An All-in-One Molecule for the One-Step Synthesis of Functional Hybrid Silica Particles with Tunable Sizes

Article abstract of DOI:10.1002/ejic.201701181

Spherical particles with well-defined diameters were obtained by self-assembly of trityl-based molecules. Thanks to the robustness of the organic scaffold, a variety of modifications could be covalently introduced into the network so as to stabilize the s

Full text of DOI:10.1002/ejic.201701181

A Journal of
Accepted Article
Title: An all-in-one molecule for the one-step synthesis of functional
hybrid silica particles with tunable size
Authors: Julien Graffion, Dounia Dems, Mesut Demirelli, Thibaud
Coradin, Nicolas Delsuc, and Carole Aimé
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701181
Link to VoR: http://dx.doi.org/10.1002/ejic.201701181

10.1002/ejic.201701181
European Journal of Inorganic Chemistry
COMMUNICATION
An all-in-one molecule for the one-step synthesis of functional
hybrid silica particles with tunable size
Julien Graffion,[a,b] Dounia Dems,[a,b] Mesut Demirelli,[a,b] Thibaud Coradin,[a,b] Nicolas Delsuc,[c] and
Carole Aimé*[a,b]
Abstract: Spherical particles with well-defined diameters are
obtained by self-assembly of trityl-based molecules. Thanks to the
robustness of the organic scaffold, a variety of modifications can be
covalently introduced into the network so as to stabilize the
supramolecular structure by a sol-gel route. Using supramolecular
chemistry, we show that the synthesis of hybrid small molecules
allows engineering nanomaterials with tunable size and functionality.
The use of a combination of different characterization techniques
including dynamic light scattering, cryoTEM and solid-state NMR
materials.[11,12] As recently reviewed,[13] silsesquioxane NPs have
been synthesized from organotrialkoxysilane precursors by
different routes including hydrolytic[14-17] and non-hydrolytic[18] sol-
gel routes, and emulsion polymerization.[19-22] With such
processes, spherical,[14,15,23-25] hollow,[26-30] and Janus[31] NPs can
be obtained. Their surface can be easily functionalized through
silanization reactions of superficial silanol groups.[32,33] This offers
a large number of possibilities to bind targeting moieties for
imaging or drug delivery systems[34] or enhance cell compatibility
and internalization.[35,36]
provides
a careful understanding of the relationship between
molecular and supramolecular structures for further chemical
engineering of supramolecular hybrid materials.
Among polysilsesquioxanes, phenylsilsesquioxanes have
drawn much attention, and synthesis of PhSiO3/2 particles
reported.[16,37] In another study, Dirè et al synthesized NPs from a
series of alkyltriethoxysilane (methyl-, ethyl-, vinyl-, phenyl-, amyl-
and octyltriethoxysilane) with a systematic assessment of the
influence of the different organic groups on the synthesis and
properties of silsesquioxane NPs.[25] Such molecular design may
allow the doping of particles, either by physical entrapment or
covalent linking, with representative examples using fluorophores
such as Nile red,[38] rhodamine B,[17,24,39] or rhodamine 6G.[25] It is
worth mentioning that for the above-cited alkyltriethoxysilanes,
the formation of nanoparticles results from nucleation and growth
induced by sol-gel polymerization, typically following a two-steps
hydrolysis-condensation process as in the case of Dirè et al works.
On the other hand, the self-assembly of silsesquioxanes has been
reported for the design of helical or lamellar structures with
organogelator-like behavior.[40-42]
In this work, we exploit the supramolecular interaction
properties of the organic moiety of organotrialkoxysilanes as the
only molecular key towards nanoparticles. We use different
molecular designs based on triphenylmethane (trityl) group
(Figure 1) to take advantage of the trityl moiety to drive the
formation of well-defined objects. The addition of a trialkoxysilane
group (2 Figure 1) aims at allowing their stabilization through sol-
gel chemistry, preventing aggregation and Oswald ripening.
Finally, in order to investigate the scope of the tolerated
modifications that preserve the structure of the objects, we have
introduced a chiral multifunctional backbone that is a L cystein
amino acid. Its thiol group has been functionalized with the trityl
group as for 1 and 2 and the trialkoxysilane has been introduced
Anti-solvent precipitation is an attractive technique for the
elaboration of nanoparticles (NPs) finding applications in various
fields such as electro-optics, catalysis, and nanomedicine notably
with the elaboration of imaging agents and for improving drug
formulation. Alternatively, the design and synthesis of nanoscale
metal-organic frameworks have provided tunable nanoobjects to
serve as functional platforms.[1-6] However, despite the size
tunability of the resulting particles, their high interfacial area
renders them prone to aggregation and Oswald ripening that
affect their stability.[7] Research efforts have been devoted to the
selection of stabilizers to be added to the precipitating
nanoparticles.[8] To this aim, amphiphilic diblock copolymers have
been used, typically a hydrophilic poly(ethylene glycol) (PEG)
block chemically linked to a hydrophobic block.[9] Thanks to its
amphiphilic properties, the polymer adsorbs at the surface of the
NPs limiting further growth or dissolution, and preventing
aggregation. Polyelectrolytes such as polylysine, poly(ethylene
imine) or chitosan have also been used to electrostatically and
sterically stabilize the NPs and ensure narrow size distribution.[10]
Alternatively, hybrid (organic-inorganic) materials have been
intensively investigated for two decades due to their unique
properties that combine hardness and stability of the inorganic
phase with the flexibility and mild processing of polymer
[a]
Dr. J. Graffion, D. Dems, M. Demirelli, Dr. T. Coradin, Dr. C. Aimé
Sorbonne Universités, UPMC Univ Paris 06, Collège de France,
UMR CNRS 7574, Laboratoire de Chimie de la Matière Condensée
de Paris, Paris cedex 05, France.
E-mail: carole.aime@upmc.fr
[b]
[c]
Dr. J. Graffion, D. Dems, M. Demirelli, Dr. T. Coradin, Dr. C. Aimé
PSL Research University
Dr. N. Delsuc
Laboratoire des Biomolécules, Département de chimie, École
normale supérieure, PSL Research University, Sorbonne
Universités, UPMC Univ. Paris 06, CNRS, 24 rue Lhomond, 75005
Paris, France.
Figure 1. Molecular structures synthesized from an alkyl-S-trityl moiety (1),
combining a triethoxysilane group (2), and belonging to a cystein functionalized
with an anthracene (3).
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejic.201701181
European Journal of Inorganic Chemistry
COMMUNICATION
Figure 2. DLS of the supramolecular structures of 1, 2, and 3 as a function of
(a) water content (100 µM), and (b) concentration (90 % water). Inset cryoTEM
of 3 (200 µM, 90 % water).
Figure 3. (a) DLS of the supramolecular structures obtained from 1 and 3 with
(stabilized) or without (non-stabilized) ammonia vapors and (b) TEM images of
the stabilized spheres obtained from 2 and 3 respectively (90 % water, 100 µM).
via a DCC/NHS coupling with (3-aminopropyl)triethoxysilane
(APTES). A fluorescent anthracene moiety has been conjugated
to the amine function of the cystein. This provides cues for a
functional implementation of the resulting supramolecular
structures in an “all-in-one molecular structure” (3 Figure 1). The
three molecules have been synthesized as described in schemes
S1 and S2 and were obtained with a high purity (> 95 %, no
detectable impurities by 1H NMR).
of the previously described characteristics of the nanomaterials,
this process is very tolerant to a wide range of modifications.
The introduction of the alkoxysilane group may offer a way of
stabilizing the supramolecular particles of 2 and 3. Indeed, the
size of objects from 1 increases progressively up to 633 ± 40 nm
after one month (Figure 3a). In the case of precursors 2 and 3,
after the nanoparticles formation, a sol-gel route was used by
placing the samples under ammonia vapors for 24 h to catalyze
their hydrolysis-condensation under basic conditions. For
example, in the case of 3, after this treatment, the size of the
spheres levels at 127 ± 3 nm after 1 day, while in absence of
ammonia stable spherical structures could be obtained after 3
days exhibiting a size of 170 ± 7 nm. This shows (i) the role of the
alkoxysilane moiety in the stabilization of the final structures and
(ii) that ammonia is not mandatory for the stabilization of 3 but
speeds up the kinetics of the sol-gel process. TEM observations
after stabilization of 2 and 3 showed the preservation of the
spherical structures (Figure 3b). In terms of chemical structure,
the hydrolysis-condensation of the alkoxysilane and the formation
of the siloxane shell at the surface were ascertained using Zeta
potential measurements and 29Si solid state NMR. Stabilized
particles from 2 and 3 show negative zeta potentials indicative of
the presence of silanolate groups, resulting from the hydrolysis of
ethoxysilanes, on their surface (Table S2). Probing the silicon
chemical environment of 3 after stabilization by 29Si NMR
showed broad signals around -45.4, -57.1 and -66.8 ppm
attributed respectively to R-Si(OEt)3, R-Si(OSi)2(OH) (T2) and R-
Si(OSi)3 (T3), which confirm partial alkoxysilane condensation
(Figure S1). Further investigations by FTIR show that the Si-O
deformation region (900-1145 cm-1) does not change when
comparing 3 as molecular precursor and as stabilized particles
(Figure S2). In addition, no condensed siloxane bond (νas
(SiOSi)) could be identified due to their low concentration,
restricted to the surface. These results provide evidences that the
precursor remains intact within the nanoparticles due to the
hydrophobic character of the core that prevents water and
ammonia internal diffusion. Further investigations using powder
X-ray diffraction (PXRD) showed the presence of amorphous
silica, which could be expected given the huge number of
molecules involved in the formation of 100 nm diameter particles
(Figure S4).
Antisolvent precipitation in an ethanol/water mixture was used
to obtain supramolecular objects from 1. Precipitation could be
monitored by dynamic light scattering (DLS) in the range 60 to
95 % water leading to well-defined objects with sizes from 210 nm
to ca. 100 nm (Figure 2a). No supramolecular structure could be
detected below this range due to the solubility of 1 in ethanol,
while macroscopic objects sedimented above 95 % water. Very
interestingly, similar trends could be observed by precipitating 2
and 3, with a constant decrease in size from 60 to 80 % water
giving rise to well-defined objects with a mean hydrodynamic
diameter above 200 nm at 60 % (210 nm for 1, 260 nm for 3)
levelling around 90 nm from 80 to 95 % water. It is worth
mentioning that as the water content increases the size
distribution becomes narrower (Table S1). Playing with the
tritylated molecule concentration at a given water content is an
additional way of tuning the size of the resulting supramolecular
structures. At 90 % water, when increasing the alkoxysilane
concentration from 100 to 400 µM, the hydrodynamic diameter of
2 can be steadily varied from 95 to 125 nm, and from 80 to 100
nm for 3 (Figure 2b). CryoTEM observations show the formation
of well-defined spherical objects in solution (Figure 2B, inset).
Overall, the precipitation of 1 and the similar trends observed with
2 and 3 show that the strong hydrophobic character and the non-
planar structure (one sp3 carbon) of trityl favor pi-stacking
interactions over a short range, which makes it particularly
interesting for antisolvent precipitation to obtain well-defined
spherical objects. Trityl assembly being the driving force for the
formation of spherical particles, its scaffolding role is strong
enough to ensure particle formation upon addition of even large
organic molecules. Interestingly, neither the alkoxysilane, nor the
chiral centre and anthracene moiety seemed to play an important
role for obtaining well-defined nanostructures since 1, 2 and 3
behaved similarly. In presence of a chiral center, the preservation
of a chiral environment within hybrid particle could be ascertained
by circular dichroism spectropolarimetry (Figure S3). Because
this supramolecular chirality is expressed without modifying any
As a mean of implementing the particle with functionality, a
fluorescent probe, namely an anthracene, was introduced to the
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10.1002/ejic.201701181
European Journal of Inorganic Chemistry
COMMUNICATION
initial concentration, while the emission intensity of 3 remains
constant (Figure 4b). The ratio of the emission band area of rhod-
B over 3 rapidly increases with rhod-B concentration before it
starts to level off around 2 mM, which may indicate that saturation
is approaching (Figure S6). The saturation regime could not be
investigated further due to the destruction of hybrid particles at
higher rhod-B concentrations. Importantly, up to 2 mM rhod-B, the
integrity of the particles could be preserved (Figure S7). These
results show the robustness of the molecular design, where stable
spherical nanoparticles could still be obtained even after addition
of rhod-B.
Figure 4. Emission spectra of 3 (a) as a function of water content (100 µM, λexc
375 nm), and (b) after rhod-B addition at different concentrations ([3] 200 µM,
90 % water, λexc 378 nm).
In conclusion, spherical nanoparticles with well-defined
tunable diameters could be obtained in a single step by
antisolvent precipitation. Our “all-in-one molecule” is based on an
organic moiety, trityl, which is solely responsible for nanoparticles
formation. The addition of an alkoxysilane group allows the
stabilization of the hybrid particles by hydrolysis and
condensation, to freeze the final system and avoid further shape
and size evolution. We show that the propensity of the trityl group
to generate supramolecular spheres provides this molecular
design with a unique robustness that allows the covalent
introduction of large organic groups without changing the
structural properties of the particles. This opens the doors towards
a broad range of functional implementations as illustrated by the
covalent conjugation of fluorophores. In addition, such
nanoparticles allow the encapsulation of large molecules without
modifying their structure, which indeed opens up additional
opportunities. Finally, we have to keep in mind that the
functionality of those nanoparticles could even be broaden given
the versatility of silane chemistry for further functionalization of the
nanoparticles surface, in particular when envisioning applications
in biotechnologies and nanomedicine.
molecular design (3). The covalent conjugation of the anthracene
probe allows preventing the fluorophore leaching. Figure 4a
shows the emission spectra of 3 with increasing water content up
to 90 %. From 0 to 50 % water, the emission of the anthracene
(well-defined components, maximum intensity at 407 nm)
indicates that the anthracene moiety exists as a monomer in
solution. From 60 to 90 % water, the emission spectra drastically
broaden and red-shift (maximum intensity around 470 nm). These
changes are attributed to the transition from soluble 3 to its
precipitated state, in good agreement with DLS measurements
where no supramolecular structure could be detected below 60 %
water. As expected, the excitation spectrum was also slightly red-
shifted (7 nm) with increasing water content (Figure S5a).
Since 3 was shown to be an efficient multifunctional scaffold
to form hybrid nanoparticles with easily tunable diameters, we
investigated further the possibility to increase their functionality by
physical encapsulation. As a proof of concept, the encapsulation
ability of the hybrid particles was assessed by the addition of
rhodamine-B (rhod-B) during the precipitation of 3. Rhod-B was
chosen to get insights into the impact of adding sizeable
molecules on the stability and size of the hybrid particles. In
Experimental Section
addition, rhod-B was selected because it provides
a
Preparation of 1, 2 and 3 hybrid nanoparticles
straightforward read-out of the encapsulation, using Förster
Resonance Energy Transfer (FRET) with the anthracene moiety.
Different concentrations of rhod-B were added during the
precipitation of 3 (200 µM, 90 % water). After stabilization and
removal of non-encapsulated dye upon centrifugation, a pink
precipitate consisting of hybrid particles incorporating rhod-B
could be recovered and further redispersed in water (Figure 4b
inset). DLS measurements showed an increase in size from 90
nm to ca. 160 nm upon rhod-B encapsulation while no variation in
zeta potential could be detected, signing for dye encapsulation
Solutions of 1, 2 or 3 in ethanol were quickly added onto freshly deionized
water under vigorous stirring (always the same speed) at room
temperature for 30 seconds. For each precursor, water-ethanol ratio (from
0% to 95% water) and concentration (100, 200 and 400 µM), the final
volume was always kept at 1.5 mL for reproducibility reasons.
For non-stabilized systems, the suspension was left without further stirring.
For the stabilized, the suspension was placed in sealed environment for
24h in presence of ammonia vapours followed by 48h of ageing in the
newly basified suspension through ammonia transfer.
To recover the stabilized hybrid nanoparticles, centrifugations and cycle of
washing, with a mixture of ethanol-deionized water 1:1 first then with
deionized water (4 times), were used.
rather
than
surface
adsorption
(Table
S3,S4).
A
photoluminescence study was performed to provide additional
evidence of the encapsulation of rhod-B in stabilized hybrid
particles of 3. Emission spectra recorded at an excitation
wavelength in the anthracene region (378 nm) allowed the
detection of emissions of both the anthracene (centered at 460
nm) and rhod-B (at 580 nm) through FRET (Figure 4b). Excitation
spectra recorded at the maximum intensity of rhod-B emission
(λem 587 nm) also show the contribution of the anthracene moiety
in 3, which confirms the FRET phenomenon between rhod-B and
3, further evidencing the encapsulation of rhod-B (Figure S5b).
Noteworthy, the emission intensity of rhod-B increases with its
Preparation of 3 hybrid nanoparticles containing rhodamine-B
Solutions of 3 in ethanol were quickly added onto solutions of freshly
deionized water (90% water content in all cases) containing 0.2 (42 µM),
0.5 (104 µM), 1 (208 µM), 2 (417 µM), 5 (834 µM) or 10 mg (2080 µM) of
rhodamine-B. The conditions of stirring, temperatures, volumes,
stabilizations and washing were the same than for the preparation of 3
hybrid Nanoparticles (see above). Although in this case, the final
concentration of 3 was kept at 200 µM only.
Dynamic light scattering (DLS) and zeta potential measurements
Zeta potential and size distribution measurements were carried out using
a Malvern Zetasizer Nano ZS90 instrument. The autocorrelation functions
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10.1002/ejic.201701181
European Journal of Inorganic Chemistry
COMMUNICATION
were recorded at a scattering angle θ = 90o and analyzed by the non-
negatively constrained least squares technique (NNLS-Multiple Pass) for
the determination of particles diameter. All the suspensions were
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Spherical particles with well-defined
diameters are obtained by self-
assembly of trityl-based molecules.
Thanks to the robustness of the
Julien Graffion, Dounia Dems, Mesut
Demirelli, Thibaud Coradin, Nicolas
Delsuc, Carole Aimé*
Page No. – Page No.
organic scaffold,
a
variety of
modifications can be covalently
introduced into the network. Using
supramolecular chemistry, we show
that the synthesis of hybrid small
An all-in-one molecule for the one-
step synthesis of functional hybrid
silica particles with tunable size
molecules
allows
engineering
nanomaterials with tunable size and
functionality.
Layout 2:
COMMUNICATION
((Insert TOC Graphic here))
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Text for Table of Contents
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