Study on influence of size and surface properties of silica nanobeads in performance of optical sensors

Aleksandar Szchenyi b , Barbara Horvth a, Sndor Kunsgi-Mt a,b, Barna Kovcs a,b
a

Department of General and Physical Chemistry, University of Pcs, H-7624 Pcs, Ifjsg 6, Hungary b Jnos Szentgothai Research Center, H-7624 Pcs, Ifjsg 20, Hungary
Experimental: The synthesis of NPs were performed in closed 8 ml vials, thermostated at 25 C and stirred with 8 mm magnetic bar with 600 RPM. The beads, with in the experiment series, has been synthesized simultaneously for better comparison. The composition of the reactants were calculated from data obtained form the original Stber method, and predicted to obtain silica NPs in size rang 10-100 nm. The molar compositions of the initial coctails are shown in Table 1. The ratio of alkoxi silanes and ammonia were kept constant (at a ratio 1:1), while their concentration were varied from 0,020,23 M; the water amount was kept constant and was use in the large access compared to the alkoxi silanes. The components, with exception of ammonia solution, were mixed in the glass vial and sonicated for 20 minutes. After addition of ammonia catalyst solution the reaction was left to proceed for 24 hours. After the reaction was completed the temperature was elevated to 80 C and the wails were opened to let the ammonia to evaporate from the solution. The influence of functionalized alkoxi silanes were examined regarding its molar content and its chemical properties. In series of experiments the molar ratio of TEOS to modified alkoxi silanes have been kept constant (98:2) while their total concentrations have been varied, in an other set of experiments the total concentration of alkoxi silanes have been fixed and their molar ratio (table 2) have been changed. In other experiments we kept the concentration and the ratio of alkoxi silanes constant and vary the chemical properties of the functional group. The synthesized NPs were functionalized with fluorescein isothiocyanate (FITC, CFITC=1 *10-6mol/dm3), at pH=10. The suspension was centrifuged (5-30 nm 15000 rpm 30 minutes, 30-300 nm 5000 rpm 30 minutes) washed three times with 5 ml of acetone, and redispersed in 5 cm3 EtOH. The size measurements were performed with MALVERN NanoS DLS instrument, SEM images were taken with JEOL JSM-6300 scanning electron microscope. The fluorescence measurements were made with AVANTES EDU spectrophotometer, by exciting the samples with LED (470 nm) through a 450 broad range IF filter, long pass filter with cut off wavelength of 510 nmwas placed in front of detector.
CTEOS =0,12M APTES content 2 n/n %

Introduction:Silica nanoparticles (NPs) are widely used in many applications; as substrate for label indicators, they could serve as chemical nanosensors, in drug delivery. They are biocompatible, easily functionalizable and they provide stable matrix for the applications. In this work we present our results on the synthesis of modified surface silica NPs used for optical chemical sensors. NPs have been synthesized by modified Stber method [1].

CTEOS
(mol/dm3) TEOS

Molar Ratios
NH4OH EtOH H2O pH

CTEOS=0,006M, r= 9nm
size [nm]

0,2294 0,1198 0,0612 0,0248 0,0125 0,0025

1 1 1 1 1 1

1 1 1 1 1 1

181,3 354,8 725,2 1813 3626 18130

7,2 14 28,7 71,8 143,6 717,8

11,32
n/n % MeTES EtTES

PrTE S

VTES

PhTES

nOctTES

APTES

11,18 2 11,04 10,84 10,69 10,34 4 6 8 20 22 22 23 23 22 24 27 24 111 23 20 162 18 22 20

Table 1. Molar compositions of the initial coctails

Table 2. Molar compositions of the initial coctails

300

Size of the nanoparticles vs APTES content

Particle size[nm]
250 200

250 200 150 100 50 0 0,00

Size of the nanoparticles vs TEOS concentration

Particle size[nm]

150 100 50 0 0,00

C silanol=0,23 M C silanol=0,12 M

0,50

1,00

1,50

2,00

0,05

0,10

0,15

0,20

0,25

APTES content [n/n %]

CTEOS [mol/dm3]

Fig. 1. Influence of APTES content

CTEOS=0,12 M, APTES content 2 n/n%, r=194 nm

Fig. 2. Influence of TEOS concentration

CTEOS=0,12 M, APTES content 2 n/n%, r=194 nm

Fluorescence intnsity [cps]

6000

6000 5000 4000 3000 2000 1000 0 2,5 3,5 4,5 5,5 6,5 7,5 8,5 9,5

Fluorescence intnsity [cps]

5000 4000 3000 2000 1000 0 450

500

550

600

650

Wavelenght [nm]

pH

Fig. 3.Fluorescence spectra of FITC functionalized NPs

Fig 4. calibration of FITC functionalized NPs

CTEOS =0,06M APTES content 2 n/n %

Results: The size of the NP1s samples determined with DLS is in good agreement with those obtained by SEM (Fig. 5.). All the NPs heve a spherical shape, and a narrow size distribution (typically +/- 5% of the given size).even. The functionalized alkoxi silanes resulted in increasing NPs size (Fig. 2.); in a case of APTES the largest increase was obtained (Fig. 1.). NPs functionalized with FITC showed bright luminescence, and response to pH changes (Fig 3. and Fig. 4.). No dye leaching was observed.

Fig. 5. SEM images of silica nano particles

Conclusion: We have presented a simple way to obtain silica nanospheres with tailored size and surface properties. With decreasing TEOS concentration the particle size is decreasing have, until it reaches its theoretical lower limit (3 nm). Further decrease of TEOS concentration results increasing size of the resulted NPs (Fig. 2.). Significant increment in size of nano spheres was with APTES, most probably due to the auto catalytic properties of the amino group. pH sensitive nanospheres have been prepared with covalently bonded pH sensitive dye. The size of the NPs does not effect the pKa of the surface bounded indicator. It was founded that in the pH 3-5 range the luminescence intensity increased with increasing hidrofobicity oh the NPs surface. The cross sensitivity to ionic strength of the pH sensitive NPs to be examined in the future.
Acknowledgement: Financial supports of TT_10-1-2011-0126,
[1] Stber, W.; Fink, A.; Bohn E. J. Colloid Interface Sci. 1968, 26, 62-69. SROP-4.2.1.B-10/2/KONV-2010-0002 and SROP-4.2.2.A-11/1/KONV-2012-0065 projects are gratefully acknowledged