SYNTHESIS OF CORE/SHELL FLUORESCENT SILICA NANOSPHERES

FOR GAS SENSING APPLICATIONS

Aleksandar SZCHENYI a, Barna KOVCS
a

University of Pcs, Faculty of Natural Sciences, Institute of Chemistry, Department of General and Physical
Chemistry, PCS, Hungary
kovacs1@gamma.ttk.pte.hu

The optical detection of gaseous CO 2 and NH3 is often based on a pH sensitive, colorimetric or
luminescent indicator. Usually different indicators are selected for the measurement of the two different
gases. In case of CO2, indicators having a pKa value greater than 7-8 are commonly used, while
molecules with a pKa lower than 6 are proper for sensing ammonia. Having a broad range pH indicator, it
is possible to construct sensors for the two gases by using the proper (and different) additives and
matrices for CO2 and NH3, respectively. The use of the same indicator in two sensors for the two gases
means, that we are working close to the two ends on the optical property vs. pH curve: reduced optical
signal change, and, hence, a reduced dynamic range should be paid for that. The benefit could be,
however, that the same optical design, filter setup, detector and electronics could be used for sensing.
In the present work the use of fluorescent, broad range pH sensitive nanospheres immobilized in different
matrices for indirect sensing of gaseous CO 2 and NH3 are investigated and tested. Dual lifetime
referencing (DLR) method has been used to overcome fluorescence intensity measurement
interferences. It is a method to reference fluorescence intensities via fluorescence decay times. This
method use a long fluorescence lifetime reference with a fluorescence decay time in s or ms range and
a sensing dye with short fluorescence decay time. Ruthenium(II) tris(diphenylphenanthroline) (Ru(dpp)3)
complex has been used as a reference fluorophore. N-allyl-4-piperazinyl-1,8-naphthalimide (APN) have
been used as sensing dye. The fluorescence enhancement of the APN in the presence of hydrogen ions
is based on the photon-induced electron transfer mechanism (PET).
The core of the sensing nanospheres was prepared by modified Stber method. The appropriate amount
of Ru(dpp)3 an tetraethoxysilane (TEOS) was dissolved in ethanol, after the addition of deionized water,
the mixture was stirred for 2 h and sonicated for 30 minutes. After sonication the reaction vessel was
placed on the magnetic stirrer and the stirring speed vas adjusted to 1200 rpm. The calculated amount of
the NH4OH catalyst was injected rapidly in to the reactant solution and the stirring speed was reduced to
600 rpm. The reaction was proceeded for 24 h. The nanospheres were centrifuged and washed with
ethanol and deionized water. The residual white powder was dried in the oven at 80 C for 3 h. Dried
powder was placed in to the sealed glass capillary and flushed with Argon. The capillary was placed in the
oven at 200 C over night. The reference nano beds were re-suspended in ethanol and kept in
refrigerator until further use. Mixture for the synthesis of the shell was prepared in two steps. For
preventing the leaching of pH sensing dye, APN was covalently bond the to sol-gel precursor
vinyltriethoxysilane (VTES) by irradiating their mixture (molar ratio 1:3) with UV lamp (366nm) for 30
minutes. Core nanobeads were diluted in ethanol, water and APN/VTES were added, sonicated for 5
minutes and stirred for 1 hour. The shell was formed by adding the calculated amount of the NH4OH and
stirred for one hour at room temperature. The silica spheres was separated by centrifugation and washed
with ethanol to remove the unreacted components. The resulted particles were dispersed and stored in
the ethanol until use.
Phase shift measurements were performed with dual-phase lock-in amplifier (DSP830, Stanford
Research inc.) in a home made flow through cell. Optical system consisted of a blue led (430 nm) a band
pass filter, bifurcated fiber bundle, and Hamamatsu (H5783-01) PMT with long pass filter (510 nm).
For CO2 sensing the pH sensitive nanoparticles were co-immobilized in D4 hydrogel with
tetraoctylammoniumhidroxide (TOA). The pH in the sensing membrane is depending on the pCO 2 which
is indicated by the increasing fluorescence. The influence of the nanospheres: quaternary ammonium
hydroxide ratio was tested.
For the sensing of gaseous NH3 the APN containing nanospheres were protonated and co-immobilized
with different polymer soluble protonic acids (acetic acid, dodecylbenzene sulfonic acid) in different
matrices. The ammonia concentration is related to the negative response of the fluorescence. The effect
of the acidic additive, its concentration, the influence of the matrices on the sensitivity, and performance of
the sensors were tested and compared.

Acknowledgment: Developing competitiveness of Universities in the South Transdanubian Region (SROP-4.2.1.B10/2/KONV-2010-0002).