A halogen anion sensor based on the hydrophobic entrapment of a fluorescent probe in silica sol-gel thin films

doi:10.1016/S0022-3093(97)00256-1

Journal of Non-Crystalline Solids

Volume 220, Issues 2–3, 1 November 1997, Pages 316-322

https://doi.org/10.1016/S0022-3093(97)00256-1 Get rights and content

Abstract

A halogen anion (Cl⁻, Br⁻, I⁻) sensor has been designed, based on the entrapment of a fluorescent molecule in a sol-gel silica film deposited on a glass substrate. A key factor is the use of the newly synthesized hydrophobic fluorophore, N-dodecyl-6-methoxyquinolinium, so as to avoid the problem of leaching. This probe allows detection and measurement of chloride concentrations in the physiological range (100 mM) coupled with a response time less than 1 s. The fluorescence quenching data are fitted to a model which assumes two quenching sites.

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The large-area and color-tunable fluorescent (FL) films have great potential applications in light-emitting devices and color displays. Yet, the challenge of realizing truly color-tunable emissions using a single fluorophore remains. Herein, we present a large-area, transparent and ultra-stable free-standing FL silica-based film (FSFSF) with color-tunable emissions prepared by using an amphiphilic aggregation-induced emission (AIE) luminogen (AIEgen) as both a structure-directing agent and a light-emitting source. The color-tunable FSFSFs have been facilely prepared at the gas–liquid (GL-FSFSF) and solid–liquid interfaces (SL-FSFSF) by simply stacking the AIEgen/SiO₂ composite layers with different self-assembled structures using an approach combining self-assembly with sol-gel process. These films exhibited variable excitation-dependent emission colors, emitting bright blue and green fluorescences as well as dark red fluorescence from one single visual field under excitation with UV, blue, and green lights, respectively. The research found that the resulting GL-FSFSF had a sandwich-like structure with an alternate arrangement of cylindrical and spherical AIEgen micelles in the silica matrix, and exhibited unusual excitation-dependent multi-wavelength and morphology-dependent dual-center emission characteristics. It has been reported that the luminescence of many AIE compounds is morphology-dependent. Therefore, we speculate that the two emission centers of the film are related to the two self-assembled morphologies of amphiphilic AIEgen. Its bright blue and green fluorescence is attributed to the same emission intensity of the two luminescent centers. This study has demonstrated that morphology- and excitation-dependent color-tunable emissions based on one AIE fluorophore can be achieved by incorporating AIEgen aggregates with different self-assembled morphologies in the matrix. Such a simple strategy can be extended to construct other multicolor-tunable FL hybrid materials.
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Citation Excerpt :
The properties of the support for the dye have a strong influence on the performance of the sensor. Hydrogel membranes [7], plasticized polymer membranes [8], glass slides [9] and sol–gel materials [10] have been reported as sensing probe supports or as host matrices for embedding sensing species. Among them, hybrid sol–gel systems present several advantages with respect to other supports from both the chemical and the synthetic point of view: low processing temperatures, chemical inertness, high photochemical and thermal stability, optical transparency down to the UV, cheap apparatus for sensor preparation [11–15].
A halogen-anion fluorescent solid-state sensor based on natively porous films doped with a quinolinium derivative is reported. The sensitive films are prepared with a low temperature sol–gel synthesis starting from bridged silsesquioxane precursors, and 6-methoxyquinolinium moieties are covalently linked to the organic–inorganic hybrid network. This sensor system is reversible and allows selective detection and measurement of halogen anion concentrations in the physiological range by a dynamic quenching effect of the sensitive fluorophore. The quenching constants are unaffected by dye inclusion in the bridged polysilsesquioxane matrix.
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These wide applications based on various areas produce a requirement for increased selectivity and sensitivity to detect the halogen anion. Several methods including laser-induced breakdown spectroscopy [10], ion chromatography [11] and fluorescence technology [12,13] have been used for the determination of halogen anion. The drawbacks of these methods are that they are expensive, time consuming, require large sample volumes as well as large amount of organic solvent with separation and extraction procedures, and must be undertaken by an analytical chemist in a dedicated analytical laboratory.
A novel method for sensitive determination of chloride anion at multilayer nano-silver modified indium-tin oxide (ITO) electrode has been developed. The multilayer films were fabricated via self-assembly/electrochemical-assembly methods, in which the 3-aminopropyltriethoxysilane (APTS) was used to modify ITO conducting glass, layer-by-layer (LBL) method was applied to prepare the multilayer films and poly (diallyldimethylammonium chloride) (PDDA) was employed as a bridging ligand. The resulting electrode (Ag/{PDDA/Ag}_m/APTS/ITO) surface was characterized with SEM and UV–vis. The electrochemical behavior of Cl⁻ at the Ag/{PDDA/Ag}_m/APTS/ITO electrode was studied by cyclic voltammetry. The results indicated that the modified electrode exhibited substantial enhancement in electrochemical sensitivity for Cl⁻ due to its large surface area and particular absorbability. The Ag/{PDDA/Ag}_m/APTS/ITO electrode detected Cl⁻ by voltammetry based on the oxidation of Ag/Cl⁻ that generated from a specific reaction of chloride ions with nano-silver. After accumulation of 3 min for Cl⁻ at Ag/{PDDA/Ag}_m/APTS/ITO electrode, the peak height (Ag/Cl⁻) increased linearly with the concentrations of Cl⁻ in the range of 1.0 × 10⁻⁸–1.0 × 10⁻⁶ mol L⁻¹. The detection limit was 5.2 × 10⁻⁹ mol L⁻¹ at 3σ level. This modified electrode could be successfully applied in water samples with low cost and high sensitivity.
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Natively porous hybrid organic–inorganic sol–gel systems have been engineered to be used as functional positive photoresists, aimed to the realization of microsensors in a single-step process.
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The photoprocessable porous films have been synthesized starting from a Bridged Polysilsesquioxane (BPS) precursor, 1,4-bis(triethoxysilyl)benzene. The correlation between chemical properties of the sol–gel material and its patternability is described in detail. X-ray exposure leads to a progressive alkyl and aromatic compound elimination and promotes inorganic condensation in the system, allowing the selective dissolution of irradiated cross-linked films in suitable etchants. Patterns of final resolution lower than 100 nm have been realized on BPS-based films synthesized in acid conditions, a procedure that allows to take advantage of a straightforward embedding protocol for active species in the sol–gel matrix. The BPS-based system has been doped with a covalently linked quinolinium dye, obtaining thin sensing films patternable by X-ray lithography. A feasibility test for the fabrication of optical microdevices, where fluorescence properties are obtained directly on the patterned coatings, has been provided.
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The sol–gel technology is being increasingly used for the development of optical sensors and biosensors, due to its simplicity and versatility. By this process, porous thin films incorporating different chemical and biochemical sensing agents are easily obtained at room temperature, allowing final structures with mechanical and thermal stability as well as good optical characteristics. In this article, an overview of the state-of-the-art of sol–gel thin films-based optical sensors is presented. Applications reviewed include sensors for determination of pH, gases, ionic species and solvents, as well as biosensors.
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A halogen anion sensor based on the hydrophobic entrapment of a fluorescent probe in silica sol-gel thin films

Abstract

J. Non-Cryst. Solids

J. Non-Cryst. Solids

Tetrahedron Lett.

Tetrahedron Lett.

Anal. Biochem.

Anal. Biochem.

Mater. Lett.

J. Non-Cryst. Solids

J. Molec. Struct.

J. Non-Cryst. Solids

Sol-Gel Glasses, Supramolecular Architecture: Synthetic Control in Thin Films and Solids

Sol-Gel Sciences — The Physics and Chemistry of Sol-Gel Processing

Acc. Chem. Res.