Fibre optic chemical sensors based on evanescent wave interactions in sol-gel-derived porous coatings

A simple, low-cost technique for fabricating reagent-mediated fibre-optic chemical sensors (optrodes) is described and the performance of a range of such sensors is reported. The technique is based on coating an unclad portion of an optical fibre with a microporous glass film prepared by the sol-gel process. Although tip- and side-coating are both possible with this technique, the latter, which employs evanescent wave interactions, offers particular advantages in terms of sensor performance, control of sensitivity and quality of coating. The sol-gel-derived film is used to provide a robust support matrix in which analyte-sensitive dyes are entrapped and into which smaller analyte molecules may diffuse. The benefits of this sol-gel approach to sensor fabrication are illustrated by results from a range of sensors for pH, ammonia and oxygen based on both evanescent wave absorption and evanescent wave excitation of fluorescence.     

LED-compatible fluorosensor for measurement of near-neutral pH values

We report on an optical sensor material suitable for fluorimetric measurement of pH in the 6–9 range using a new, fully LED-compatible fluorescent dye. Its base form has a strong absorption between 580 and 630 nm that matches the emission band of conventional yellow or orange light-emitting diodes. Two kinds of dye immobilization are reported. The first is based on covalent binding to a cellulosic matrix and the resulting material is intended for use in sensing membranes. The second involves physical entrapment of the dye in a sol-gel matrix which can be used for optical fiber tip coating as well as in evanescent wave type sensors. Both kinds of sensor materials are studied with respect to dynamic pH ranges, response times, sensitivity toward ion strength, and stability.Dedicated to Professor G. Werner, Leipzig, on the occasion of his 60th birthday.     

A Chemical Recognition Element for Lithium Ions Based on Optical Electronic Absorption

Xerogel samples with entrapped series of four optical absorption chemosensors were prepared by sol-gel process. These materials are proposed as chemical recognition elements of an optical chemical sensor. The roles of the chemosensors play proton-dissociable chromogenic azocrown ethers bearing phenol and two azo groups as parts of macrocycles. Occurrence of the alkali ion—receptor interaction is signalled by the chemosensors changing their electronic absorption spectra. By this way chemosensor 4O-CH₃ is able to distinguish Li⁺ ions from other alkali metal ions present in aqueous solution, if the chemosensor is entrapped in Glymo-silica (1:1) xerogel matrix. The proposed recognition element for Li⁺ has been exposed to the cycles chemisorption—desorption many times. Besides DRIFT spectra of the used xerogel matrices were analyzed.     

Optical sensors and biosensors based on sol-gel films

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.     

光导纤维光谱法——Ⅴ.光导纤维化学传感器

本文介绍了光导纤维化学传感器的基本原理,传光型和传感型化学传感器的各种探头设计和构型,以及它们在无机和有机分析方面的应用。涉及参考文献105篇。     

Characteristics of dye-impregnated tetraethylorthosilane (TEOS) derived sol-gel coatings

An investigation has been carried out on a cross-comparison study into several sol-gel coatings, impregnated with a pH-sensitive fluorescent dye, to determine their optimum characteristics, with the aim of their application as thin film sensor elements in fibre optic chemical sensors. In this test of the coatings, they were applied to standard, cleaned microscope slides and several characteristics, such as the ability of the sol to wet the glass substrate and the optical clarity of the subsequent coating were investigated and found to depend mainly on the water: tetraethylorthosilane (H₂O: TEOS) ratio used in their preparation but also on the extent of aging and the level of catalyst used. It was found that thicker coatings could be created through the use of suitable chemical additives in the preparation process.     

A New Sol-Gel Derived Optical Fiber Sensor for High Acidity Measurements: Application in Nuclear Fuel Reprocessing

Nuclear fuel reprocessing requires high acidity levels that should be accurately and rapidly controlled in order to optimize extraction yields and process efficiency. A new optical fiber sensor based on a sol-gel film doped with an acid-sensitive indicator has been developed to improve remote and on-line monitoring.The organic molecule was physically incorporated in an acid-catalyzed sol-gel matrix and coated onto the core of a denuded optical fiber. The sensor response was evaluated in synthetic solutions of nitric acid, concentrations ranging from 1 to 10 mol · l^–1. Changes in absorption properties and response characteristics of the sensor, when compared to the indicator in solution, have been discussed. Analytical performances of the sensor, i.e. sensitivity, response time, reversibility and repeatability are very encouraging for the on-line analysis. Viability of the sensor for process measurements depends on the stability which might be improved by a strict control of the sensitive film porosity.     

Optical Chemical Hydrazine Sensor from Hybrid Organic-Inorganic Materials

Original hybrid organic-inorganic materials have been synthesised, characterised and used as optical chemical hydrazine sensors. Because of its optical and chemical properties, 4-(dimethyl)aminobenzaldehyde (DMAB) was chosen as indicator. DMAB has been immobilised by physical entrapment in a microporous silica network or by a chemical bonding on a colloidal silica network. The response time of the sensor was essentially governed by the diffusion of hydrazine in the host matrix whereas its life time was dependent on the retention of DMAB. These two features were controlled by the nature and the quantity of the network agent and the catalyst, by the ageing time of the sol, and the drying and thermal treatment of the films.     

Micro- and nanomechanical sensors for environmental, chemical, and biological detection

Micro- and nanoelectromechanical systems, including cantilevers and other small scale structures, have been studied for sensor applications. Accurate sensing of gaseous or aqueous environments, chemical vapors, and biomolecules have been demonstrated using a variety of these devices that undergo static deflections or shifts in resonant frequency upon analyte binding. In particular, biological detection of viruses, antigens, DNA, and other proteins is of great interest. While the majority of currently used detection schemes are reliant on biomarkers, such as fluorescent labels, time, effort, and chemical activity could be saved by developing an ultrasensitive method of label-free mass detection. Micro- and nanoscale sensors have been effectively applied as label-free detectors. In the following, we review the technologies and recent developments in the field of micro- and nanoelectromechanical sensors with particular emphasis on their application as biological sensors and recent work towards integrating these sensors in microfluidic systems.     

基于荧光内滤效应的荧光增强型钠离子光纤传感器

在吸收型钠离子光化学传感器的敏感膜中加入合适的荧光试剂,应用荧光内滤效应研制成的荧光增强型光纤传感器,在测量灵敏度和抗背景干扰能力方面均有较大的改善,对血清和矿泉水样品中的钠离子含量进行了分析,获得了满意的结果。     

Polymeric Sensor Materials: Toward an Alliance of Combinatorial and Rational Design Tools?

Increased selectivity, response speed, and sensitivity in the chemical and biological determinations of gases and liquids are of great interest. Particular attention is paid to polymeric sensor materials, which are applicable to sensors exploiting various energy transduction principles, such as radiant, electrical, mechanical, and thermal energy. Ideally, numerous functional parameters of sensor materials can be tailored to meet specific needs using rational design approaches. However, increasing the structural and functional complexity of polymeric sensor materials makes it more difficult to predict the desired properties. Combinatorial and high-throughput methods have had an impact on all areas of research on polymer-based sensor materials including homo- and copolymers, formulated materials, polymeric structures with engineered morphology, and molecular shape-recognition materials. Herein we report on the state-of-the-art, the development trends, and the remaining knowledge gaps in the area of combinatorial polymeric sensor materials design.     

Stabilizing structure-switching signaling RNA aptamers by entrapment in sol-gel derived materials for solid-phase assays

Structure-switching, fluorescence-signaling DNA and RNA aptamers have been reported as highly versatile molecular recognition elements for biosensor development. While structure-switching DNA aptamers have been utilized for solid-phase sensing, equivalent RNA aptamers have yet to be successfully utilized in solid-phase sensors due to their lack of chemical stability and susceptibility to nuclease attack. In this study, we examined entrapment into sol-gel derived organic-inorganic composite materials as a platform for immobilization of structure-switching fluorescence-signaling RNA aptamer reporters, using both the synthetic theophylline- and naturally occurring thiamine pyrophosphate-binding RNA aptamers as test cases. Structure-switching versions of both aptamers were entrapped into a series of sol-gel derived composites, ranging from highly polar silica to hydrophobic methylsilsesquioxane-based materials, and the target-binding and signaling capabilities of these immobilized aptamers were assessed relative to solution. Both immobilized aptamers demonstrated sensitivity and selectivity similar to that of free aptamers when entrapped in a composite material derived from 40% (v/v) methyltrimethoxysilane/tetramethoxysilane. Importantly, this material also conferred protection from nuclease degradation and imparted long-term chemical stability to the RNA reporter systems. Given the versatility of sol-gel entrapment for development of biosensors, microarrays, bioaffinity columns, and other devices, this entrapment method should provide a useful platform for numerous solid-phase RNA aptamer-based devices.     

A fluorescent PEBBLE nanosensor for intracellular free zinc

The development and characterisation of a fluorescent optical PEBBLE (Probe Encapsulated By Biologically Localised Embedding) nanosensor for the detection of zinc is detailed. A ratiometric sensor has been fabricated that incorporates two fluorescent dyes; one is sensitive to zinc and the other acts as a reference. The sensing components are entrapped within a polymer matrix by a microemulsion polymerisation process that produces spherical sensors that are in the size region of 20 to 200 nm. Cellular measurements are made possible by the small sensor size and the biocompatibility of the matrix. The effects of reversibility, photobleaching and leaching have been examined, as well as the selectivity towards zinc over other cellular ions such as Na+, Ca2+, K+, and Mg2+. The dynamic range of these sensors was found to be 4 to 50 microM Zn2+ with a linear range from 15 to 40 microM. The response time for the PEBBLE is less than 4 s and the sensor is reversible. In addition, the nanosensors are photostable and leaching from the matrix, determined using a novel method, is minimal. These sensors are capable of real-time inter- and intra-cellular imaging and are insensitive to interference from proteins.     

Silicate Xerogels with Dopant-Induced Chirality

A series of silicate xerogels with entrapped chiral amino acids have been obtained via sol-gel technology. The transparent, glassy samples obtained exhibit chirality in the bulk due to the presence of the entrapped asymmetric molecules. Measurements of the optical activity of the doped xerogel samples revealed that the entrapment did not significantly influence the optical activity observed for liquid solutions of the amino acids. Thus, the sol-gel method enables the preparation of amorphous optical materials exhibiting properties of strictly spatially defined molecular systems. Apart from the obvious optical applications, such porous materials with asymmetric centers might find interesting applications in chiral chemical syntheses and separations.     

基于荧光内滤效应的锂离子荧光化学传感器研究

报道了一种基于荧光内滤效应的荧光增强型锂离子光化学传感器,将荧光试剂、亲脂性pH指示剂和锂离子中性载体结合在增塑的PVC膜中,Li⁺与H⁺在膜相中的竞争萃取效应引起受亲脂性pH指示剂调制的敏感膜荧光值的变化.推导了有关理论关系式,研究了该传感器的响应特性,并对人工合成样品进行测试,结果较为满意.     

Optical chemical sensors based on hybrid organic-inorganic sol-gel nanoreactors

Sol-gel porous materials with tailored or nanostructured cavities have been increasingly used as nanoreactors for the enhancement of reactions between entrapped chemical reactants. The domains of applications issued from these designs and engineering are extremely wide. This tutorial review will focus on one of these domains, in particular on optical chemical sensors, which are the subject of extensive research and development in environment, industry and health.     

A wide pH range optical sensing system based on a sol-gel encapsulated amino-functionalized corrole

The synthesis of a new compound, 10-(4-aminophenyl)-5,15-dimesitylcorrole, and its application for the preparation of optical chemical pH sensors is described. The dye materials were immobilized in a sol-gel glass matrix and characterised upon exposure to aqueous buffer solutions. The response of the sensor is based on the fluorescence intensity changing of corrole owing to multiple steps of protonation and deprotonation. Due to its containing several proton sensitive centers, the 10-(4-aminophenyl)-5,15-dimesitylcorrole based optode shows a wider response range toward pH than that of tetraphenylporphyrin (TPPH(2)) and 5,10,15-tris(pentafluorophenyl)corrole (H(3)(tpfc)). It shows a linear pH response in the range of 2.17-10.30. The effect of the composition of the sensor membrane has been studied and the experimental conditions were optimized. The optode showed good reproducibility and reversibility, and common co-existing inorganic ions did not show obvious interference to its pH measurement.     

Mesostructured materials for optical applications: from low-k dielectrics to sensors and lasers

Recent advances on the use of mesoporous and mesostructured materials for electronic and optical applications are reported. The focus is on materials which are processed by block-copolymer templating of silica under weakly acidic conditions and by employing dip- and spin-coating as well as soft lithographic methods to bring them into a well-defined macroscopic shape. Several chemical strategies allow the mesostructure architecture to be used for electronic/optical applications: Removal of the block-copolymers results in highly porous, mechanically and thermally robust materials which are promising candidates for low dielectric constant materials. Since the pores are easily accessible, these structures are also ideal hosts for optical sensors, when suitable are incorporated during synthesis. For example, a fast response optical pH sensor was implemented on this principle. As-synthesized mesostructured silica/block-copolymer composites, on the other hand, are excellently suited as host systems for laser dyes and photochromic molecules. Laser dyes like rhodamine 6G can be incorporated during synthesis in high concentrations with reduced dimerization. This leads to very-low-threshold laser materials which also show a good photostability of the occluded dye. In the case of photochromic molecules, the inorganic-organic nanoseparation enables a fast switching between the colorless and colored form of a spirooxazine molecule, attributed to a partitioning of the dye between the block-copolymer chains. The spectroscopic properties of these dye-doped nanocomposite materials suggest a silica/block-copolymer/dye co-assembly process, whereby the block-copolymers help to highly disperse the organic dye molecules.     

多荧光光纤传感器及其在混合溶剂检测中的应用

微纳光纤与其他微纳结构的集成可以拓展荧光光纤传感器检测范围和集成度,是光纤传感领域的研究热点。目前,国际上关于荧光光纤传感器这一领域的研究还处于单一检测物荧光响应的阶段,对多检测物的多通道荧光响应仍存在很大挑战。本文结合微纳光纤的光波导性能以及有机荧光材料的光功能特性,制备了能够同时激发和收集多种荧光的微纳光纤,并将之应用于高性能荧光光纤传感器的制备。通过选用不同荧光波长的有机材料与凝胶掺杂,制备了多荧光发射的光纤涂层材料,可控构筑了多组分荧光检测剂掺杂凝胶涂层。利用荧光光谱结合色度图分析,确定检测物与色坐标的关系,实现了多检测物的多通道荧光响应,为实现多荧光光纤传感器的可控构筑提供了有益的借鉴和指导意义。     

共价嫁接Ru(Ⅱ)配合物杂化材料的制备及氧气传感性能研究

利用十六烷基三甲基溴化铵制备了一种具有MSU型蠕虫状孔道结构, 同时共价嫁接了Ru(Ⅱ)配合物的介孔杂化功能材料, 并研究了其氧气传感性能. 双功能有机改性硅酸酯Bpy-Si不仅是配合物Ru(bpy)2Cl2·2H2O的一个配体, 而且通过与正硅酸乙酯的水解和共聚反应, 把Ru(bpy)2(bpy-Si)Cl2配合物通过Si—C共价键嫁接到二氧化硅的骨架上. 研究结果表明, Ru(Ⅱ)分子在杂化材料中的发光受氧气猝灭明显, 而且具有较快的响应时间, 所得材料具有作为性能优良的氧气传感材料研究的潜质. 由于介孔材料的独特孔道结构有利于氧气在载体中的扩散, 介孔样品表现出比无定形样品更高的灵敏度.