Spacer layer screening effect: a novel fluorescent film sensor for organic copper(II) salts

A fluorescent film sensor was prepared by chemical assembly of pyrene on a glass plate surface via a long flexible spacer. It was found that the film is highly selective for some organic Cu2+ salts, such as copper acetate and copper propionate. The presence of inorganic Cu2+ salts and other metal(II) acetates, including Ni2+, Co2+, Pb2+, Cd2+, Zn2+, etc., had little effect upon the sensing behavior of the film for copper acetate or copper propionate. The observation was explained by employing a proposed "two-dimensional solution" model. The quenching by copper acetate of the emission of the film is static in nature due to complexation of the spacers to the metal ions. Furthermore, the response of the film sensor to copper acetate is fully reversible. To the best of our knowledge, this film sensor may be the first one that can differentiate greasy copper salts from inorganic copper salts.     

芘在玻璃基片表面的单层组装及其对有机铜盐的选择性传感

将多环芳烃芘经含三乙基四胺结构的连接臂化学单层组装于玻璃基质表面, 制备了一种荧光薄膜材料. 荧光测量结果表明, 醋酸铜、酒石酸铜、柠檬酸铜等有机铜盐可以显著猝灭薄膜荧光, 而且猝灭过程可逆; 硫酸铜、氯化铜、硝酸铜等无机铜盐对薄膜荧光影响不大; 醋酸锌、醋酸铅、醋酸钴、醋酸镍等其它醋酸盐对有机铜盐的检测影响轻微. 荧光寿命测定表明, 醋酸铜对上述薄膜荧光的猝灭遵循静态猝灭机制.     

Monolayer Assembly of Pyrene on Glass Plate Surface and Its Selective Sensing Performances to Organic Copper (II) Salts

A novel fluorescent sensing film was developed by covalently attaching pyrene moieties onto a glass plate surface via triethylenetetramine in a self-assembled monolayer manner. Fluorescence measurements demonstrated that the emission of the film could be quenched by organic copper (II) salts, including copper acetate, copper tartrate, and copper citrate, with high selectivity and sensitivity, and the response of the film to Cu(Ac)₂ is fully reversible. In contrast, the presence of inorganic copper salts, such as Cu(NO₃)₂, CuSO₄, and CuCl₂, showed lower quenching efficiency. The sensing performance of the film to Cu(Ac)₂ is slightly influenced by other divalent metal acetates, including Zn(Ac)₂,Pb(Ac)₂, Co(Ac)₂,andNi(Ac)₂.Furthermore,thequenchingof Cu(Ac)₂ to the emission of the film is static in nature.     

A Novel Thin‐Film Copper Array Based on an Organic/Inorganic Sensor Hybrid: Microfabrication,Potentiometric Characterization,and Flow‐Injection Analysis Application

A first step towards the microfabrication of a thin‐film array based on an organic/inorganic sensor hybrid has been realized. The inorganic microsensor part incorporates a sensor membrane based on a chalcogenide glass material (Cu‐Ag‐As‐Se) prepared by pulsed laser deposition technique (PLD) combined with an PVC organic membrane‐based organic microsensor part that includes an o‐xylyene bis(N,N‐diisobutyl‐dithiocarbamate) ionophore. Both types of materials have been electrochemically evaluated as sensing materials for copper(II) ions. The integrated hybrid sensor array based on these sensing materials provides a linear Nernstian response covering the range 1×10^?6–1×10^?1 mol L^?1 of copper(II) ion concentration with a fast, reliable and reproducible response. The merit offered by the new type of thin‐film hybrid array includes the high selectivity feature of the organic membrane‐based thin‐film microsensor part in addition to the high stability of the inorganic thin‐film microsensor part. Moreover, the thin‐film sensor hybrid has been successfully applied in flow‐injection analysis (FIA) for the determination of copper(II) ions using a miniaturized home‐made flow‐through cell. Realization of the organic/inorganic thin‐film sensor hybrid array facilitates the development of a promising sophisticated electronic tongue for recognition and classification of various liquid media.     

杯[4]芳烃的表面化学组装及其在气态四氢呋喃荧光传感薄膜创制中的应用

挥发性有机化合物(Volatile Organic Compounds,VOCs)是重要的大气污染物,严重地危害着人类健康.本文设计合成了一种末端携带反应活性硅氧烷基团的杯[4]芳烃衍生物,通过自组装和表面化学反应将其共价结合于玻璃基质表面,获得了一种杯[4]芳烃修饰玻璃基质.以此基质物理担载荧光活性物质--芘封端三聚噻吩(Py-3T),得到了一种对气相四氢呋喃具有"turn-on"及快速灵敏(26.7 μg/mL)响应特性的荧光传感薄膜.实验表明:除苯和甲苯之外,其它常见有机溶剂和化学物质蒸汽对该薄膜荧光发射基本没有影响.苯和甲苯也因响应程度小、响应速度慢而难以干扰测定过程.据此,可以预期该荧光薄膜有可能在THF气体传感上获得应用.     

An Ultrasensitive Fluorescent Sensing Nanofilm for Organic Amines Based on Cholesterol‐Modified Perylene Bisimide

A stable, ultrasensitive, and fully reversible fluorescent sensing film for organic amines has been fabricated by assembling cholesterol (Chol)‐derived perylene bisimide on a glass plate surface. The compound exhibits excellent film formation properties and forms well‐defined nanofibers, as evidenced by SEM and AFM measurements. It has been revealed that besides the molecular structure of the specially designed perylene derivative, the existence of nanofibers in the film is another key factor to endow the film with superior sensing ability for organic amines, including aniline. The detection limit of the amine is ca. 150.0 ppt in the vapor phase and at room temperature. Furthermore, the sensing process is free of interference from common organic solvents, nitroaromatics, and particularly phenols, which makes the film a potential candidate to be used in lung cancer diagnoses and related applications.     

Cyclodextrin Polymer Films Optical Waveguide Sensor for Volatile Organic Gas Detection

A sensitive optical waveguide(OWG) sensor which can be used to detect volatile organic compounds(VOCs) was presented. The sensing device(element) was fabricated by means of the immobilization of polyvinyl pyrrolidone(PVP)-cyclodextrin(CD) composite film over a single-mode potassium ion exchanged glass OWG via spin-coating method. The sensor shows higher response to styrene gas than to other VOCs and displays a linear response to styrene gas in a range of 1-1000 μL/L.     

Determination of Nitroaromatics Using a Double-Layer of Gelatin Nanofibers and a Pyrene-Doped Polystyrene Membrane

ABSTRACT

A double-layered sensor was prepared by an electrospinning method using pyrene, polystyrene, and gelatine to prepare a pyrene-polystyrene/gelatin/glass device for the determination of nitroaromatics. The pyrene- polystyrene top layer, which was an electronspun membrane from a mixture of the starting materials in 3:1?N, N-dimethylformaide:tetrahydrofuan, served as the sensing layer for detecting 2,4-dinitrotoluene. The bottom layer was the gelatin electrospun membrane that served as an intermediate between the top layer and the glass slide. The dinitrotoluene analyte was transferred into the sensing layer above and below due to the porosity of the gelatin layer. With a large number of hydroxyl and amino groups, the gelatin layer formed hydrogen bonds with the 2,4-dinitrotoluene molecules, which caused the enrichment of the analyte around the gelatin layer. Additionally, single-layer pyrene-polystyrene/glass sensor was also prepared for control measurements. The quenching efficiency of the pyrene-polystyrene/gelatin/glass sensor was 76.7% at equilibrium obtained within 6 minutes, while the monolayer sensor pyrene–polystyrene/glass device provided 65.8% quenching efficiency within 6 minutes. The gelatin layer played an important role in the superior performance of the double-layered sensor.     

Optical waveguide sensor of volatile organic compounds based on PTA thin film

In this study, a sensitive optical waveguide (OWG) sensor for the detection and identification of volatile organic compounds (VOCs) was reported. The sensing membrane is constructed by immobilization of peroxopolytungsten acid (PTA) thin film over a single-mode potassium ion (K⁺) exchanged glass OWG by spin-coating method. A laser beam was coupled into and out of the glass optical waveguide using prism couplers, and dry air functioned as a carrier gas. The sensor was tested for various volatile organic compounds (VOCs), and it showed higher response to the chlorobenzene gas compared to other VOCs. Therefore, we used the OWG sensor to detect chlorobenzene gas as a typical example of VOCs. The sensor exhibits a linear response to chlorobenzene gas in the range of 0.4-1000 ppm with rapid response and good reversibility. The constructed sensor is easy to fabricate and it has some unique qualities which can be characterized as inexpensive, sensitive, and reusable.     

Toward Sol-Gel-Processed Chemical Sensing Platforms: Effects of Dopant Addition Time on Sensor Performance

The development of new chemical and biochemical sensing schemes has been a topic of growing interest. Simplicity of preparation and mild processing conditions have made sol-gel-derived composites attractive for many chemical sensing schemes. A portion of our research centers on using sol-gel-processed materials for the development of selective sensors. Over the years we have aimed to characterize the analytical performance of these types of sol-gel-based sensing platforms. In the course of this work we recently discovered that the time (prior to casting) when the sensing chemistry is actually doped into the sol-gel processing solution plays a critical role in a given sensor's analytical performance. In this paper we report on the effects of doping time on the behavior of a model organic dopant (pyrene) sequestered within sol-gel-derived microfiber tips and films. We use O₂ as the analyte and determine the sensor sensitivity and temporal response as a function of doping time. We also quantify the local dipolarity of the immediate environment surrounding the average pyrene molecule as a function of doping time.     

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.     

Photosensitizing properties of the porphycene immobilized in sol-gel derived silica coating films

Porphycene was covalently immobilized in a sol-gel silica film deposited on a glass plate, and the immobilized porphycene showed a photosensitizing property with recycling for the photo-oxidation of 1,5-dihydroxynaphthalene.     

Characterization of N-cyclohexylmethacrylamide LB thin films for room temperature vapor sensor application

This study reports the synthesis, characterization and gas sensing applications of N-cyclohexylmethacrylamide (NCMA) monomer material using FT-IR, ¹H and ¹³C NMR, UV-visible spectroscopy, Quartz Crystal Microbalance (QCM) and Langmuir-Blodgett (LB) thin film deposition techniques. The thin film deposition conditions of NCMA monomer material, which are prepared by LB film technique, are characterized by UV-visible spectroscopy and QCM system. The sensing behaviors of the LB film with respect to volatile organic compounds (VOCs) at room temperature are investigated. Surface pressure change as a function of surface area of NCMA molecule at the water surface shows a well-organized and stable monolayer at 18 mN m^?1 surface pressure value for LB film deposition. Transfer ratio values are found to be ≥ 0.94 for quartz glass and ≥ 0.93 for quartz crystal substrate. The typical frequency shift per layer is obtained 20.10 Hz/layer and the deposited mass onto a quartz crystal is calculated as 824.62 ng/layer. The sensing responses of the LB films against chloroform, dichloromethane, acetone, toluene, benzene and ethanol are measured by QCM system. The sensitivities of the NCMA LB film sensor are determined between 0.085 and 0.029 Hz ppm^?1. Sensitivities with detection limits are between 35.29 and 100.33 ppm against organic vapors. These results can be concluded that the monomer LB film sample is found to be significantly more sensitive to chloroform and dichloromethane vapors than others organic vapors used in this work. This material may find potential applications in the development of room temperature organic vapor sensing.     

Fluorescent film sensor for nitroaromatics prepared via grafting a conjugated polymer on a glass slide surface

A functionalized glass sensor (G-P) was prepared for detecting nitroaromatic compounds (NACs) by chemically immobilizing a conjugated polymer P on the surface of a glass slide. The monolayer film sensor had several advantages: the signal amplification effect of conjugated polymers, no leakage of sensing materials in solution, and good permeability for the analytes. Fluorescence quenching studies demonstrated that the sensor was highly sensitive to NACs. When the DNT concentration was 1.03 × 10^–7 mol/L, the quenching efficiency (1–I/I ₀) of G-P reached 52.8%. Moreover, the excellent properties of reversibility, selectivity and sensitivity indicated the glass G-P might be a promising sensor in the field of explosives detection.     

氧化锌薄膜/锡掺杂玻璃光波导元件及其对氯苯的气敏性研究

建立了玻璃光波导气敏元件检测氯苯气体的方法.采用浸渍-提拉法将ZnO敏感膜固定在锡掺杂玻璃光波导表面,研制出了检测氯苯气体的ZnO薄膜/锡掺杂玻璃光波导气敏元件,并用该玻璃光波导气敏元件对挥发性有机气体进行了检测.实验结果表明,在室温下,气敏元件对氯苯气体有明显的响应,而对相同浓度的其它挥发性有机气体的响应相对较小,对...     

Optical Sol-Gel-Based Dissolved Oxygen Sensor: Progress Towards a Commercial Instrument

A dissolved oxygen sensor based on fluorescence quenching of the oxygen-sensitive ruthenium complex, [Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline]2+, which has been immobilized in a porous silica sol-gel-derived film, is reported. Ormosil sensing films were fabricated using modified silica precursors such as methyltriethoxysilane (MTEOS) and ethyltriethoxysilane (ETEOS) and were dip-coated onto planar glass substrates. Tailoring of the films for dissolved oxygen (DO) sensing is described whereby sensor response is optimized by maximizing film hydrophobicity by the use of the modified precursors. Sensor performance parameters such as limit of detection and sensor resolution are reported. Issues such as dye leaching and photobleaching are discussed. Progress towards a commercial instrument is reported.     

Humidity sensors using in situ synthesized sodium polystyrenesulfonate/ZnO nanocomposites

Thin film humidity sensors have been prepared using in situ synthesized inorganic/organic nanocomposites of sodium polystyrenesulfonate (NaPSS) and ZnO. Its humidity sensing characteristics and the sensing mechanism have been investigated by measuring the complex impedance spectra of the sensor at different humidities. The logarithm of the impedance of sensor based on composite film changes linearly by four-orders of magnitude over almost whole humidity range (11-97% RH). Furthermore, the sensor exhibits a quick response (absorption: 2 s, desorption: 2 s) and small hysteresis (less than 2% RH). The composite film shows better sensing properties than NaPSS film, such as better linearity, quicker response. Explanation to the improvement is attempted by taking into account of the composition and structure of the nanocomposites.     

Filter-free integrated sensor array based on luminescence and absorbance measurements using ring-shaped organic photodiodes

An optical waveguiding sensor array featuring monolithically integrated organic photodiodes as integrated photo-detector, which simplifies the readout system by minimizing the required parts, is presented. The necessity of any optical filters becomes redundant due to the proposed platform geometry, which discriminates between excitation light and sensing signal. The sensor array is capable of measuring luminescence or absorption, and both sensing geometries are based on the identical substrate. It is demonstrated that background light is virtually non-existent. All sensing and waveguide layers, as well as in- and out-coupling elements are assembled by conventional screen-printing techniques. Organic photodiodes are integrated by layer-by-layer vacuum deposition onto glass or common polymer foils. The universal and simple applicability of this sensor chip is demonstrated by sensing schemes for four different analytes. Relative humidity, oxygen, and carbon dioxide are measured in gas phase using luminescence-based sensor schemes; the latter two analytes are also measured by absorbance-based sensor schemes. Furthermore, oxygen and pH in aqueous media were enabled. The consistency of calibration characteristics extending over different sensor chips is verified.

PVA薄膜光波导气敏元件及其应用研究

将纯聚乙烯醇(PVA)和掺有维生素C的PVA作为敏感试剂,通过旋转甩涂法分别研制出了PVA薄膜/锡掺杂玻璃光波导元件和VC-PVA薄膜/锡掺杂玻璃光波导元件并检测其气敏特性.实验结果表明,PVA薄膜/锡掺杂玻璃光波导元件对二甲苯气体有良好的选择性响应,其响应浓度范围为10-4～10-7(体积比);加入VC后,使此敏感元...     

光波导传感元件在检测酸性气体中的应用

采用旋转甩涂法将甲基紫传感薄膜固定在特制的锡(Sn2+,Sn4+)掺杂玻璃光波导(Sn doped glass slide)表面,研究了该传感薄膜与HCl、H2S、以及SO2作用前后的可见吸收光谱的变化,并在此基础上研制了玻璃光波导酸性气体(HCl、H2S、SO2)传感元件。传感薄膜与酸性气体作用时,薄膜的颜色发生变化,从而降低薄膜对倏逝波的吸收,使传感器的输出光强度(信号)增强。本文采用流动注射法对酸性气体进行了检测。实验结果表明,在室温下,该传感元件对硫化氢气体具有明显的响应,而对相同浓度的其他酸性气体的响应相对较小,对浓度在6×10-4～2.5×10-5(V/V)的硫化氢气体具有良好的线性响应(R=0.9979,n=4),相对标准偏差(RSD)为±3.5%,具有响应快、可逆性和重复性好、容易制备、可以在室温下工作等特点。