Materials Chemistry and Physics 126 (2011) 909917

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Materials Chemistry and Physics
j our nal homepage: www. el sevi er . com/ l ocat e/ mat chemphys
Effect of functional groups on condensation and properties of solgel silica
nanoparticles prepared by direct synthesis from organoalkoxysilanes
Sandra Dir

, Valeria Tagliazucca, Emanuela Callone, Alberto Quaranta

Dipartimento di Ingegneria dei Materiali e Tecnologie Industriali, Universit di Trento, via Mesiano 77, 38123 Trento, Italy
a r t i c l e i n f o
Article history:
Received 4 August 2010
Received in revised form 25 October 2010
Accepted 3 December 2010
Keywords:
Nanostructures
NMR
Surface properties
Photoluminescence spectroscopy
a b s t r a c t
Silsesquioxane nanoparticles were synthesized from organotrialkoxysilanes in ethanol/water medium
by a two-step hydrolysiscondensation process. Regular shaped spheres functionalized by vinyl, methyl,
ethyl, phenyl, amyl, octyl, 3-aminopropyl groups were obtained, with sizes in the range 100400nm. The
integrity of the organic functional groups and the condensation degree of the silsesquioxane networks
were detectedby multinuclear solidstate Nuclear Magnetic Resonance (NMR). The nanoparticles thermal
behavior was studied by thermogravimetric analyses, and N
2
sorption was used to measure the particles
porosity. Coatings were obtained from particles suspensions by spin coating technique and the surface
properties were studied by contact angle measurements. The emission of Rhodamine 6Gdoped nanopar-
ticles was analyzed in the visible light region. The uorescence experiments highlight the inuence of
the different matrices on amount of dye retained into the network and uorescence intensity.
2010 Elsevier B.V. All rights reserved.
1. Introduction
Silica particles nd applications in different elds ranging
from chemistry to materials science and biology [15]. Exploit-
ing the solgel process, silica particles are generally synthesized
through the well-known Stber method (SFB) developed by
Stber, Fink and Bohn in the late 1960s, which allows the synthesis
of spherical particles by hydrolysiscondensation of tetraethoxysi-
lane (TEOS) under basic conditions [6]. Silica particles are used
for the preparation of photonic devices, thermal insulators, sen-
sors, catalysts, adsorbents, pigments, detergents, pharmaceuticals,
cosmetics, medical diagnostics, immuno-assays. One of the most
popular applications is the use as llers in the preparation of
polymer-based nanocomposites [79]. Unfortunately, the main
disadvantage of incorporating SiO
2
into polymer-based matrices,
particularly in the case of polyolens, stays in particle aggregation
owing to the low chemical afnity between ller and matrix. The
agglomeration process or phase separation leads to poor mechan-
ical, optical and electrical properties of the resulting polymer
nanocomposites, and the aggregation bent increases as the par-
ticles size decreases [10]. Thus, the modication of the particles
surface is required for improving the chemical compatibility for
several applications [1116]: besides the preparation of polymer
nanocomposites, the ability of changing the acid/base properties
for sensors andcatalysts, thetuningof thehydrophilic/hydrophobic

Corresponding author. Tel.: +39 0461 282456; fax: +39 0461 281945.
E-mail address: sandra.dire@ing.unitn.it (S. Dir).
features in microuidics and chromatography, and for the prepa-
ration of emulsions in cosmetics and drugs production, represent
suited examples.
In order to achieve a uniform dispersion of silica-based parti-
cles in the matrix, a commonly used method is the treatment of
inorganic particles surface through silanization, by reaction with
organosilanes under stirring or reuxing in appropriate solvents
[1720], in vapor phase or using anhydrous supercritical methods
[2123]. An alternative route is the preparation of hybrid particles
by adapting the Stber synthesis, starting from tetraalkoxysilanes
and organic modied silicon alkoxides [2427].
Our approach is addressed to the solgel synthesis of
organic/inorganic (O/I) hybrid materials starting fromtrifunctional
organosilanes, RSi(OR

)
3
, without the aid of tetrafunctional silicon
alkoxides. This procedure can be exploited to enhance the surface
functionalization however, in order to control the solgel process
and the spheres growth, great attention must be devoted to the
choice of the R group linked to silicon. As a matter of fact, by steric
and inductive effects the R group exerts a strong inuence on the
silane solgel reactivity, on the crosslinking degree of the obtained
silsesquioxane network, on tendency to aggregation and acidbase
behavior of particles [13,28].
According to this synthesis procedure, we were able to pro-
duce hybrid nanoparticles with a wide variety of organic functional
groups. The syntheses were performed using triethoxysilanes
RSi(OEt)
3
with R=CH
3
, methyl (MTES), C
2
H
5
, ethyl (ETES),
C
5
H
11
, C
6
H
5
, phenyl (PhTES), and CH=CH
2
, vinyl (VTES),
through acidbase two steps hydrolysiscondensation process in
hydro-alcoholic medium. The synthesis parameters were changed
0254-0584/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.12.015
910 S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917
ETES
OTES
ATES
1
PhTES
2
VTES
MTES
1
2
3
4
5
6
7
8
1
2
3
4
5
1'
2'
RTES
1v
2v
3
APTES
Si
Si
Si
Si
Si C H
3
Si N H
2
Si
EtO
EtO
EtO
OEt
EtO
EtO
OEt
EtO
EtO
OEt
EtO
EtO
OEt
EtO
RSi-O
EtO
OEt
EtO
EtO
OEt
EtO
OEt
Fig. 1. Chemical structures of the silane precursors and labels of carbon atoms of
the samples analyzed by
13
C MAS NMR.
in order to study the ability of spheres preparation and the inu-
ence on particles size and size distribution. Following the same
approach, binary systems were prepared by co-condensation of
MTES and VTES with a second triethoxysilane bearing a long
aliphatic chain, R=C
5
H
11
, amyl (ATES) and C
8
H
17
, octyl (OTES)
or the aminopropyl functional group ((CH
2
)
3
NH
2
, APTES).
The effects of the functional groups on the condensation and
microstructure of the particles were investigated by means of solid
state NMR, N
2
sorption and SEM measurements, the surface prop-
erties were inspected by contact angle measurements and the
thermal stability by DTATGAthermal analyses. Moreover, the par-
ticle capability to retain uorescent dyes was studied by dispersing
Rhodamine 6G (R6G) in the different matrixes.
The doping of solgel materials has been widely investigated,
and the ability of hybrid silica networks of incorporating organic
molecules has been established since many years [2931]. The
organic molecules entrapped into solgel materials are isolated
in individual cages and this fact preserves from easy leaching and
increases the dye photostability. Moreover, the possibility of tuning
the acidbase behavior in hybrid networks allows increasing the
dyes concentration ensuring good dispersion and optical response
[3234]. In recent years, the incorporation of organic dyes in sil-
ica nanoparticles has found much interest in the eld of cosmetics
[35,36], and biochemical applications such as biosensing, bioana-
lytical assays and imaging [3739].
R6G was added to the silane/ethanol solution and absorption
and uorescence spectra were recorded on the dye-doped particles
in order to investigate the effect of the different hybrid matrices on
the optical properties.
2. Experimental methods
2.1. Reagents
Methyltriethoxysilane (MTES), ethyltriethoxysilane (ETES),
vinyltriethoxysilane (VTES), phenyltriethoxysilane (PhTES),
amyltriethoxysilane (ATES), octyltrietoxysilane (OTES), 3-
aminopropyltriethoxysilane (APTES), were purchased from
ABCR and SigmaAldrich. The organosilanes chemical structures
are shown in Fig. 1. Rhodamine 6-G, ethanol, hydrochloric acid
(37%) and ammonia (30%), were purchased from SigmaAldrich
and Fluka and used without any further purication.
2.2. Particles synthesis
Reactions were carried out in air at room temperature. The
organotriethoxysilane, RTES, was dissolved in ethanol and reacted
under stirring with the appropriate amount of HCl for 4h (Step I).
In the second hydrolysiscondensation step (Step II), an ammo-
Table 1
Synthesis conditions of particles prepared from MTES.
Sample label EtOH
a
HCl
a
NH
3
a
M1 20 20 180
M2 100 20 180
M4 20 40 180
a
Molar ratio (reagent/Si).
nia solution (2.3M) was added to the sol and the mixture was
kept stirring for 20h. A white suspension was obtained and cen-
trifuged at 5000rpm for 15min to separate the silica particles.
The solid sample was collected and dried at 50

C for 24h. Sample

labels andsynthesis conditions of particles preparedfromMTES are
reported in Table 1. The same procedure was used for the synthe-
sis of particles prepared with two different organotrialkoxysilanes
(Table 2), employing the synthesis conditions reported for sample
M1 (Table 1). Doping of silica particles was obtained by adding R6G
(10
4
mol mol
1
of silicon) to the pristine ethanol solution of silane
precursors.
2.3. Coatings
Coatings were prepared by spin coating of particles suspensions
on clean soda-lime sheets. The suspensions were prepared adding
particles to a mixture of ethylene glycol, ethanol and acetone. The
coatings were dried in air for 24h at 50

C and used for the contact

angle measurements.
2.4. Characterization techniques
29
Si and
13
C NMR spectra were recorded with a Bruker 400 WB
spectrometer with carrier frequency of 400.13MHz (
1
H) equipped
with a double band probe. Samples were packed in 4mm zirconia
rotors and spun at 6kHz.
29
Si SP spectra were obtained with pulse
length 4.3s, delay 5s; CPMAS ct 5ms, ct pulse 3s, decoupling
pulse 5.3s. Q
8
M
8
was used as external secondary reference (12.6
and 108ppm). Si units are labeled according to the usual NMR
notation: T
n
represents a trifunctional SiCO3 unit and n is the num-
ber of oxo-bridges.
13
C proton decoupling spectra were acquired
with 90

pulse length, 3.36s, decoupling pulse length 4.90s,

delay 7.5s. Adamantane was used a external secondary reference
(38.56 and 29.6ppm). The labeling of organosilanes carbon atoms
in the analyzed samples is shown in Fig. 1.
Scanning electron microscopy (SEM) was run using a JEOL
JSM-5500 instrument, operating at 10kV. The morphology charac-
terization was also conducted on a FE-SEM Supra 40 Zeiss in high
vacuum modality. The particles size distribution has been evalu-
ated using the software ImageJ [40].
Table 2
Compositions and average sizes of particles prepared fromsingle precursor and two
organosilanes.
Sample label R
I
TES/R
II
TES R
II
mol% Average size (nm)
M1 MTES 170 39
E ETES 466106
V VTES 201 37
Ph PhTES - 255 62
MA10 MTES/ATES 10 423 88
MA25 MTES/ATES 25 380 78
MA50 MTES/ATES 50 175 87
MA75 MTES/ATES 75 149 60
MO10 MTES/OTES 10 158 111
MO25 MTES/OTES 25 213 113
VO10 VTES/OTES 10 91 29
VO25 VTES/OTES 25 60 28
MAp01 MTES/APTES 1 290 42
S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917 911
Fig. 2. Inuence of synthesis conditions: from left to right, SEM micrographs of M1, M2 and M4 samples.
Specic surface area and porosity measurements were obtained
by N
2
sorption using a Micromeritics ASAP 2010.
Thermal analyses (TG-DTA) were performed on a Netzsch
STA 409 instrument; the samples were heated in owing air
(100cc min
1
) from 20

to 1000

C with a heating rate of

10

Cmin
1
.
Contact anglemeasurements wereperformedusingwater drops
(3ml) and measuring both sessile (static) and equilibrium angle
(after drop vibration for 15s at 20Hz).
For optical measurements, 5mg of particles doped with R6G
were mixed with 95mg of KBr and pressed in forms of pellets.
In this way, every sample was composed with the same amount
of doped powder, in order to compare the absorption and u-
orescence spectra. Diffuse reectance measurements were made
with an Ocean Optics reectance probe R600-7, constituted by
one input and six output silica bers. The pellets were irradiated
with an Avantes 2000HD optical source, and the reected spec-
trum was analyzed with a USB4000 Ocean Optics spectrometer.
The reference was taken, for each spectrum, froma WS-1-SL Ocean
Optics diffuse reectance standard. Then, the reectance spectra
were converted following the KubelkaMunk relationship, since
the resulting amplitude reproduces the shape of the absorption
spectragivingvalues proportional totheconcentrationof dispersed
dye molecules. Excitation and emission uorescence spectra were
collected with a Jasco FP-6300 spectrouorimeter, with 5nm of
bandwidth, and were corrected for the spectral response of the
system.
3. Results
3.1. Synthesis conditions and morphology study by electron
microscopy
The research of the most favorable synthesis conditions for the
preparation of small spherical particles has been performed using
MTES precursor and changing solvent and acid amounts. The SEM
study (Fig. 2) reveals that suitable conditions are those employed
for M1synthesis (Table 1): particles are characterizedbyanaverage
size of 17039nm. A higher alcohol ratio (M2) leads to a marked
Oswald ripening effect: a coral-like structure of fused spheres is
observable instead of separate spheres. On the other hand, a lower
EtOH/MTES ratio leads to the increase in particle size as in the
case of a higher molar concentration of ammonia. The increase of
the acid catalyst amount produces large particles with broad size
distribution (0.61.6m), for instance M4 presents particles with
average diameter of about 1m.
For these reasons, the synthesis conditions of M1 particles have
been adopted for the preparation of samples from one and two
organosilanes (Table 2). Spherical particles are in general obtained
for all compositions (Fig. 3) but size, size distribution and propen-
sity to aggregation of particles strongly depend on the nature of
precursors. Particles prepared from a single organosilane present
anincreaseinaverageparticles diameter intheorder M1<V<Ph<E
(Table 2) and the size distribution becomes very large particularly
for E sample.
The addition of 1mol% APTES (MAp01, Table 2) leads to almost
doubling the average size and size range broadens. Adding a higher
loadof APTES produces further increase inparticle size, aggregation
between particles and generation of raspberry-like spheres. Parti-
cles prepared from MTES and ATES show a net increase in average
size for MA10 andthe following decrease of particles diameter with
increasing the ATES load. MA samples present a relevant broaden-
ing of particles size distribution with a slight increase of average
size for MO25. On the contrary, the addition of OTES to VTES leads
to a strong decrease in particle sizes.
3.2. Solid state NMR
The degree of condensation of the silsesquioxane networks is
obtained fromsilicon NMR. Table 3 reports chemical shifts, assign-
ments, percentages of every species and the calculated degree of
condensation (DOC) according to the following equation:
DOC =
T
1
+2T
2
+3T
3
3(T
0
+T
1
+T
2
+T
3
)
100 (1)
Table 3
29
Si NMR chemical shifts, percentage of Si units and calculated degree of condensation of selected particles.
Sample label T
1
(ppm) T
2
(ppm) T
3
(ppm) T
1
(%) T
2
(%) T
3
(%) DOC (%)
M1 55.5 65.0 29.2 70.8 90.3
MAp01 55.7 65.1 20.2 79.8 93.3
E 46.2 55.3 65.0 1.8 39.7 58.5 85.6
V 70.5 79.7 17.6 82.4 94.1
Ph 68.8 76.9 25 75 91.7
MA10 55.6 65.1 29.2 70.8 90.3
MA75 56.7 66.9 28.1 71.9 90.6
MO10 56.7 .65.2 27.8 72.2 90.7
MO25 55.7 65.4 28.3 71.7 90.6
VO10 70.8 (V)
56.9 (O)
80.2 (V)
66.5 (O)
15.0 (V)
16.5 (O)
85.0 (V)
83.5 (O)
95.0 (V)
94.5 (O)
VO25 70.9 (V)
56.9 (O)
80.4 (V)
65.9 (O)
12.0 (V)
12.6 (O)
88.0 (V)
87.4 (O)
96.0 (V)
95.8 (O)
912 S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917
Fig. 3. FE-SEM images of selected particles (Table 2).
S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917 913
Fig. 4.
29
Si CP MAS spectra of M1 and E particles.
All samples are characterized by a network made of T
2
and T
3
units, as it can be seen in the spectrum of M1 particles reported
in Fig. 4. The only exception is presented by ETES-derived sample
(Fig. 4E) that shows also a small amount of T
1
units and the low-
est condensation degree (Table 3). All the other samples show an
amount of T
3
units between 70 and 80%. Vinyl-modied particles
(V) present the highest condensation degree, and a DOC increase is
found for MAp01 particles prepared with the addition of 1% APTES
to MTES.
The particles prepared adding a second organosilane to MTES
appear as a homogenous family (Table 3), showing similar chemical
shift and DOC. Unfortunately, this means that it is possible only to
calculate the overall condensation degree but not the contribution
of the Si units derived from methyl and C
5
or C
8
alkyl-modied
organosilanes.
Ontheother hand, theuseof VTESinsteadof MTESfor theprepa-
ration of octyl-modied particles leads to different chemical shifts
of Si units (Fig. 5), and the assignment and the evaluation of the
condensation degree is possible via peak deconvolution. Relative
amounts and chemical shifts of VOsamples are reported in Table 3.
Fig. 5.
29
Si CP MAS NMR spectra of VO10 and VO25 particles (v: vinyl; o: octyl).
The degree of condensation increases with increasing the amount
of OTES and is slightly higher for VTES derived units.
13
C NMR experiments have been run in order to check the
hydrolysis degree of the samples. The main results obtained from
13
C SP MAS NMR spectra are reported in Table 4: carbon number-
ing follows Fig. 1 and the assignments have been compared with
literature data [4145]. The ethoxy group produces two signals at
18.5 (CH
3
) and 58.7ppm(CH
2
) that are detectable in a percent-
age lower than 2.5% in most of the MTES-based samples, with the
exception of MAp01, which is fully hydrolyzed. The signicant dif-
ference in the extent of hydrolysiscondensation with respect to
M1 sample derives from the addition of 1mol% APTES, which acts
as a promoter of the hydrolysiscondensation process.
13
C NMR spectra recorded on Ph and V samples allow check-
ing the stability of the organic functions linked to silicon. This is
assessed for the phenyl group in Ph sample; the V spectrum(Fig. 6)
shows a peak at 22.81ppm, which was possible to detect only by
largely increasing the scans number. This peak represents 0.1% of
the main species and, in absence of a corresponding methyl group,
can be attributed to a methylene carbon, suggesting a negligible
Table 4
Experimental ratio between precursors calculated from
13
C SP MAS spectra, chemical shifts and related carbon species of selected particles (according to Fig. 1).
MAp01 MA75 MA10 MO25 MO10 V Ph
Exp. ratio
99.4:0.6
Exp. ratio
17:83
Exp. ratio
88:12
Exp. ratio
74:26
Exp. ratio
83:17
CH
3
2.8 CH
3
2.8 CH
3
2.8 CH
3
2.8 CH
3
2.8
1 11.1 12.3 12.3 1.6
13.8 13.8 13.1 13.1
1. 5 14.5 1. 5 14.5 1. 8 14.7 1.8 14.7
2

18.8 2

18.8 2

18.4 2

18.4 2

18.6 2

18.9
2 26.7 2. 4 23.2 2. 4 23.2 7. 2 23.6 7. 2 23.6 22.8
3 45.1 31.2 5. 4 30.2 5. 4 30.2 1

59.0 1

58.6
33.0 6 32.9 6 32.9 1v 131.1 Ortho 128
3 36.1 3 36.1 3 37.0 3 37.0 2v 136.7 Para 130.7
1

58.7 1

58.8 1

58.7 1

58.5 Meta 134.3

914 S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917
Table 5
TG characteristic data, specic surface area (SSA) and total pore volume (TPV) from N
2
sorption analyses.
Sample label Total weight loss (%) T
Onset
(

C) SSA
a
(m
2
g
1
) TPV
b
(cm
3
g
1
)
M1 13.5 220 47 0.063
V 28.3 279 22 0.044
E 30.0 212 8 0.032
Ph 78.8 400 20 0.106
MA10 22.9 209 25 0.055
MA25 25.7 231 27 0.057
MA50 33.7 212 30 0.307
MA75 43.3 202 2 0.003
MO10 56.0 212 55 0.129
MO25 22.5 218 36 0.072
VO10 32.3 212 45 0.486
VO25 34.7 258 65 0.760
a
BET equation.
b
Calculated at P/P

=0.95.
polymerization of the vinyl group. In the case of binary VO sam-
ples, all the carbon peaks of the two silanes are present (Fig. 6) and
the vinyl function is kept unmodied in the samples.
Calculating the integral values of selectedpeaks, the experimen-
tal composition of particles prepared from two organosilanes has
been evaluated. The CH
3
group of MTES at 2.8ppm and the 2,7
or 2,4 CH
2
of OTES and ATES, whose area accounts for 2 car-
bons, have been considered for MO and MA samples. The results
are reported in Table 4. For VO samples (Fig. 6), the CH at and
CH
2
signals of VTES, respectively at 131.4 and 136.5ppm and
the 2.7 CH
2
of or OTES, have been considered. The experimental
composition of VO10 is 86:14, the calculated ratio of VO25 is 64:36.
3.3. Thermal behavior and N
2
sorption analyses
The particles thermal behavior has been studied by DTATGA
in air up to 1000

C, and the results are summarized in Table 5.

For particles prepared from a single organosilane, the total
weight loss increases from methyl- to phenyl-modied parti-
cles, and the thermal stability decreases following the trend:
phenyl >vinyl >methyl >ethyl.
According to T
onset
values, the addition of the second organosi-
lane with amyl (ATES) or octyl (OTES) chains leads to the decrease
in thermal stability and the increase in total weight loss.
Particles prepared from a single organosilane and two silane
precursors have been characterized by nitrogen sorption analysis.
Generally, the samples present lowporosity with type II isotherms,
and E behaves as a non-porous solid. From M1 to Ph i.e. with
increasing the complexity of the organic group linked to silicon,
the average pore diameters increase and this trend is related to
Fig. 6.
13
C CPMAS spectra of Vand VO25 particles (* methylene peaks; ssb: spinning
sidebands).
the decrease in SSA and the increase in TPV (Table 5). The addition
of ATES to MTES does not produce a signicant change in SSA but
affects the TPV, which increases as a consequence of the forma-
tion of large pores. OTES addition generates a different inuence
on MTES and VTES based particles; 10% OTES leads to the increase
in SSA and TPV, whereas a higher OTES load in MO25 reduces both
values and in VO25 further increases surface and pore volume.
3.4. Contact angle measurements
The surface properties of particles have been evaluated by con-
tact angle measurements using water, oncoatings preparedby spin
coating of particles suspensions. Thick and almost homogeneous
layers were obtained, in agreement with the SEM observations.
Both sessile and equilibrium angles were measured (Table 6). All
samples present high sessile contact angle; however, after drop
vibration, only Ph and MA75 still show high values of the equi-
librium angle. It is noteworthy the behavior of MA75 lm, which
exhibits a roll over effect i.e. the drop tends to slip on the surface
when it is poured on the lm.
3.5. Optical measurements
Optical measurements, performed one year later the synthesis
of the particles, do not show any difference in the absorption and
uorescence features, indicating the stable dye entrapment in all
the particles. To conrm the stability of the embedding, a water
leaching test with ultrasound application was also performed and
no traces of released R6G or siloxane oligomers were found in the
liquid after the treatment.
Fig. 7 shows the absorbance spectra of the pellets obtained from
the samples M1, V, E, Ph, MO25, MA25, and MA75, and Table 7
reports the height andthe wavelengths of the corresponding peaks.
The spectra collected on bare KBr pellets, under the same experi-
mental conditions, were featureless, within the sensitivity of the
technique.
Table 6
Sessile and equilibrium angles of coatings prepared by spin coating of particles
suspensions.
Sample Sessile angle (

)
a
Equilibrium angle (

)
a
M1 120 4 81 6
E 134 2 91 4
V 116 4 62 7
Ph 141 4 129 4
MA25 108 4 68 6
MA75 146 4 146 4
MO25 114 1 71 9
a
Measured with water.
S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917 915
Table 7
Amplitude and position of the absorption peaks, intensity of the emission peaks, position of excitation and emission peaks for all the examined samples.
Sample I
abs
(km)
abs
(nm) I
500
/I
abs
a
IF (a. u.)
b
ex (nm)
c
em (nm)
c
M1 0.0705 523 0.532 394 530 559
V 0.0349 525 0.409 311 532 558
E 0.0245 525 0.483 150 533 554
Ph 0.0182 528 0.525 117 537 561
MO25 0.0318 524 0.465 162 530 550
MA25 0.0345 528 0.521 113 534 553
MA75 0.0012 527 0.454 9.4 533 547
a
Ratio of absorbance values at 500nm and at the maximum wavelength.
b
ex =480nm.
c
em =580nm.
The amount of R6G retained by the different networks is pro-
portional to I
ass
, while the ratio between the absorbance value at
500nmand I
ass
gives an indication on the formation of dimers [46].
The higher amount of R6G is present in M1, while V, MA25 and
MO25 present similar absorbance values, about one half of M1.
In E and Ph an even lower amount of dye is present and, nally,
MA75 exhibits a very low absorbance value, indicating a very low
capability to retain R6G.
As far as the uorescence spectra are concerned, the peak posi-
tions do not depend on the excitation or emission wavelengths,
thus indicating both a quite homogeneous distribution of the dye
environments and the absence of uorescent dimers [33]. The posi-
tion of the emission peaks can be related to the polarity and to
the specic interactions of the environment [47,48]. In Fig. 8, the
emission spectra of the different samples obtained by exciting the
pellets at 480nm are reported. The emission yields and the peak
positions are reported in Table 7. As it can be observed, the ratios
of the uorescence intensities from the different samples do not
follow the absorbance amplitude probably due to the presence of
dimers giving rise to concentrationquenching effects. The presence
of non-uorescent H-dimers can be also inferred by the difference
between the peak position of absorption and excitation spectra.
In M1 particles, the R6G concentration is higher, as evidenced
by both the absorption and emission spectra. Moreover, the higher
relative absorbance, at 500nm, with respect to the other samples,
indicates the formation of non-uorescent dimers. In V, R6G is
dispersed at lower concentrations with respect to M1, in fact the
Fig. 7. Absorbance spectra of R6G doped samples in KBr pellets.
Fig. 8. Emission spectra of RG6 doped samples in KBr pellets (ex =480nm).
absorption band is about one half. On the other hand, the lumi-
nescence yield ratio is higher, indicating a higher uorescence
efciency for R6G in V with respect to MTES. In fact, the rela-
tive absorption of V at 500nm is lower due to the presence of a
lower amount of dimers. The amount of dispersed dye, and the
corresponding uorescence intensity, decreases in E and in Ph. In
particular, in Ph the low concentration is accompanied by a small
red shift of both absorption/excitation and emission spectra and by
the formation of dimers.
The insertion of OTES or ATES in the MTES network gives rise to
a decrease of the R6G concentration, as observed from the absorp-
tion spectra. In particular, MO25 and MA25 have nearly the same
amount of dye. The uorescence intensity inMA25is slightly lower,
probably due to a higher trend to the formation of dimers, as
observed by the relative absorbance at 500nm, giving rise to con-
centrationquenchingeffects. Afurther increaseof ATES, as inMA75,
dramatically reduces both absorbance and uorescence features.
4. Discussion
The two step hydrolysiscondensation process employed for
organosilsesquioxane particles synthesis is suitable for the pro-
duction of sub-micrometer regular spheres in most cases. The
advantage of using a rst acidic step stays in the possibility to
enhance the nucleation process and reduces the increase of parti-
cle sizes. Indeed, particles prepared fromMTES using base catalysis
in one-step hydrolysiscondensation process presented a narrow
size distribution but with diameters higher than one micrometer.
916 S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917
However, the nature of the organic group linked to silicon in
trifunctional alkoxides stronglyaffects nucleationandgrowthsteps
in solution. Indeed, changing from CH
3
(M1) to C
2
H
5
(E) leads
to doubling the particles average diameter whereas the CH CH
2
group (V) produces a small increase in sizes respect to M1 particles
(Table 2).
The addition of 1mol% APTES generates the growth of higher
diameter particles, probably by the catalytic promotion of the con-
densation reaction ascribable to the amino-group, as observed for
the calculated value of DOC (Table 3).
For binary systems, the particle size distribution tends to
broaden as the long-chain organosilane is added to MTES (Fig. 3,
Table 2). The increase of particle sizes is noteworthy for MA10,
whereas adding higher loads of ATES to MTES produces an oppo-
site trend with the decrease in particles dimensions. Taking into
account the polarity of the aqueous-alcoholic medium of the reac-
tion, this trend could be the result of the balance between the
inductive effects of the alkyl chains on the solgel reactions and
the increase of lipophilicity of the particles surface, which can pre-
vent the reactants diffusioninsolutiontowards the particle surface.
The increased presence of C
5
alkyl chains could act as a barrier for
condensation of polar monomers and oligomers dissolved in the
solution with the inhibition of particles growth. This interpretation
is supported by the almost constant degree of condensation calcu-
lated from silicon NMR spectra (Table 3). The inuence of OTES is
different. In the case of MTES-derived particles, the broadening of
particle size is remarkable and the average particles size slightly
increases with 25% OTES addition, whereas an inverse trend is
found for addition to VTES. VO10 and VO25 present particle dimen-
sions lower than V, with the formation of a large amount of very
small particles and a strong tendency to aggregation. The octyl
chains seem very efcient in hampering the particles growth by
polarity and steric hindrance effects, particularly with vinyl-based
system. Moreover, VO10 and VO25 samples deserve further com-
ments concerning the high DOC of silsesquioxane networks. From
Table 3, V appears the most condensed network, probably as a con-
sequence of the very small steric hindrance of the vinyl group and
the better availability of the silicon atom to nucleophilic substi-
tution (SN) reactions, due to the withdrawing effect of sp
2
carbons
that enhances the condensationrate. Probably, the additionof OTES
leads to the stabilization of reaction intermediates, inducing the
overall polymerization process.
The thermal evolution in air is sensitive to the nature of the
organic function linked to silicon. The highest thermal stability is
detected for networks modied by the unsaturated groups and
particularly for Ph particles, which present a signicant onset
temperature (Table 5). Loading with long alkyl chains leads to
increasing the total weight loss without seriously affecting the
onset temperature for MTES-derived particles. Again, different is
the behavior of VTES-derived particles. A relevant decrease of the
onset temperature is foundfor 10%OTES addition, as a consequence
of the lower stability of long alkyl chains (Table 5). The differ-
ent effect of OTES addition to methyl and vinyl-derived particles
also concerns the porosity features. The presence of amyl and octyl
chains generally affects the textural properties of particle surface
producing an increase in TPV, which is related to the increase of
pore diameters with small inuence on SSA values (Table 5). How-
ever, the TPV increase is noteworthy for VO10 and VO25, and a
remarkable SSA increase respect to pure vinyl-modied particles is
also found, as the consequence of micropores presence. This sug-
gests that, during particle formation and drying, the organic chains
lookfor afavorablesteric organizationas afunctionof their amount.
The presence on the surface of octyl chains in VTES-based systems
prevents the particles growth in solution and hinders the surface
shrinkage. Onthe other hand, MTES-derivednetworks are probably
more compliant and this fact leads to small changes in SSA values.
The addition of C
5
chains progressively increases the TPV with-
out affecting SSA values, in agreement with the constant degree
of condensation of the silsesquioxane networks. However, when
the amount of ATES reaches 75%, the supercial coverage is com-
pleteandN
2
cannot access thesurface. Thus, MA75surfacepresents
also the most hydrophobic behavior as reported in Table 6. More-
over, the full surface coverage does not allowthe water drop to nd
preferential polar sites after drop vibration and consequently the
equilibrium angle value resembles that of the sessile angle. This is
also the case of Ph particles, which present on the surface the cum-
bersome phenyl rings. On the contrary, the other samples show
equilibrium angles lower than the respective static angles, sug-
gesting the presence of inhomogeneous surfaces or coating defects.
The local heterogeneity could be the reason also for the creation of
stacking defects during lm formation by particles self-assembly,
and consequently allow the water drop to accommodate on the
surface after vibration.
The features of the silsesquioxane networks strongly inuence
the amount of Rhodamine 6G retained in the hybrid networks and
the emission ability of the dye.
The highest amount of R6Gis retained by M1 network, as a con-
sequence of the valuable condensation degree associated to the
formation of small size pores, as shown by the values of specic
surface area and total pore volume (Table 5), with the contribution
of the small steric hindrance of the methyl groups that improve the
placing of dye molecules inside the network cavities.
Indeed, the ability to embedding high dye amounts is related to
the degree of condensation. V sample presents a DOC value higher
than M1, leading to a more rigid inorganic structure. This makes
more difcult for the dye to settle in the cavities of the network,
reducing the number of entrapped molecules. At the same time,
the uorescence intensity is the highest in V sample because the
network cavities are not able to host more than one molecule and
prevent the formationof dimers, withbenecial effect for the emis-
sion ability. In spite of the low SSA due to few large size pores, E
presents a low DOC value with a positive effect on the dyes reten-
tion.
In the case of Ph, the presence of very large pores, together
with small size pores that can be detected from the pore size dis-
tribution calculated by the BJH method, allows during particles
formationthe leaching of dye molecules, reducing the total amount
of retained dye. The entrapment of the dye can also be hampered
by the cumbersome organic functions, like phenyl rings and long
alkyl chains, with detrimental effect on the emission yield because
of the increased amount of non-uorescent H-dimers. In fact, sam-
ples MO25 and MA25 exhibit a lower retention capability with
respect to M1 and the uorescence yield of sample MA25 is lower
with respect to the absorbance, due to concentration quenching
effects. This nding can be explained by an inhomogeneous distri-
bution of dye molecules into the network, as evidenced also by a
high relative absorbance at 500nm, which indicates the presence
of non-uorescent dimers. The decrease of the absorbance ampli-
tude by increasing the ATES concentration in the particles appears
almost linear. This result can be reasonably explained by the devel-
opment into the hybrid network of two different kinds of cages
for the dye molecules: the former characterized mainly by methyl
groups and the latter by a more relevant presence of long chains,
hindering the accommodation of the dye. Increasing the amount of
ATES, like in sample MA75, gives rise to a lower amount of cavities
rich in methyl groups capable to retain the dye.
5. Conclusions
Hybrid silica nanoparticles have been prepared by
hydrolysiscondensation of organotriethoxysilanes, with a wide
S. Dir et al. / Materials Chemistry and Physics 126 (2011) 909917 917
range of organic functions and without tetraalkoxysilane addition.
The degree of condensation of the silsesquioxane networks is high
even when precursors bearing long alkyl chains have been used.
The chemical features of the organic groups are preserved in the
particles and affect the assembling ability and the surface prop-
erties of coatings prepared from particles suspension. Particles
modied by phenyl (Ph) and methyl/amyl groups in 25/75 ratio
(MA75) show very high equilibrium contact angles. The different
behavior of the networks and the sterical demand of the organic
functions inuence the ability of embedding Rhodamine 6G. The
highest amount of dye is retained in methyl-modied particles
but the vinyl-modied network minimizes dimers formation and
leads to the highest yield in R6G emission.
Acknowledgements
The nancial support of MIUR(PRIN2007) is gratefullyacknowl-
edged. The authors acknowledge Dr. C. Della Volpe for the contact
angle measurements and BIOtech(University of Trento) for FE-SEM
analyses.
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