Optical parameters of calix[4]arene films and their response to volatile organic vapors

The Langmuir-Blodgett (LB) technique was employed to produce thin LB films using an amphiphilic calix-4-resorcinarene onto different substrates such as quartz, gold coated glass and quartz crystals. The characteristics of the calix LB films are assessed by UV-visible, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) measurements. UV-vis and QCM measurements indicated that this material deposited very well onto the solid substrates with a transfer ratio of >0.95. Using SPR data, the thickness and refractive index of this LB film are determined to be 1.14 nm/deposited layer and 1.6 respectively. The sensing application of calixarene LB films towards volatile organic vapors such as chloroform, benzene, toluene and ethanol vapors is studied by the SPR technique. The response of this LB film to saturated chloroform vapor is much larger than for the other vapors. The response is fast and fully recoverable. It can be proposed that this sensing material deposited onto gold coated glass substrates has a good sensitivity and selectivity for chloroform vapor. This material may also find potential applications in the development of room temperature organic vapor sensing devices.     

Self-assembly of polyelectrolytic multilayer thin films of polyelectrolytes on quartz crystal microbalance for detecting low humidity

Low-humidity sensors were made by layer-by-layer (LBL) self-assembly of poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA) or poly(styrenesulfonic acid) sodium salt (PSS) and poly(allylamine hydrochloride) (PAH) into multilayer thin films on a gold electrode of quartz crystal microbalance (QCM). The thin films were characterized by QCM and atomic force microscopy (AFM). The effects of maleic acid (MA) in PSSMA, the number of layers and the ionic strength on the low-humidity sensing properties (sensitivity) were compared with those of PSS. The sensitivity of the PSSMA/PAH multilayer thin film exceeded that of the PSS/PAH multilayer thin film when the multilayered thin films of polyelectrolytes were prepared from solutions without NaCl. The sensitivity of both PSSMA/PAH and PSS/PAH multilayered thin films was increased by increasing the number of layers and by adding salt to the deposition solution. The PSS/PAH multilayered thin film that was prepared from the solutions with NaCl had the highest sensitivity (1.923 −ΔHz/Δppm_v at 27.5 ppm_v) and a short response time. Spin-coating was also adopted to fabricate PSS-based low-humidity sensors for comparison.     

Polyaniline–TiO2 nano-composite-based trimethylamine QCM sensor and its thermal behavior studies

Inorganic/organic composites are very attractive due to synergetic behavior and a wide range of potential use. A polyaniline–TiO₂ nano-composite, obtained by combination of chemical polymerization and a sol–gel method, was deposited on the electrode of quartz crystal to implement a quartz crystal microbalance (QCM) chemical sensor. The morphology of the composite film was studied by scanning electron microscopy (SEM) measurements. The coated quartz crystal and a non-coated quartz crystal were mounted in a sealed chamber, and their frequency difference was monitored. When analyte vapor was injected into the chamber, gas absorption decreased the frequency of the coated quartz crystal and thereby caused an increase of the frequency difference between the two crystals. The frequency difference change response towards trimethylamine was evident and could be recovered by N₂ purgation easily. The calibration curve towards trimethylamine, its long-term stability and selectivity were investigated. The thermal behavior of the sensing characteristics was compared with that of a polyaniline QCM sensor. Fourier transform infrared (FTIR) spectra of polyaniline and polyaniline–TiO₂ nano-composite and QCM data under various conditions were used to study the effect of thermal treatment.     

基于PVDF膜的QCM对DMMP的气敏特性研究

神经性毒剂是化学战剂的重要分支.为了检测神经性毒剂模拟剂甲基膦酸二甲酯(DMMP),使用毛细管在压电石英晶体(QCM)的电极上滴涂上不同质量的聚偏氟乙烯(PVDF)溶液,干燥后作为敏感膜.室温下测试QCM对不同浓度的DMMP的响应情况,发现QCM的频率变化与气体浓度有着良好的线性关系.该实验结果表明,PVDF可以作为检测DMMP的很好的敏感材料.     

测定DMMP的PMPS-QCM传感器的研究

研究了新型敏感材料PMPS对神经性毒剂模拟剂甲基膦酸二甲酯(DMMP)的响应特性.在石英晶体微天平(QCM)的电极上滴涂上PMPS溶液得到敏感膜,发现QCM当响应、恢复时间为30-60 s时,可以产生大约11.83 Hz/ppm(ppm i.e.×10-6)的频率响应,理论上LOD为0.25 ppm(ppm i.e.×10-6),并具有较好的重复性和选择性.该实验结果表明,与PVDF相比,PMPS是一种更适宜检测DMMP的敏感材料.     

涂敷脲醛树脂的石英晶体微天平湿度传感器

在碱性条件下预先合成脲醛树脂单体,然后在酸性条件下于石英晶体的电极上原位合成脲醛树脂高分子薄膜,制备了石英晶体微天平湿度传感器。同时考察敏感膜厚度对检测灵敏度的影响以及传感器的响应特性、重复性和稳定性。试验结果表明:涂敷脲醛树脂薄膜的传感器频率随测试的相对湿度变化明显,传感器具有良好的重复性和稳定性。制作的湿度传感器可应用于实际的生产、生活中。     

Chemically modified copolymer coatings for mass-sensitive toluene vapor sensors

Styrene-co-chloromethyl styrene copolymers chemically modified with various kinds of monoamines or diamines were synthesized. Their sensing properties based on toluene vapor sorption/desorption behaviors were measured using a quartz crystal microbalance (QCM) technique. Introduction of aliphatic diamine compounds having a proper chain length (e.g., N,N-dimethyl-1,3-propanediamine (DMPDA)) into the structure of the copolymer realized improvements to the toluene vapor sorption capacity, the response time, and reversibility compared to the conventional polymer coatings. FTIR analysis suggests the formation of a loosely cross-linked structure, resulting in the promotion of toluene vapor diffusion into the film.     

Mixed self-assembled lipopolymers with spacer lipids enhancing sensitivity of lipid-derivative QCMs for odor sensors

An odor sensing system using a quartz crystal microbalance (QCM) sensor array and pattern recognition technique has been for years a main research topic in our group. For the general field of artificial olfaction using acoustic-wave based sensors such as QCMs it is vital to search for novel sensing materials. Here we present recent results of our ongoing study on application of pegylated lipids as coatings for QCM odor-sensors. The method presented herein is based on self-assembling of lipids and lipid-derivatives on the QCM surfaces. The disulphide-terminated lipids and lipopolymers are co-chemisorbed onto gold electrodes of QCM sensors by simple immersion in ethanolic solutions. This creates porous supports onto which additional layers of lipopolymers are physisorbed. The method allows for fabrication of lipopolymeric QCM odor-sensors with enhanced sensitivity to odorants, capable of very good discrimination among odorant samples—according to the functional group of an odorant.     

Development and evaluation of piezoelectric-polymer thin film sensors for low concentration detection of volatile organic compounds related to food safety applications

In this study, the regioregular poly (3-hexyl thiophene) (rr-P3HT) based piezoelectric sensors were developed and evaluated to detect alcoholic volatile organic compounds (VOCs) associated with spoiled and Salmonella typhimurium contaminated packaged beef headspace. The drop coating technique was used to deposit thin films of rr-P3HT on both the sides of quartz crystal microbalance (QCM) electrode. The QCM polymer sensors were found to provide repeatable and reproducible sensor response to alcohol VOCs with a fast recovery (<2 min) at room temperature (25 °C). The principal component analysis on the sensors sensitivities was performed to discriminate the sensed alcohol VOCs, namely: 3-methyl-1-butanol from 1-hexanol. The QCM polymer sensors demonstrated selective response to low concentration of 3-methyl-1-butanol (average estimated lowest detection limit (LDL): 4.35 ppm) and to 1-hexanol (average estimated LDL: 3.20 ppm). The 30 days storage study performed on QCM sensors showed identical sensitivity responses for sensing 3-methyl-1-butanol and 1-hexanol at low concentrations.     

ZnO纳米棒修饰的QCM气体传感器检测NH_3研究

主要介绍了ZnO纳米棒修饰的石英晶体微天平(QCM)气体传感器的制备与测试。采用两步法在石英晶振片表面制备直径为100 nm的ZnO纳米棒敏感膜,构成QCM NH3传感器。检测系统为自主研发的基于LabVIEW平台的QCM气体传感器频率测试软件。检测NH3的体积分数为5×10-6~50×10-6,响应时间均在10 s以内,最大频差值为10.9 Hz,响应最大频差值与NH3体积分数呈现良好的线性关系。室温条件下,ZnO纳米棒敏感膜可以完全实现吸附解吸过程,具有可逆性。该传感器性能稳定,响应灵敏,具有重复性。     

Dew point measurement for organic vapor mixture using a quartz crystal sensor

A dew point measurement device for organic vapor mixtures using a quartz crystal sensor was proposed, and its performance was examined with acetone–methanol mixtures. The device has a sensor module to accommodate the quartz crystal sensor and a cooling system. The variation in resonant frequency of the sensor indicates the condensation of sample vapor, which tells the beginning moment of condensation, i.e., dew point. The measurement results with the proposed device were compared with the predicted dew points from the UNIQUAC equation and other experimental outcome to examine the performance of the device. Though some measurement error was yielded, it is proved that the proposed device is useful for measuring the dew points of organic vapors at different pressures.     

Enhancing the sensitivity of ionic liquid sensors for methane detection with polyaniline template

Flammable gas sensors are essential in occupational health and safety to prevent fire or explosion in gas facilities and underground mining. Our early study demonstrated that ionic liquid (IL)/quartz crystal microbalance (QCM) gas sensors and sensor arrays were excellent for the detection of various organic vapors at both room temperature and elevated temperatures. In this paper, we developed a general method that significantly enhanced the sensitivity of the IL/QCM sensors for flammable gases detection by immobilizing IL on a conductive polymer polyaniline (PAn) template. Studies were performed to optimize the PAn oxidation states, thickness, and IL concentrations. Results showed that the sensitivity increased with increasing the PAn film thickness and the amount of IL immobilized within the PAn film. The sensitivity depended also on the oxidation state and doping state of PAn. With doped and partially oxidized PAn (emeraldine salt) the IL/QCM sensor showed the best performance. The current detection limit for methane was as low as about 115 ppm at room temperature. The sensitivity also depended on the structure of the IL used. Among the four ILs tested, two of them showed excellent sensitivities after being immobilized in the PAn film.     

Application of sulfuric acid doped poly (m-aminophenol) as aliphatic alcohol vapor sensor material

Chemically synthesized processable poly (m-aminophenol) (PmAP) film was cast from dimethyl sulfoxide solution and doped with sulfuric acid by solution doping technique. This sulfuric acid doped PmAP film shows a good electrical conductivity. The response of doped film under continuous flow of various aliphatic alcohols vapor and air mixture was examined at room temperature (30 °C) and humidity (65% RH). The doped polymer only showed good result for methanol and ethanol vapor and some week response for the isopropanol vapor. A decrease in resistivity of the doped PmAP film was separately observed in air–alcohol vapor at different concentrations. The response of the film increases as the concentration of the alcohol vapor increases in air–alcohols vapor mixture. The kinetics of the response with respect to the alcohol concentration was studied for methanol and ethanol. Sulfuric acid doped and methanol vapor absorbed doped films were characterized by ultraviolet–visible spectroscopic, attenuated total reflectance Fourier transformed infrared spectroscopic and X-ray diffraction analyses. The mechanism of alcohol vapor sensing by sulfuric acid doped PmAP film has been explained on the basis of the above characterizations. All the above facts are trying to explain from the proposed mechanistic point of view.     

Enantioselective molecular imprinting polymer coated QCM for the recognition of l-tryptophan

A new quartz crystal microbalance (QCM) sensor that provides enantioselectivity to tryptophan enantiomers, with a high selectivity and sensitivity, was fabricated by the use of the molecularly imprinted polymers (MIPs) as the artificial biomimetic recognition material. Non-covalent molecular imprinting polymers were synthesized using acrylamide (AM) and trimethylolpropane trimethacrylate (TRIM) as a functional monomer and a cross-linking agent, respectively. The preparation of the thin permeable film coatings on QCM surface is described as well as the results and discussion on the sensitivity and selectivity of the coatings to tryptophan enatiomers under different conditions. The sensor was able to discriminate between the l- and d-tryptophan enantiomers in citric acid buffer solutions owing to the enantioselectivity of the imprinted sites. The detection limit is 8.8 μM. The influence of the cross-linking agent concentration on the sensitivity and selectivity of the fabricated polymer films was investigated and optimized. The enantionmeric composition of l- and d-tryptophan enantiomer mixtures can be determined by measuring the frequency shifts of the sample. The characteristics of the thiol monolayer and MIP film on the surface of the QCM were studied by atomic force microscopy (AFM).     

三氯甲烷在金属有机框架膜上的吸附过程监测

采用石英晶体微天平（QCM）技术动态监测三氯甲烷在[Cu（C24H22N4O3）]·CH2Cl2金属有机框架膜（Cu—MOFs）上的吸附动力学．吸附与解吸过程中膜质量的变化由QCM的频率变化实时传感测量,结果表明,吸附过程符合假二级动力学模型,其中在三氯甲烷蒸气压条件下的吸附速率常数为在1．01×10^5PaNz存在下速率常数的1．4-2．1倍,半数以上的吸附量相对于气相浓度稀释呈现可逆吸附特征。吸附等温线符合Langmuir等温式,在蒸气压与1．01×10^5PaN2存在条件下（25℃）,三氯甲烷在厚度为0．337μm Cu—MOFs上吸附的平衡常数分别为6．47与3．93L／g,最大吸附量分别为27．2与24．7μg／cm^2。     

基于QCM的湿度传感器等效电路模型研究

基于石英晶体微天平(QCM)的湿度传感器是一种以石英晶体为核心元件的新型高灵敏度传感器.根据气相中晶体振荡电路的起振和稳定条件,对晶体表面敏感薄膜吸附水分时等效电路参数的变化进行建模,得到了一种新型的基于QCM的湿度传感器等效电路模型.通过电路仿真软件PSPICE对模型进行仿真,并搭建QCM湿度传感器实验测量平台,结果验证了基于QCM的湿度传感器等效电路模型的有效性和正确性,对QCM湿度传感器的振荡电路的进一步设计和优化具有指导意义.     

Formaldehyde sensors based on nanofibrous polyethyleneimine/bacterial cellulose membranes coated quartz crystal microbalance

A novel formaldehyde sensor based on nanofibrous polyethyleneimine (PEI)/bacterial cellulose (BC) membranes coated quartz crystal microbalance (QCM) has been successfully fabricated. The nanoporous three-dimensional PEI/BC membranes are composed of nanofibers with diameter of 30-60 nm. The sensor showed high sensitivity with good linearity and exhibited a good reversibility and repeatability towards formaldehyde in the concentration range of 1-100 ppm at room temperature. Moreover, the results showed that the sensing properties were mainly affected by the content of PEI component in nanofibrous membranes, concentration of formaldehyde and relative humidity. Additionally, the nanofibrous PEI/BC membrane coated QCM sensors exhibited a good selectivity to formaldehyde when tested with competing vapors. The simple and feasible method to prepare and coat the PEI/BC sensing membranes on QCM makes it promising for mass production at a low cost.     

Ionic liquid thin layer EQCM explosives sensor

An integrated sensor that combines electrochemical and piezoelectric transduction mechanisms into a single miniaturized platform was developed and validated for the detection of nitro aromatic compounds such as ethyl nitrobenzene (ENB) and dinitrotoluene that are analogues of redox active explosives. An ionic liquid (IL) BMIBF₄ was used as both the electrolyte and the sorption solvent for the two-dimensional electrochemical and piezoelectric gas sensors.The electrochemical behaviors of these nitro compounds in BMIBF₄ were studied by cyclic voltammetry, differential pulse voltammetry and square wave voltammetry, in parallel. The electrochemical properties of these compounds resembled the electrochemical reduction processes in their aprotic solutions, showing first a reversible reduction process and then subsequently an irreversible reduction processes. The redox properties of these compounds also depend on the number of nitro groups and the position of the nitro groups on the benzene ring. Square wave voltammetry was used to quantitatively analyze the ENB in BMIBF₄. Reduction peaks in the square wave voltammetric curves could be obtained when the concentrations were at ppm level. A small amount of moisture in the IL electrolyte did not significantly affect the redox behaviors. Piezoelectric quartz crystal microbalance (QCM) electrodes and the electrodes for amperometry were fabricated on a single piece of quartz plate. Detection of the volatile ENB vapor with this integrated EQCM chip was tested with both QCM and amperometric methods. The sensor's signal was related quantitatively to the ENB vapors adsorbed in BMIBF₄ from air. Combining amperometric and QCM detection simultaneously can cross-validate the detection technology, reduce false positives and false negatives and increase the accuracy of the detection.     

Olfactory receptor based piezoelectric biosensors for detection of alcohols related to food safety applications

Our major goal in developing intelligent quality sensors is to detect bacterial pathogens such as Salmonella in the packaged beef. Olfactory sensing of specific volatile organic compounds released by the bacterial pathogens is one of the unique ways for determining contamination in food products. This work aims at developing a biomimetic piezoelectric olfactory sensor for detecting specific gases (alcohols) at low concentrations.The computational simulation was used to determine the biomimetic peptide-based sensing material to be deposited on the quartz crystal microbalance (QCM) sensor. Tripos/Sybyl^®8.0 was used to predict the binding site of an olfactory receptor and determine the binding affinity as well as orientation of the selected ligands (specific molecules) to the olfactory receptor. The designed polypeptide sequence based on the simulation program was synthesized and used as a sensing layer in the QCM crystal. The developed QCM sensors were sensitive to 1-hexanol as well as 1-pentanol as predicted by the simulation algorithm. The estimated lower detection limits of the QCM sensors for detecting 1-hexanol and 1-pentanol were 2-3 ppm and 3-5 ppm, respectively. This study demonstrates the applicability of simulation-based peptide sequence that mimics the olfactory receptor for sensing specific gases.     

Detection of ethanol and methanol vapors using polymer-coated piezoresistive Si bridge

A novel alcohol vapor sensor based on the swelling effect of polymer film is proposed for detection of alcohol such as methanol and ethanol vapor, which is composed of a Si bridge embedded with piezoresistive Wheatstone bridge and an epoxy acrylate thin polymer layer-coated Si bridge. When the polymer layer absorbs alcohol vapor molecules from ambient air, the swelling of the thin polymer layer leads to bending of the Si bridge which causes the piezoresistive Wheatstone bridge to produce an output voltage. A theoretical model of the interaction between Si bridge and polymer layer is presented based on elastic mechanics theory. An equivalent transverse gas load is presented. The output expression of sensor is obtained. The model of the sensor is verified by the experimental results. The experimental results show that the alcohol vapor sensor has good linearity, selectivity and reproducibility. The proposed alcohol vapor sensor has simply principle, mature technology, low cost, and can be integrated with signal processing circuit using the MEMS processes.