一种新的基于折射率变化的光纤化学传感器

在光纤化学传感器中,基于样品折射率变化的传感器是其中的重要分支,并获得了广泛的实际应用^[1].根据敏感部件的不同可将其分为两大类:一类的敏感部件是裸光纤,这类传感器已用于检测苯、甲醇和丙酮^[2],测定血样中葡萄糖浓度^[3],鉴定燃油质量.     

Mode-filtered light methane gas sensor based on cryptophane A

A mode-filtered light sensor has been developed for methane (CH₄) gas determination at ambient conditions. The proposed chemosensor consisted of an annular column which was constructed by inserting an optical fiber coated with a thin silicone cladding of cryptophane A into a fused-silica capillary. When CH₄ was introduced to the sensor, selective inclusion of CH₄ into the silicone layer would cause a change in the local refractive index of the cladding, resulting in the change of mode-filtered light that emanated from the fiber. Three detection windows were set alongside the capillary to propagate the light to a charge-coupled device (CCD). The changes of mode-filtered light on exposure to various concentrations of CH₄ were thus simultaneously monitored. The mode-filtered light intensity decreased with the increase in concentration of CH₄. The dynamic concentration range of the sensor for CH₄ was 0.0-16.0% v/v with a detection limit of 0.15% v/v. The highest sensitivity was found at the channel furthest away from the excitation light source. The response time (t_95%) was about 5 min. The reproducibility was good with a relative standard deviation (RSD) of less than 7% from evaluating six cryptophane A-coated fibers. Oxygen, hydrogen and carbon dioxide showed very little interference on detection but interferences from dichloromethane and carbon tetrachloride were observed. The proposed mode-filtered light sensor has been successfully applied to determine CH₄ samples and the accuracy was good. Our work offers a promising approach for CH₄ detection.     

Dual Fiber-In-capillary Annular Column with Ternary Stationary Phase for Gas Chromatographic Separation

In the present work a novel strategy for improving and/or tuning the selectivity of gas chromatographic (GC) separation by combining three different stationary phases (SPs) without premixing was introduced. A fused silica fiber coated with polydimethylsiloxane (SE30) and another coated with cyanopropylphenylmethylpolysiloxane (OV1701) were serially inserted into an 8-m polyethylene glycol 20 M (PEG20M) capillary column to form a GC annular column with ternary SP, abbreviating as SE30-OV1701-CF/PEG20M-CC. The separation capability of this ternary SP annular column was compared with a SE30-coated fiber-in-PEG20M-coated capillary annular column and a PEG20M-coated open tubular column by a test mixture of 19 organic compounds. Among these three columns, SE30-OV1701-CF/PEG20M-CC produced the best separation when the SE30-coated fiber and OV1701-coated fiber was 3 and 5 m, respectively. Selectivity can be easily tuned by changing the length of the SP-coated fibers in the ternary SP annular column. The proposed ternary SP annular column shows additional tunability, thus making it a promising tool for separation of organic solvents that are often used in the manufacturing process of pharmaceutical formulations and lacquer thinners.     

Fiber-optic surface plasmon resonance for vapor phase analyses

Fiber-optic sensors based on surface plasmon resonance (SPR) for direct refractive index (RI) measurements of samples with the RI between 1.00 and 1.30 are described. Most applications of SPR sensors are designed to function near the refractive index of water (1.3330 RI). The RI changes of aqueous solution (RI, ca. 1.34) can easily be monitored by silica-fiber (RI, 1.4601 at 550 nm) based SPR sensor. With regard to gas species detection, the fiber-optic SPR sensor must be modified for sensitivity to changes in refractive index near 1.0008 (i.e., RI of air). However, the silica waveguide has a prohibitively high RI for unmodified monitoring of the RI changes of gas. The silica-fiber based SPR probe design presented here is based upon the modification of the probe geometry to the ability to tune the SPR coupling wavelength/angle pair. In this study, the tapered silica-based fiber SPR sensors are shown to directly determine the RI changes of gas species and the density change of dry air.     

A fiber optic evanescent field absorption sensor for monitoring organic contaminants in water

Summary A fiber optic chemical sensor for determination of organic compounds in aqueous solution has been developed. Based on the evanescent field principle, a quartz glass fiber with a polysiloxane cladding is used as in-situ measuring probe. A compact sensor built from a 6-m coiled fiber has been connected to a commercially available fast scanning dispersive NIR spectrometer. The siloxane cladding fulfils two functions: on the one hand, it acts as protecting layer of the fragile silica fiber core, and on the other hand, it is selective with respect to non-polar organic compounds due to its organophilic properties. Hence, interactions of the evanescent field at the core/cladding interface with organic species penetrating into the cladding can be measured without interferences from broad water OH absorption bands. Aqueous solutions of chlorinated hydrocarbon solvents (CHS) have been used to test the sensor response. NIR evanescent field absorbance spectra of methylene chloride, chloroform and trichloroethylene diffused into the fiber cladding are shown in the 900–2100 nm spectral range. Different amounts of CHCl₃ dissolved in water have been determined in order to evaluate the quantitative sensor response. A linear absorbance/concentration relationship has been found for solutions between 80–6800 mg l^–1. Kinetic experiments performed with CHCl₃ solutions resulted in sensor response times of 5–10 min. The sensor seems to be promising for the remote monitoring of organic contaminants, e.g. CHS, in drainage waters of contaminated areas.     

Fiber-optic evanescent-field laser sensor for in-situ gas diagnostics

A compact, rugged and portable fiber-optic evanescent-field laser sensor is developed for the detection of gaseous species in harsh environments such as volcano fumaroles or industrial combustion of glass furnaces. The sensor consists of an optical multi-mode fused silica fiber with jacket and cladding removed and the bare fiber core in direct contact with the surrounding molecules. The beam of a single-mode DFB diode laser with an emission wavelength centered at 1.5705 microm is coupled into the fiber. At the other end of the fiber an infrared detector is used to record the transmitted infrared laser light intensity. Due to the frustrated total reflection (FTR) and the attenuated total reflection (ATR) the laser intensity is attenuated when passing through the fiber. The FTR is related to a change of the index of refraction while the latter one is related to a change of the absorption coefficient. While tuning the DFB laser wavelength across absorption lines of molecules surrounding the fiber a spectral intensity profile is measured. Voigt functions are fitted to the recorded intensity profiles to estimate relative molecule concentrations. In this paper results from first field measurements at the volcano site 'Solfatara' in Italy are reported that use such a sensor device for simultaneous detection of H2S, CO2 and H2O directly in the gas stream of a volcano fumarole.     

Synchronization of separation and determination based on multichannel mode-filtered light detection with capillary electrophoresis.

A novel method for the synchronization of separation and determination is described, in which a mode-filtered light detector is used as an online detector in capillary electrophoresis. An instrument is described which has been developed for this purpose. The round capillary used in conventional capillary electrophoresis is replaced by an annular column, which is constructed from a naked optical fibre inserted into a fused-silica capillary. In fact, the annular electrophoresis column itself forms part of the mode-filtered light sensor. Along the side of the annular column are several detection channels for gathering and transmitting the mode-filtered light to a charge-coupled device (CCD). Every channel provides information on the sample from the point at which it is located. Using capillary isotachophoresis incorporating the annular column, the analytes in a sample containing alanine (10.0 mM) and glycine (9.7 mM) were simultaneously separated and determined using multichannel mode-filtered light detection with a detection limit of 1.5 mM.     

Monitoring the absorption of organic vapors to a solid phase extraction medium applications to detection of trace volatile organic compounds by integration of solid phase absorbents with fiber optic Raman spectroscopy

By combining fiber optic Raman spectroscopy with a C-18 solid phase extraction medium, real time in situ detection of organic vapors is demonstrated. The response of the probe is fully reversible for benzene, trichloroethylene and carbon tetrachloride vapors. Because of the high degree of selectivity afforded by Raman spectroscopy, the composition of mixtures of the vapors can also be determined using the C-18 probe. The detection of ppm levels of benzene in water via headspace analysis using the C-18 probe is demonstrated.     

Chemical vapor discrimination using a compact and low-power array of piezoresistive microcantilevers

A compact and low-power microcantilever-based sensor array has been developed and used to detect various chemical vapor analytes. In contrast to earlier micro-electro-mechanical systems (MEMS) array sensors, this device uses the static deflection of piezoresistive cantilevers due to the swelling of glassy polyolefin coatings during sorption of chemical vapors. To maximize the sensor response to a variety of chemical analytes, the polymers are selected based on their Hildebrand solubility parameters to span a wide range of chemical properties. We utilize a novel microcontact spotting method to reproducibly coat a single side of each cantilever in the array with the polymers. To demonstrate the utility of the sensor array we have reproducibly detected 11 chemical vapors, representing a breadth of chemical properties, in real time and over a wide range of vapor concentrations. We also report the detection of the chemical warfare agents (CWAs) VX and sulfur mustard (HD), representing the first published report of CWA vapor detection by a polymer-based, cantilever sensor array. Comparisons of the theoretical polymer/vapor partition coefficient to the experimental cantilever deflection responses show that, while general trends can be reasonably predicted, a simple linear relationship does not exist.     

基于室温离子液体的电导型气体传感器

本文利用室温离子液体对水或有机蒸气吸收后其离子导电性的改变,研制了以离子液体BmimPF6为敏感材料的电导型气体传感器.考查了BmimPF6用量对传感器响应的影响,测定了传感器对不同浓度的水蒸汽及乙醇、二氯甲烷等饱和有机蒸气的响应.实验结果显示,该传感器具有制作方便、结构简单、稳定性高及线性范围宽等优点,可被用于不同浓度的水或有机蒸气/氮气混合气氛中,水蒸汽或有机蒸气浓度的测定.此外,还针对该传感器对乙醇等不同饱和有机蒸气响应信号与这些有机溶剂的理化性质参数间的定量关系,采用化学计量学方法进行了建模分析.     

Compact fluorescence detection using in-fiber microchannels-its potential for lab-on-a-chip applications

This paper reports a compact and practical fluorescence sensor using an in-fiber microchannel. A blue LED, a multimode PMMA or silica fiber and a mini-PMT were used as an excitation source, a light guide and a fluorescence detector, respectively. Microfluidic channels of 100 microm width and 210 microm depth were fabricated in the optical fibers using a direct-write CO(2) laser system. The experimental results show that the sensor has high sensitivity, able to detect 0.005 microg L(-1) of fluorescein in the PBS solution, and the results are reproducible. The results also show that the silica fiber sensor has better sensitivity than that of the PMMA fiber sensor. This could be due to the fouling effect of the frosty layer formed at the microchannel made within the PMMA fiber. It is believed that this fiber sensor has the potential to be integrated into microfluidic chips for lab-on-a-chip applications.     

Use of the original silicone cladding of an optical fiber as a reagent-immobilization medium for intrinsic chemical sensors

It is demonstrated that extended-length sensors can be fabricated by the direct immobilization of suitable reagents into the original cladding of a plastic-clad silica (PCS) optical fiber. This cladding, a copolymer of vinyl-terminated poly(dimethylsiloxane) and poly(dimethylmethylhydrosiloxane), is an attractive immobilization matrix for a wide variety of reagents and opens up new avenues of sensor design. Unlike fibers with custom-drawn cladding, the new approach offers greater photo- and thermal stability and permits immobilization of several reagents in adjacent sections of a single fiber. Further, compared to room-termperature vulcanizable (RTV) silicone films used often in optical point sensors, the silicone cladding of a PCS optical fiber offers a number of advantages, including a dynamic fluorescence quenching constant for an immobilized fluorophore that is up to 3.4 times higher, tolerance to aggressive environments (e.g. highly alkaline solutions), lower rates of indicator leaching, high uniformity, and applicability to extended-length sensing. The homogeneity of the microenvironment of the fiber cladding, its resistance to aggressive alkaline solutions, and its ability to transport water vapor were probed by introducing a variety of reagents into the cladding, including a fluorescent ruthenium complex and acid-base and solvatochromic indicators. The new sensor-fabrication approach should find wide application, including detection of neutral species in gases and dissolved in water, and for spatial analyte mapping over extended, remote areas.     

Whole-column fluorescence-imaged capillary electrophoresis

An axially illuminating whole-column fluorescence imaging capillary electrophoresis (CE) experimental setup was developed. A 6 cm long Teflon tube with an inside diameter (ID) of 42 microm was used as separation column. Excitation light of 488 nm from Ar+ laser was introduced to one end of the separation column by an optical fiber. The excitation light propagated inside the separation column by total internal reflection, since the refractive index of the buffer solution was larger than that of the Teflon tube. The fluorescence from the whole separation column was imaged with a charge-coupled device (CCD) camera. Fluorescent compounds such as fluorescein isothiocyanate (FITC), 5-carboxyfluorescein, and FITC-labeled protein were used to test the basic performance of the experimental setup. Experimental results illustrate that the whole-column-fluorescence imaging CE is a fast and sensitive separation method for fluorescent compounds and fluorescent-labeled proteins. Furthermore, it could be used for simple, fast, and easy comparisons of the resistance to photodegradation for various fluorescent compounds.     

SAW气体传感器聚合物敏感膜材料研究进展

声表面波(surface acoustic wave,SAW)气体传感器具有灵敏度高、选择性好、响应时间短以及体积小,携带方便等优点,因而被广泛应用于环境监测、医疗卫生、化学侦检等领域中有毒有害气体的现场实时检测。敏感膜材料的特性是决定SAW传感器性能(如灵敏度、选择性、响应时间、寿命等)的关键因素。本文首先简要介绍了SAW气体传感器的响应原理和对敏感膜材料的要求,然后重点阐述了用于SAW气体传感器的有机聚合物敏感膜材料的研究进展,最后对其研究趋势做出简单预测。     

Photopolymerized sol-gel frits for packed columns in capillary electrochromatography

Porous sol-gel frits are fabricated in a capillary column by filling it with a solution of 3-(trimethoxysilyl)propyl methacrylate, hydrochloric acid, water, toluene (porogen), and a photoinitiator (Irgacure 1800) and exposing it to UV light at 365 nm for 5 min. The separation column (30 cm x 75 microm I.D.) contains between the inlet and outlet frits a 15-cm packed segment filled with 5-microm silica particles modified with the chiral compound (S)-N-3,5-dinitrobenzoyl-1-naphthylglycine. A detection window (1 mm long) is placed immediately after the outlet frit. To demonstrate the performance of this chiral separation column, mixtures of 16 different amino acids (three of which are not naturally occurring) derivatized with the fluorogenic reagent 4-fluoro-7-nitro-2,1,3-benzoxadiazole were separated by capillary chromatography. The enantiomeric separation of the column results in a resolution ranging from 1.21 to 8.29, and a plate height ranging from 8.7 to 39 microm.     

Optical response of mesoporous synthetic opals to the adsorption of chemical species

We have demonstrated the fabrication of a colloidal crystalline array (synthetic opal) from monodispersed mesoporous silica spheres (MMSS) and the control of its optical response simply by changing the amount of benzene vapor adsorbed into the pores of MMSS. It was revealed that the refractive index of the colloidal crystal of MMSS showed an 11.7% increase by taking advantage of benzene adsorption, and thereby, the structural color changed reversibly. We also conducted the same measurement on silica spheres without mesopores and observed no change in the refractive index or the structural color. This optical response gives rise to the possibility of using MMSS colloidal crystals not only for controlling light reflection but also as sensing devices based on color change due to vapor adsorption. We have also incorporated an organic dye, the porphyrin derivative alpha,beta,chi,delta,-tetrakis(1-methylpyridinium-4-yl)porphyrin rho-toluenesulfonate (TMPyP), into the pores of MMSS. By adopting an electrophoretic deposition process in ethanol, periodic arrays fabricated from TMPyP-MMSS conjugates with absolute zeta-potentials near zero were obtained. The Bragg diffraction peak of the colloidal crystalline array shifted to longer wavelengths due to an increase in the refractive index with increasing amounts of TMPyP adsorbed in the pores. The current work demonstrates the new possibility of creating colloidal crystals from MMSS with mesopores filled with various kinds of adsorbates to control the optical response effectively.     

Novel imidazolium stationary phase for high-performance liquid chromatography

A new imidazolium anion-exchange phase immobilized on silica is synthesized. HPLC separations of common inorganic anions (IO3-, Cl-, NO2-, Br-, NO3-, I-, SCN-) have been performed using a HPLC column (200 mm x 4.6 mm I.D.) packed with this stationary phase, with a phosphate buffer solution as the mobile phase and UV detection at 200 nm. The effects of pH and concentration of eluent on the separation of anions have been studied. Chromatographic parameters are calculated and the results show that the new stationary phase is of significant potential for the analysis of these anions. Successful separations of some ordinary organic anions have also been achieved with the said stationary phase. Meaningfully, organic and inorganic anions can be determined simultaneously and satisfactorily with several neutral compounds using the column. The separation of some organic compounds including hydroxybenzenes, bases and amines by this stationary phase with only water as the eluent has been investigated.     

Detecting organic vapors using a conductometric sensor prepared from Ardel®D-100 and graphite

The composites of graphite with Ardel^?D-100 which is a trademark of a polyester of bisphenol-A with terephthalic and isophthalic acid were used as a sensing material in a conductometric vapor sensor. The magnitudes of responses are increased in the order of benzene, isobutyl acetate, isoamyl acetate, ethyl benzene and chloro benzene. This suggests that Ardel^?D-100 can be used as a sensing material for chlorobenzene, ethyl benzene and isoamyl acetate. On the other hand, specific retention volumes of the sensed vapors on Ardel^?D-100 coated on graphite were determined by inverse gas chromatography at temperatures between 200 and 260 °C. The distribution coefficient, K _s of the vapors between stationary and mobile phases in the column was obtained. It was revealed for the first time that the logarithm of K _s of the solvents varies almost linearly with their responses based on conductometric resistance of the sensing polymer composite. Subsequently, the study suggests that gas chromatographic retention data can be used in prediction of the conductometric responses of a polymeric sensor to vapors. Correspondence: Ferdane Karaman, Department of Chemistry, Yildiz Technical University, 34220 Istanbul-Esenler, Turkey     

以离子液体为流动相的高效液相色谱-间接紫外检测法分析四甲基按根离子

建立了四甲基铵根离子的反相高效液相色谱-间接紫外检测分析法.以ZORBAX ODS反相色谱柱为分离柱,采用间接紫外检测方法,考察了紫外检测波长和离子液体+有机溶剂(乙腈、甲醇)流动相对分离和测定四甲基铵根离子的影响.最佳色谱条件为:以80% 1-乙基-3-甲基咪唑四氟硼酸盐水溶液(0.5 mmol/L,乙酸调pH 3....     

The Quantitative Separation of Alkyl and Phenethyl Halides by HPLC

Abstract

A method is described for the quantitative separation of alkyl and phenethyl halides in mixtures containing benzene or toluene. This method involves the isocratic chromatography separation of the mixture, using a ODS column and the detection of the compounds by means of a RI detector.