controlling the base-catalysis, these organosilica microparticles
silicon alkoxide precursors dissolved in short chain alcohols in
proved to be monodisperse with mean particle diameters rang-
the presence of ammonia. Other approaches to synthesising sil-
ing from 2 to 5 µm.
Recent approaches in diagnostic bead-based assays have
* Corresponding author. required the implementation of optical encoding strategies,
E-mail address: r.vogel1@uq.edu.au (R. Vogel). whereby the uniform incorporation of encoding elements into
0021-9797/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.01.092
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150 145

nano- and microparticles is of major importance [7,16]. Tra- 2. Materials and methods
ditional silica microsphere production has utilised the well-
known Stöber synthesis method, as mentioned above. How- 2.1. Materials
ever, the structure of the internal network of these silica par-
ticles does not allow the access of large organic molecules 3-Mercaptopropyltrimethoxysilane (MPTMS, 95%) was ob-
such as fluorescent dyes [8,17]. In order to internalise en- tained from Lancaster and used as supplied. Triethylamine
coding elements such as fluorescent dyes, several possibil- (TEA, 99%), hydrochloric acid (37%), dimethylformamide
ities are available. These include the generation of poros- (DMF), and rhodamine B isothiocyanate (RBITC) were ob-
ity within the silica network using surfactant template strate- tained from Sigma–Aldrich and used as received. Commercial
gies [18–21], template-free strategies [1] and the incorporation silica particles with a diameter of 5.17 µm (standard deviation
of encoding elements during synthesis of the silica material unspecified) were purchased from Bangs labs.
[13,22–24].
Incorporation of encoding dyes into common polymeric 2.1.1. Synthesis
particles is easily achieved by controlled swelling in suitable Organosilicate particles were produced using a two step
solvents. While Stöber silica does possess branched, micro- process. The initial acid catalysis step is described in detail by
porous internal structure, incorporation of dyes is negligi- Miller et al. [15]. The resulting emulsion was centrifuged and
ble as any swelling is of a very small scale [25]. In com- the supernatant was separated from the oil. The supernatant
parison, some organically-modified silicate (ORMOSIL) bulk phase was then diluted with pH 3.5 water, to obtain various
materials possess enough structural flexibility to allow sol- concentrations (0.1, 1, 5, 10, 50, and 100%) of the supernatant
vation, resulting in material swelling not unlike a polymer phase. These supernatant solutions are referred to as “0.1%, . . . ,
gel [26]. Research by Rao et al. investigated the swelling 100% solutions.” Finally in the base-catalysed step, 70–100 µl
properties of ORMOSIL gels in aqueous solutions and their of TEA was rapidly added to 100 ml of the supernatant–water
applications for microdevices [27,28]. These bulk materials mixtures under continuous stirring.
were touted as environmental sensors and shown to swell Approximately 30 min after the addition of TEA, the formed
in response to changes of pH, temperature, and an applied particles were separated from solution by centrifugation and
field. However, these ORMOSIL gels were not adopted for then washed in ethanol. This procedure was applied for samples
particle synthesis. In comparison, Goller et al. investigated with supernatant concentrations >3%. Due to a slower particle
the swelling of organosilica microparticles in the nonpo- formation process at lower concentrations the samples with su-
lar solvent n-heptane [29]. These microparticles were pre- pernatant concentrations of 0.1 and 1% were left under basic
pared using a combination of bi- and trifunctional silanes conditions for 24 h before being centrifuged and washed.
and resulted in relatively small particles with diameters below
1.5 µm. Overall, the organic components of these ORMOSIL 2.1.2. Dye incorporation
materials have consisted primarily of alkyl chains. In con- For investigations into dye localisation, the organosilica par-
trast to these materials, Walcarius et al. produced mercapto- ticles were covalently labeled with rhodamine B isothiocyanate
functionalised organosilica particles using the co-condensation (RBITC) in DMF. Once dye incorporation was complete, bead
of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxy- pellets were washed from DMF into ethanol for confocal mi-
silane (MPTMS) [30–32]. The resulting particles were highly croscopy analysis.
functionalised and successfully removed large amounts of mer-
cury from aqueous solutions. However, the high polydispersity 2.2. Methods
of these particles renders them unsuitable for most bioanalytical
applications. 2.2.1. Electron microscopy
It is evident from the research to date that there has not been Scanning electron microscopy (SEM) images of platinum
a successful synthetic route developed which brings together coated samples were collected on a JEOL JSM 6400F, us-
all four desirable elements required in a particle designed for ing an accelerating voltage of 5–10 kV. Images were analysed
biomolecular synthesis and screening namely: monodispersity, with Image-Pro software to determine size distributions, using
selective functionality, controlled size and robust dye incorpo- a minimum of 200 particles.
ration. Transmission electron microscopy (TEM) studies on organo-
In this report we describe a method which achieves all of silica particles were carried out on a JEOL 2010 microscope at
these objectives. The modified synthetic route demonstrates an operating voltage of 200 kV.
the size control of novel organosilica micro- and nanoparticles
and an aggregation based model for the formation of emulsion 2.2.2. Optical transmission microscopy
droplets which condense to form solid particles is proposed. The swelling of organosilica and silica microparticles (Bangs
Control of particle size (50 nm–3 µm) is achieved by varying Labs) in different solvents (water, ethanol, DMF) was inves-
the total monomer concentration. In addition, dye molecules are tigated by suspending dried microparticles in approximately
shown to be covalently bound throughout the interior of both 1 ml of solution and left for at least 48 h. A Nikon Eclipse
organosilica nano- and microparticles, enabled by solvent as- TE2000-E with a Photometrics CoolSnap HQ camera attach-
sisted swelling of the organosilica matrix. 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- monomer, dimer and trimer species [15]. The concentration of
termined by measuring over 200 particles. these species is referred to as “total monomer” concentration
(Ctotal = Cmonomer + 2Cdimer + 3Ctrimer ). The calculation of the
2.2.3. Confocal microscopy “total monomer concentration” in 0.1, 1, 5, 10, 50, and 100%
Confocal images were taken with a Zeiss 510 Meta confocal solutions (Fig. 2d) is based on a volumetric approximation.
microscope. Each support was imaged at 100× magnification Knowing the initial volume of added MPTMS precursor and
using 543 nm excitation and automatic brightness/contrast cal- measuring the volume of the separated oil (consisting of hy-
ibration. drolysed organosilane species) after centrifugation, the residual
Fluorescence intensity measurements were carried out on a amount of MPTMS in the supernatant has been estimated. Size
custom confocal microscope. Samples were illuminated with control of organosilica particles was achieved by varying the
a 532 nm diode pumped solid state laser and imaged with a total monomer concentration.
100 × free space objective with a nominal numerical aperture of In Fig. 2, TEM (a) and SEM (b and c) images of particles
0.8. Images were formed by raster scanning the stage (Physik with diameters ranging from approximately 150 nm up to 3 µm
Instrumente P-517.2CL) and photon flux was measured with are shown. The various populations of organosilica particles
an avalanche photo diode (Perkin–Elmer SPCM-AQR-14FC). (using 1, 10, and 100% solutions) all possess very narrow size
The microscope’s point spread function (spot size) was altered distributions with coefficients of variance (CV) 0.1, validat-
by decreasing the numerical aperture of the illumination and ing monodispersity.
increasing the pinhole size, in order to make it significantly Fig. 2d displays the size dependence of the organosilica
larger than the bead diameter. Also note that in general the axial spheres on the total monomer concentration (MPTMS concen-
spot size is larger than lateral spot size for a standard confocal tration). The condensation rate will be proportional to the con-
microscope [33]. For these reasons we could compare the fluo- centration of hydrolysed monomer, dimer, and trimer species.
rescence emission from each entire bead by simply comparing However, each of these species will contribute to the rate dif-
the peak intensities of the images created by raster scanning the ferently, dependent upon diffusion rate and number of free hy-
stage. droxyl groups [34]. As shown in Fig. 2d a higher concentration
of hydrolysed species will result in larger particle sizes.
3. Results and discussion The internal structures of these particles were investigated
to elucidate the accessibility of the organosilica network for or-
Monodisperse organosilica particles were produced via a ganic molecules. Fig. 3 shows a typical high-resolution bright-
two step process: acid catalysed hydrolysis and condensa- field TEM image of an organosilica particle. Particles with
tion of 3-mercaptopropyltrimethoxysilane (MPTMS), followed diameters ranging from 50–200 nm were imaged. No obvi-
by base catalysed condensation (see the experimental section ous internal structures, indicating mesoporosity were observed.
and Fig. 1). Acid catalysed condensation leads to the forma- These results are supported by N2 adsorption/desorption analy-
tion of emulsion droplets consisting of insoluble organosil- sis, resulting in Brunauer–Emmett–Teller (BET) surface areas
ica oligomers [1,15]. The supernatant, separated by centrifu- which correlate well with the geometric surface areas of solid
gation and used as a precursor solution for base catalysed particles (1–2 m2 /g). The low surface area is likely to be a
condensation, was diluted to obtain various concentrations result of shrinkage upon drying. Similar results of low BET
(0.1, 1, 5, 10, 50, and 100%). These supernatant solutions surface areas have been observed for analogous organosilica
are referred to as “0.1, . . . , 100% solutions.” The supernatant nanoparticles [30–32]. The organosilica particles appear to be
phase predominantly consists of fully hydrolysed organosilica comprised of an amorphous organosilica network with no dis-
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150 147

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
Fig. 2. TEM (a) and SEM (b and c) images of monodisperse organosilica nano- particles have comparable internal structures suggesting the for-
and microspheres. Particle size dependence on total monomer concentration is mation process is independent of particle size.
displayed in (d).
Based on the BET and TEM studies mentioned above, dye
is expected to bind preferentially onto the particle surface. This
tinguishing features. Diffuse ring electron diffraction patterns apparent contradiction to the results obtained by confocal mi-
(not displayed) support the existence of an amorphous structure. croscopy can be explained by significant swelling of the parti-
Confocal microscopy was used to confirm the ability of the cles in certain solvents, which is commonly seen in resin par-
functionalised particles to bind thiol-reactive dye molecules. ticles and is absent in Stöber particles. Hydrogel and resin ma-
Fig. 4 shows thin slices (<0.5 µm) through representative mi- terials display different volume increases depending upon the
croparticles of (a) 10, (b) 50, and (c) 100% solutions after be- 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. 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
Fig. 4. Confocal microscope images of particles synthesised using different model for the particle formation process, as illustrated in Fig. 6.
silica precursor concentrations: [(a) 10, (b) 50, and (c) 100%] and dyed with As mentioned earlier, after completion of acid-catalysed
RBITC. A plot of fluorescence intensity versus particle diameter measured with hydrolysis and condensation, the supernatant solution predom-
a confocal microscope is displayed in (d).
inantly consists of fully hydrolysed organosilica monomer,
dimer, and trimer species (Fig. 6a). The addition of base
was applied to investigate the effect of various relevant solvents (triethylamine, TEA) initiates the rapid crosslinking of these
(e.g., water, ethanol, and dimethylformamide (DMF)) on the di- fully hydrolysed organosilica species to form larger branched
ameter and volume of organosilica microparticles. Fig. 5 shows oligomer assemblies. This rapid condensation triggers self-
the volume increase of microparticles in several solvents, used emulsification by inducing a change in hydrophobicity of the
for synthesis (water), storage (ethanol), and dyeing procedure organosilica species, which become insoluble in water and
(DMF). The microparticles were observed to swell by up to thus form an emulsion. We suggest that the emulsion droplets
∼2.5 times the dry volume in DMF. This swelling will cause the (Fig. 6c) form by a coagulation process of precipitated oligomer
organosilica network porosity to increase, allowing the incorpo- assemblies, which act as nuclei (Fig. 6b). This coagulation
ration of large molecules such as organic dyes which covalently process is controlled by the charge of the oligomer assem-
bind to the thiol functionalities of the organosilica. As shown blies which rapidly coalesce to form emulsion droplets with
in previous work, these organosilica particles retain their fluo- amounting charge, finally leading to the formation of a sta-
rescence when objected to various reagents involved in a mul- bilised emulsion. Further growth of the droplets is suggested
tistep phosphoramidite oligonucleotide synthesis, whilst com- to be controlled and directed by Ostwald ripening [38] and
mercially available encoded polystyrene–divinylbenzene parti- monomer addition.
cles are unstable in most synthesis steps and lose most of their As shown in previous studies, the condensation inside the
fluorescence [36]. These findings suggest that dye is covalently emulsion droplets continues and finally yields solid organosil-
 R. Vogel et al. / Journal of Colloid and Interface Science 310 (2007) 144–150 149

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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