Hydrogen bond acidic polymers for surface acoustic wave vapor sensors and arrays

Four hydrogen bond acidic polymers are examined as sorbent layers on acoustic wave devices for the detection of basic vapors. A polysiloxane polymer with pendant hexafluoro-2-propanol groups and polymers with hexafluorobisphenol groups linked by oligosiloxane spacers yield sensors that respond more rapidly and with greater sensitivity than fluoropolyol, a material used in previous SAW sensor studies. Sensors coated with the new materials all reach 90% of full response within 6 s of the first indication of a response. Unsupervised learning techniques applied to pattern-normalized sensor array data were used to examine the spread of vapor data in feature space when the array does or does not contain hydrogen bond acidic polymers. The radial distance in degrees between pattern-normalized data points was utilized to obtain quantifiable distances that could be compared as the number and chemical diversity of the polymers in the array were varied. The hydrogen bond acidic polymers significantly increase the distances between basic vapors and nonpolar vapors when included in the array.     

Quartz crystal microbalance sensor for organic vapor detection based on molecularly imprinted polymers

Molecularly imprinted polymers on quartz crystal microbalances (QCM) are examined for their ability to detect vapors of small organic molecules with greater sensitivity and selectivity than the traditional amorphous polymer coatings. Hydroquinone and phenol serve as noncovalently bound templates that generate shape-selective cavities in a poly(acrylic) or poly(methacrylic) polymer matrix. The imprinted polymers are immobilized on the piezoelectric crystal surface via a precoated poly(isobutylene) layer. The behavior of the imprinted polymer films is characterized by the dynamic and steady-state response of the QCM frequency to pulses of organic vapors in dry air. The apparent partition coefficients are determined for imprinted and nonimprinted polymers prepared by two synthetic methods and for varying mole ratios of template to monomer. The hydroquinone-imprinted polymers and, to a lesser extent, the phenol-imprinted polymers exhibit greater sensitivity and higher selectivity than the nonimprinted polymers toward organic vapors that are structurally related to the templates. These results indicate that molecularly imprinted polymers are promising for the development of selective piezoelectric sensors for organic vapor detection.     

High-performance taste sensor made from Langmuir-Blodgett films of conducting polymers and a ruthenium complex

A sensor array made up of nanostructured Langmuir-Blodgett (LB) films is used as an electronic tongue capable of identifying sucrose, quinine, NaCl, and HCl at the parts-per-billion (ppb) level, being in some cases 3 orders of magnitude below the human threshold. The sensing units comprise LB films from conducting polymers and a ruthenium complex transferred onto gold interdigitated electrodes. Impedance spectroscopy is used as the principle of detection, and the importance of using nanostructured films is confirmed by comparing results from LB films with those obtained from cast films.     

Dechlorination of trichloroethylene in aqueous solution by noble metal-modified iron

Bimetallic particles are extremely interesting in accelerating the dechlorination of chlorinated organics. Four noble metals (Pd, Pt, Ru and Au), separately deposited onto the iron surface through a spontaneous redox process, promoted the TCE dechlorination rate, and the catalytic activity of the noble metal followed the order of Pd>Ru>Pt>Au. This order was found to be dependent on the concentrations of adsorbed atomic hydrogen, indicating that the initial reaction was cathodically controlled. Little difference in the distribution of the chlorinated products for the four catalysts (cis-DCE: 51%; 1,1-DCE: 27%; trans-DCE: 15% and VC: 7%) was observed. The chlorinated by-products accumulated in both Pt/Fe and Au/Fe (10.3% and 2.5% of the transformed TCE, respectively), but did not accumulate in Pd/Fe and Ru/Fe. Ru/Fe was further examined as an economical alternative to Pd/Fe. The 1.5% Ru/Fe was found to completely degrade TCE within 80 min. Considering the expense, the yield of chlorinated products and the lifetime of a reductive material, Ru provides a potential alternative to Pd as a catalyst in practical applications.     

Silicone emulsion-enhanced recovery of chlorinated solvents: batch and column studies

Batch and column experiments were conducted to investigate the feasibility of flushing with silicone oil emulsion for the removal of chlorinated solvents, including trichloroethylene (TCE), perchloroethylene (PCE) and 1,2-dichlorobenzene (DCB). In the batch experiments, solubilization potentials of emulsion and effects of surfactants as additives were examined. The emulsion prepared with 2% (v/v) silicone oil could solubilize 90.7% of 10,000 ppm TCE, 97.3% of 4000 ppm PCE and 99.7% of 7,800 ppm DCB. Results of one-dimensional column studies indicated that aqueous solubility and sorption of contaminants determined the flushing efficiency. The addition of surfactants below their critical micelle concentration (CMC) did not affect the removal of chlorinated solvents in batch and column experiments. The results of this study show that flushing with oil-based emulsion can be applied to treat the chlorinated solvents.     

Indium Tin Oxide Thin-Film Sensor for Detection of Volatile Organic Compounds (VOCs)

Indium tin oxide (ITO) (In₂O₃ + 17% SnO₂) thin films were grown on glass substrate by direct evaporation method. Two thick gold pads were deposited to take out contacts. The response of these films at different operating temperatures, when exposed to various volatile organic compounds (VOCs) such as methanol, ethanol, butanol, and acetone in the concentration range 200-2500 ppm was evaluated. Additionally, the effect of film thickness on the response charateristics of methanol and acetone was studied. The linearity and sensitivity of the sensors were measured. The ITO thin-film sensors showed a sensitivity of 0.256 ohms/ppm to acetone vapors, which was almost linear in the range 200-2500 ppm. In order to improve sensitivity and selectivity, a thin layer of various metal and metal oxides such as Cu and PbO was deposited on the sensor surface to work as catalytic layer and the effect on the performance of the sensor was studied. The response and recovery times of the sensor were determined for acetone vapors and were found to be 155 sec and 110 sec, respectively.     

Reactivity of Fe(II)/cement systems in dechlorinating chlorinated ethylenes

Ferrous iron (Fe(II)) in combination with Portland cement is effective in reductively dechlorinating chlorinated organics and can be used to achieve immobilization and degradation of contaminants simultaneously. Reactivities of chlorinated ethylenes (perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC)) in Fe(II)/cement systems were characterized using batch slurry reactors. Reduction kinetics of the chlorinated ethylenes were sufficiently fast to be utilized for the proposed treatment scheme, and were described by a pseudo-first-order rate law. The order of reactivity of the chlorinated ethylenes was TCE>1,1-DCE>PCE>VC. Reduction of TCE and PCE mainly yielded acetylene, implying that the transformation of the two compounds occurred principally via reductive beta-elimination pathways. Transformation of 1,1-DCE and VC gave rise to primarily ethylene, implying that major degradation pathways were a reductive alpha-elimination for the former and a hydrogenolysis for the latter. The reactivity of the Fe(II)/cement systems in dechlorinating TCE was proportional to Fe(II) dose when the Fe(II)/cement mass ratio varied between 5.6 and 22.3%. The Fe(II)/cement systems with a higher Fe(II) loading were less extensively affected by pH in reductive reactions for TCE than in the previous experiments with PCE or chlorinated methanes. Amendment of Fe(II)/cement systems with Fe(III) addition was found effective in increasing the reactivity in the previous study, but the current findings indicated that the extent to which the reaction rate increased by the amendment might be dependent on the source of the cement and/or the compounds tested.     

Detection of low levels of trichloroethylene vapor with Raman spectrometry

The response of a novel fiber-optic Raman probe to low levels of trichloroethylene (TCE) vapors is characterized. The detection limit of the current probe for TCE vapor is 34 mg/L, and the probe exhibits a fully reversible response. The probe uses an organic-polymer, low-density polyethylene to concentrate TCE vapors in the optical path of the fiber-optic Raman spectrometer. The relative standard deviation for measurement of 677 mg/L of TCE in the vapor is 0.3%.     

A universal sensor for mercury (Hg, Hg(I), Hg(II)) based on silver nanoparticle-embedded polymer thin film

Detection of mercury at concentration levels down to parts-per-billion is a problem of fundamental and practical interest due to the high toxicity of the metal and its role in environmental pollution. The extensive research in this area has been focused primarily on specific sensing of mercuric (Hg(2+)) ion. As mercury exists in the oxidation states, +2, +1 and 0 all of which are highly toxic, a universal sensor covering all the three while ensuring high sensitivity, selectivity, and linearity of response, and facilitating in situ as well as ex situ deployment, would be very valuable. Silver nanoparticle-embedded poly(vinyl alcohol) (Ag-PVA) thin film fabricated through a facile protocol is shown to be a fast, efficient and selective sensor for Hg(2+), Hg(2)(2+) and Hg in aqueous medium with a detection limit of 1 ppb. The sensor response is linear in the 10 ppb to 1 ppm concentration regime. A unique characteristic of the thin film based sensor is the blue shift occurring concomitantly with the decrease in the surface plasmon resonance absorption upon interaction with mercury, making the sensing highly selective. Unlike the majority of known sensors that work only in situ, the thin film sensor can be used ex situ as well. Examination of the thin film using microscopy and spectroscopy through the sensing process provides detailed insight into the sensing event.     

Preparation and properties of vapor detector arrays formed from poly(3,4-ethylenedioxy)thiophene-poly(styrene sulfonate)/insulating polymer composites

Poly(3,4-ethylenedioxy)thiophene-poly(styrene sulfonate) (PEDOT-PSS) was used as the conductive component in a matrix of chemically different insulating polymers to form an array of vapor detectors. Such composites produced larger relative differential resistance responses when exposed to polar analytes than did the corresponding carbon black filled polymer composite detectors. However, the PEDOT-PSS composites produced smaller responses than carbon black composites when exposed to nonpolar analytes. The resolving power of a PEDOT-PSS detector array was compared to that of a carbon black composite array for a broadly construed set of organic vapors. The PEDOT-PSS array exhibited better, on average, discrimination between pairs of polar analytes and polar/nonpolar analytes than did the carbon black composite array. The carbon black composite array out-performed the PEDOT-PSS array in discriminating between nonpolar compounds. The addition of PEDOT-PSS composites to an array of carbon black composite detectors therefore can produce improved overall discrimination in a vapor sensor system when used in tasks to differentiate between of a broad set of analyte vapors.     

Benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier

This study simulated benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier (ZVI PRB) that reduces trichloroethylene (TCE). The effects of elevated pH (10.5) and the presence of a common TCE dechlorination by product [cis-1,2-dichloroethene (cis-1,2-DCE)] on benzene and toluene biodegradation were evaluated in batch experiments. The data suggest that alkaline pH (pH 10.5), often observed down gradient of ZVI PRBs, inhibits Fe(III)-mediated biotransformation of both benzene and toluene. Removal was reduced by 43% for benzene and 26% for toluene as compared to the controls. The effect of the addition of cis-1,2-DCE on benzene and toluene biodegradation was positive and resulted in removal that was greater than or equal to the controls. These results suggest that, at least for cis-1,2-DCE, its formation may not be toxic to iron-reducing benzene and toluene degrading bacteria; however, for microbial benzene and toluene removal down gradient of a ZVI PRB, it may be necessary to provide pH control, especially in the case of a biological PRB that is downstream from a ZVI PRB.     

Ordered‐Assembly Conductive Nanowires Array with Tunable Polymeric Structure for Specific Organic Vapor Detection

An artificial organic vapor sensor based on a finite number of 1D nanowires arrays can provide a strategy to allow classification and identification of different analytes with high efficiency, but fabricating a 1D nanowires array is challenging. Here, a coaxial Ag/polymer nanowires array is prepared as an organic vapor sensor with specific recognition, using a strategy combining superwettability‐based nanofabrication and polymeric swelling‐induced resistance change. Such organic vapor sensor containing commercial polymers can successfully classify and identify various organic vapors with good separation efficiency. An Ag/polymer nanowires array with synthetic polyethersulfone polymers is also fabricated, through molecular structure modification of the polymers, to distinguish the similar organic vapors of methanol and ethanol. Theoretical simulation results demonstrate introduction of specific molecular interaction between the designed polymers and organic vapors can improve the specific recognition performance of the sensors.     

Multianalyte chemical identification and quantitation using a single radio frequency identification sensor

We demonstrate an approach for multianalyte chemical identification and quantitation using a single conventional radio frequency identification (RFID) tag that has been adapted for chemical sensing. Unlike other approaches of using RFID sensors, where a special tag should be designed at a much higher cost, we utilize a conventional RFID tag and coat it with a chemically sensitive film. As an example, we demonstrate detection of several vapors of industrial, health, law enforcement, and security interest (ethanol, methanol, acetonitrile, water vapors) with a single 13.56-MHz RFID tag coated with a solid polymer electrolyte sensing film. By measuring simultaneously several parameters of the complex impedance from such an RFID sensor and applying multivariate statistical analysis methods, we were able to identify and quantify several vapors of interest. With a careful selection of the sensing film and measurement conditions, we achieved parts-per-billion vapor detection limits in air. These RFID sensors are very attractive as ubiquitous multianalyte distributed sensor networks.     

Microfabricated gas chromatograph for the selective determination of trichloroethylene vapor at sub-parts-per-billion concentrations in complex mixtures

A complete field-deployable microfabricated gas chromatograph (μGC) is described, and its adaptation to the analysis of low- and subparts-per-billion (ppb) concentrations of trichloroethylene (TCE) vapors in complex mixtures is demonstrated through laboratory testing. The specific application being addressed concerns the problem of indoor air contamination by TCE vapor intrusion. The μGC prototype employs a microfabricated focuser, dual microfabricated separation columns, and a microsensor array. These are interfaced to a nonmicrofabricated front-end pretrap and high-volume sampler module to reduce analysis time and limits of detection (LOD). Selective preconcentration and focusing are coupled with rapid chromatographic separation and multisensor detection for the determination of TCE in the presence of up to 45 interferences. Autonomous operation is possible via a laptop computer. Preconcentration factors as high as 500?000 are achieved. Sensitivities are constant over the range of captured TCE masses tested (i.e., 9-390 ng), and TCE is measured in a test atmosphere at 120 parts-per-trillion (ppt), with a projected LOD of 40 ppt (4.2 ng captured, 20 L sample) and a maximum sampling + analytical cycle time of 36 min. Short- and medium-term (1 month) variations in retention time, absolute responses, and response patterns are within acceptable limits.     

Highly Sorbent Films Derived from Ni(SCN)(2)(4-picoline)(4) for the Detection of Chlorinated and Aromatic Hydrocarbons with Quartz Crystal Microbalance Sensors

A quartz crystal microbalance (QCM) spray-coated with a Ni(SCN)(2)(4-picoline)(4) film is a sensitive detector for small aromatic (benzene, toluene) and chlorinated (trichloroethylene, perchloroethylene) vapors with a planar molecular geometry. Frequency changes during transient exposures to these vapors are rapid and reversible. In contrast, frequency changes during transient exposures to carbon tetrachloride vapor exhibit a very slow rise and decay. Impedance studies demonstrate that the QCMs are responding only to mass changes in the film. Calibration curves exhibit both linear and near-saturation responses, depending on the vapor and vapor concentration. Partition coefficients obtained from the linear response regimes of the calibration curves are in the 10?000-100?000 range, more than an order of magnitude larger than the partition coefficients for a prototypical soft polymer, poly(isobutylene). Despite the absence of evidence for crystallinity by optical or X-ray diffraction methods, the spray-coated films appear to be forming clathrates with the organic vapors. The Ni(SCN)(2)(4-picoline)(4) film is promising for the development of very sensitive and partially selective piezoelectric sensors for nonpolar or weakly polar organic vapors in air.     

Hole doping and surface functionalization of single-walled carbon nanotube chemiresistive sensors for ultrasensitive and highly selective organophosphor vapor detection

We developed a chemiresistive sensor based on doped and functionalized semiconducting single-walled carbon nanotube (SWNT) networks for ultrasensitive and rapid detection of dimethyl methylphosphonate (DMMP) (simulant of nerve agent sarin) vapor. The semiconducting SWNT network was deposited between interdigitated electrodes and modified by solid organic acid tetrafluorohydroquinone (TFQ). The TFQ molecules could not only selectively bind DMMP onto the sidewalls of SWNTs via the strong hydrogen bonding interaction, but also tailor the electronic properties of SWNTs via heavy hole doping. This synergetic effect significantly improved the sensitivity of the devices, and enabled the sensors to easily detect DMMP at 20 parts-per-trillion (ppt) concentration with a response time of less than 2 min, without the need for pre-concentration of the analytes. This sensitivity is about five orders of magnitude higher than that of the unmodified SWNT chemiresistor, and also significantly higher than that of the functionalized SWNT chemiresistors previously reported. Moreover, the SWNT-TFQ sensors could be recovered when DMMP is replaced with referencing gas. The SWNT-TFQ sensors also show excellent selectivity toward DMMP over some interfering organic vapors. The response mechanism, i.e. charge transfer and dedoping was investigated.     

Dual-chemiresistor GC detector employing monolayer-protected metal nanocluster interfaces

The synthesis and testing of two gold-thiolate monolayer-protected (nano)clusters as interfacial layers on a dual-chemiresistor vapor sensor array are described. Responses (changes in dc resistance) to each of 11 organic solvent vapors are rapid, reversible, and linear with concentration at low vapor concentrations, becoming sublinear at higher concentrations. Limits of detection (LODs) range from 0.1 to 24 parts per million and vary inversely with solvent vapor pressure. When configured as a GC detector and used to analyze 0.5-L preconcentrated samples of the 11-vapor mixture, the array provides LODs of < or = 700 parts per trillion for most vapors, comparing favorably with those from an integrated array of polymer-coated surface acoustic wave sensors configured and tested similarly. This first report on the use of such an array as a GC detector shows that the combination of response patterns and GC retention times improves capabilities for vapor recognition compared to the sensor array alone or to single-detector GC systems. Spray-coated nanocluster thin films can be deposited reproducibly and exhibit response stability in air that ranges from fair to excellent for up to several months. Scaling the active device area down by a factor of 16 has no significant effect on sensitivity. Implications of these results for portable vapor sensing systems are discussed.     

聚甲基丙烯酸丁酯/炭黑导电复合材料用于空气中有机蒸气检测

研究了聚甲基丙烯酸丁酯/炭黑(PBMA/CB)复合材料在空气中低浓度有机蒸气检测方面的应用.结果表明,在相同蒸气浓度时,复合材料对乙酸乙酯和甲苯蒸气的电阻响应灵敏度更高,这是因为复合材料对有机蒸气的气敏响应性能不仅与聚合物基体和有机溶剂间的相溶性有关,而且与有机蒸气分压有关.复合材料的电阻响应程度随有机蒸气分压的变化与Ⅲ型吸附曲线相似.另外,通过改变发黑的质量分数、测试温度等,可以有效地改善复合材料对空气中低浓度有机蒸气的电阻响应性能.