基于纳米CuZSM-5分子筛的传感器用于沙林检测的研究

将纳米ZSM-5或CuZSM-5分子筛作为敏感膜,结合石英晶体微天平(QCM)制备了对神经毒剂沙林(GB)敏感的传感器,研究了硅铝摩尔比和铜离子修饰对毒剂检测性能的影响.结果表明,硅铝摩尔比为25的纳米CuZSM-5分子筛对GB响应最好,并可对GB进行连续多次检测,其灵敏度为19.1 Hz/(mg·m-3),检出限达1.1 mg·m-3(S/N＝3);线性范围为1.5 ～20.0 mg·m-3,线性相关系数为0.995 8,在毒剂检测中具有较强的应用前景.     

预富集装置在QCM传感器检测芥子气中的运用

在化学战剂的诸种检测方法中, 质量型微传感器以其响应快速、使用简便等优点成为一种理想的检测手段. 但是这种传感器的使用往往受到检出限的限制, 对于低浓度的毒剂不能及时报警. 预富集技术的运用可以提高微传感器的检测限. 本文研制了一种预富集装置并对其进行了初步测试. 芥子气通过此预富集装置之后在QCM(石英晶体微天平)传感器上的检出限可以达到0.1 mg/m3.     

基于纳米β分子筛的石英晶体微天平沙林传感器研究

以纳米β(Cuβ)分子筛为敏感膜,结合石英晶体微天平(QCM)制备了对神经毒剂沙林(GB)敏感的传感器。结果表明,纳米β(Cuβ)分子筛对GB响应较纳米ZSM-5更灵敏,在热空气吹扫下可连续多次检测,其灵敏度为23.6Hz/(mg.m-3)(26.8Hz/(mg.m-3)),检出限(S/N=3)为0.96mg.m-3(0.90mg.m-3);线性范围1.50～18.24mg.m-3,线性相关系数为0.9910(0.9888)。该法在毒剂检测中具有一定的应用前景。     

超支化敏感聚合物基于QCM检测痕量TNT爆炸物

为对TNT类爆炸物进行痕量检测,以石英晶体微天平(QCM)传感器为平台,用具有氢键酸性的氟化醇为敏感端基的超支化敏感聚合物材料构造了化学传感器。制备的QCM传感器可以在室温下对2.2×10~(-10)mol/L浓度以上的TNT气体进行响应;连续循环检测3次TNT气体未见信号衰减;对H_2O、乙醇、H_2、H_2S、SO_2、甲烷和NO_2等气体有良好的抗干扰能力;QCM传感器可以用于对TNT类爆炸物的痕量检测。     

分子印迹纳米膜的制备及其在检测神经性毒剂沙林中的应用

采用电化学聚合法首次合成了对有机磷毒剂沙林有快速响应和高灵敏度的分子印迹纳米膜。用压电晶体频移法测出其膜厚约为35nm，对影响电聚合反应的因素(如模板分子浓度、单体浓度、扫描电位和扫描次数)进行了筛选，进而在石英晶体微天平(QCM)上制成了纳米分子印迹传感器。这种新型传感器响应速度快(最初响应时间2s)，抗干扰能力强，检测范围宽(O．7～50μL/L)，灵敏度高(1nL/L)。     

石英晶体微天平传感器及其在生物检测中应用的研究进展

石英晶体微天平(Quartz crystal microbalance,QCM)是一种具有灵敏度高、免标记、可实时在线检测等优点的重要分析工具。在生物检测领域,QCM与多种信号放大方法相结合,广泛应用于对生物分子的高灵敏检测。新型耗散型QCM(QCM-D)通过对薄膜厚度、粘弹性等的研究,主要用于考察生物分子的吸附分离、构型变化等微观过程。本文主要阐述了QCM及QCM-D生物传感器的构建及其在DNA、蛋白质、细胞和微生物检测中的研究进展。     

甲基磷酸二甲酯气体的石英晶体微天平流动检测方法研究

制作了以乙基纤维素为敏感膜的石英晶体微天平(QCM)传感器,设计了可配制不同气体浓度的QCM流动检测系统,并用气相色谱/火焰光度检测器(GC/FPD)作为气体浓度的分析手段,建立了QCM流动检测方法。用该方法对甲基磷酸二甲酯(DMMP)的分析结果表明,在16.5~1.47×103μg/L范围内呈现良好的线性关系(r=0.998 8),检出限可达1.64μg/L,RSD为4.21%。该方法稳定性好,灵敏度高,重现性好,为进一步研究化学战剂的检测提供了方法和依据。     

基于石英晶体微天平的信号放大技术在肿瘤标志物检测中的应用

石英晶体微天平(quartz crystal microbalance, QCM)是一种质量敏感型传感器,近年来被广泛应用于多个领域的分析检测.为了进一步提高检测灵敏度,开发了多种QCM信号放大方法.本文综合介绍了各种QCM信号放大方法,主要聚焦于肿瘤标志物检测中的应用,涉及对核酸序列、蛋白以及肿瘤细胞的检测. QCM的信号放大方法主要是基于质量放大的原理,主要放大技术包括:生物分子偶联、纳米颗粒偶联、生物催化产生不溶物沉淀、金属还原沉积、DNA复制/杂交、晶体原位生长.质量放大子的设计和使用大大增强了QCM的检测能力,提高了其检测灵敏度,拓宽了QCM的应用范围.     

石英晶体微天平在手性识别中的应用

石英晶体微天平(QCM)是一类重要的质量型检测器,因具有灵敏度高、分析速度快、检测成本低等优点而具有极好的应用前景,现已广泛应用于环境监测、药物分析、食品质量控制等诸多领域。手性工程的崛起对简单、快速、在线的手性检测技术提出了挑战,QCM手性传感器就是其中一个重要的发展分支。该文简要介绍了QCM的典型实验装置和基本传感原理,详细综述了近年来QCM在手性识别领域的研究进展,包括以环糊精衍生物、分子印迹聚合物、氨基酸衍生物等为手性主体的QCM在手性识别中的应用,并对其今后的发展进行了展望。     

不同种类敏感膜修饰的QCM气体传感器研究现状

石英晶体微天平(quartz crystal microbalance,QCM)是一种对质量变化敏感的器件,具有灵敏度高、成本低廉、操作简单、可实时在线检测等优点,在气体传感领域受到了广泛关注。敏感材料是石英晶体微天平气体传感器的关键组成部分,本文综述了不同敏感材料包括有机聚合物、超分子化合物、离子液体和分子液体以及近年来备受关注的纳米材料修饰的QCM对特定气体传感检测的研究现状,详细介绍了纳米材料为敏感膜的QCM气体传感器对不同气体传感检测的研究现状及相关敏感机理。最后,在国内外研究现状的基础上,展望了敏感材料的发展前景。QCM作为一种成本低廉、操作方便、测量精度高的气体传感检测器件,将会有更加广阔的应用前景。     

Array of Love-wave sensors based on quartz/Novolac to detect CWA simulants

An array of Love-wave sensors based on quartz and Novolac has been developed to detect chemical warfare agents (CWAs). These weapons are a risk for human health due to their efficiency and high lethality; therefore an early and clear detection is of enormous importance for the people safety. Love-wave devices realized on quartz as piezoelectric substrate and Novolac as guiding layer have been used to make up an array of six sensors, which have been coated with specific polymers by spin coating. The CWAs are very dangerous and for safety reasons their well known simulants have been used: dimethylmethyl phosphonate (DMMP), dipropyleneglycol methyl ether (DPGME), dimethylmethyl acetamide (DMA), dichloroethane (DCE), dichloromethane (DCM) and dichloropentane (DCP). The array has been exposed to these CWA simulants detecting very low concentrations, such as 25 ppb of DMMP, a simulant of nerve agent sarin. Finally, principal component analysis (PCA) as data pre-processing and discrimination technique, and probabilistic neural networks (PNN) as patterns classification technique have been applied. The performance of the sensor array has shown stability, accuracy, high sensitivity and good selectivity to these simulants.     

Electrocatalysis of Chemical Warfare Agent Sulfur Mustard in Room Temperature Ionic Liquid

Room temperature ionic liquids (RTILs) have the potential for being ideal alternatives for organic solvents in chemical warfare agent (CWA) electrochemical reactions. In this paper, electrocatalysis of CWA sulfur mustard (SM) was achieved by exploring the potential advantage of RTIL methyltrioctylammonium bis (trifluoromethylsulfonyl) imide and further this methodology was used for the detection of CWA. The hydrophobicity of this RTIL offers the opportunity to use this methodology in field condition without environmental humidity effect. The diffusion coefficient calculated for SM in RTIL was 0.196×10⁻⁹ cm²/s. The electrochemical parameters deduced from cyclic voltammetry such as electron transfer coefficient (α), electron transfer number (n) and heterogenous rate constant were estimated 0.11, 2 and 4.41 s⁻¹, respectively. The electrocatalytic activity of the RTIL toward the electrochemical reduction and oxidation of CWA is evidenced, showing the potential of this novel approach for the oxidation of other toxic CWAs. The new RTIL based strategy provides an opportunity to develop field deployable detection of CWA and could provide a new paradigm shift in CWA detection approach, addressing the escalating threat of CWA.     

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.     

Determination of soman and VX degradation products by an aspiration ion mobility spectrometry

An aspiration type ion mobility spectrometry (IMS) has been used to determine chemical warfare agent (CWA) degradation products from liquid samples. This technique is based on ion mobility which depends on the molecular weight, charge and shape. With this method, it is possible to measure the mobility distribution of positive and negative ion clusters simultaneously in six different electrodes. Each measuring electrode determines a different portion of the ion mobility distribution formed within the cell’s radioactive source. The strongest responses for all CWA degradation products and 2-propanol were seen in the order of sixth, fifth and second channels. On the basis of projection calculation, the fingerprints for 2-propanol and soman (GD; pinacolyl methylphosphonofluoridate) and VX o-ethyl-S-[2(diisopropylamino)ethyl] methylphosphonothioate) degradation products can be separated from each other. The detection levels for ethyl methylphosphonate (EMPA), pinacolyl methylphosphonate (PMPA), and ethylphosphonic acid (EPA) were 37.2 (37.2 μg/ml), 54.1 (54.1 μg/ml) and 55.1 ppm (55.1 μg/ml), respectively. However, the separation efficiency between different CWA degradation products was quite poor. The projections of these compounds were between 0.9976 and 0.9989, and this means that these fingerprints were identical. Thus, it is only possible to get one profile for all these degradation products of soman and VX. The data provided show that IMS is suitable as a simple technique for screening of CWA degradation products.     

Facility monitoring of chemical warfare agent simulants in air using an automated, field-deployable, miniature mass spectrometer

Vapors of four chemical warfare agent (CWA) stimulants, 2-chloroethyl ethyl sulfide (CEES), diethyl malonate (DEM), dimethyl methylphosphonate (DMMP), and methyl salicylate (MeS), were detected, identified, and quantitated using a fully automated, field-deployable, miniature mass spectrometer. Samples were ionized using a glow discharge electron ionization (GDEI) source, and ions were mass analyzed with a cylindrical ion trap (CIT) mass analyzer. A dual-tube thermal desorption system was used to trap compounds on 50:50 Tenax TA/Carboxen 569 sorbent before their thermal release. The sample concentrations ranged from low parts per billion [ppb] to two parts per million [ppm]. Limits of detection (LODs) ranged from 0.26 to 5.0 ppb. Receiver operating characteristic (ROC) curves are presented for each analyte. A sample of CEES at low ppb concentration was combined separately with two interferents, bleach (saturated vapor) and diesel fuel exhaust (1%), as a way to explore the capability of detecting the simulant in an environmental matrix. Also investigated was a mixture of the four CWA simulants (at concentrations in air ranging from 270 to 380 ppb). Tandem mass (MS/MS) spectral data were used to identify and quantify the individual components.     

Recent Advances in Electrochemical Sensors for Detecting Weapons of Mass Destruction. A Review

The detection of chemical warfare agents (CWA) has become a worldwide security concern in light of the many recent international threats utilizing nerve agents. Among a variety of detection methods that have been developed for CWA, electrochemical sensors offer the unrivaled merits of high sensitivity, specificity and operational simplicity. Recent insights into novel fabrication methodologies and electrochemical techniques have resulted in the demonstration of electrochemical sensors able to address many of the limitations of conventional methodologies. This article reviews recent advances and developments in the field of electrochemical biosensors based detection of nerve agent and their utility for decentralized threat detection. With continued innovations and attention to key challenges, it is expected that electrochemical sensors will play a pivotal role in the CWA detection scenario. This review concludes with the implications of the electrochemical sensing platforms along with future prospects and challenges.     

Ion-pair solid-phase extraction and gas chromatography-mass spectrometric determination of acidic hydrolysis products of chemical warfare agents from aqueous samples

The chemical warfare agents (CWA) degrade rapidly in aqueous samples and convert to acidic degradation products. Extraction and identification of the degradation products from complex matrices using simple sample preparation and sensitive detection and identification is the most important step in the off-site analysis of samples. In this present study, we report a simple sample preparation step based on ion-pair (IP) solid-phase extraction (SPE) for the extraction of acidic degradation products of CWA namely methyl, ethyl, propyl phosphonic acids, thiodiglycolic acid and benzilic acid. The analysis was performed on GC-MS in electron impact ionization mode. Three IP reagents triethylamine (TEA), tetrabutylammonium bromide (TBAB) and cetyltrimethyl ammonium bromide (CTAB) were used. The recoveries were estimated using the internal and external standard methods. The recovery of the compounds was almost negligible when TEA was used as IP reagent. The recoveries obtained when TBAB and CTAB were used as IP reagents were high and reproducible. The recovery of test chemicals is above 90%, except for methyl phosphonic acid and ethylphosphonic acid (20.6 +/- 3.2% and 35.8 +/- 2.5%, respectively). The minimum detection limits of the method were calculated for all chemicals in both full scan and selected ion monitoring modes. The test chemicals could be detected in microgram per litre quantities by the IP-SPE method.     

Electrochemical Sensing of Chemical Warfare Agent Based on Hybrid Material Silver‐aminosilane Graphene Oxide

The threat from chemical warfare agents (CWAs) imparts an alarming call for the global community not limited to human being but also extends as unprecedented environmental threat, hence, timely detection and degradation in the event of CWAs attack is very crucial. Herein, we describe a hybrid material of 3‐aminopropyltriethoxysilane (APTES) modified graphene oxide (GO) on glassy carbon (GC) electrode along with electrodeposited silver nanodendrimers (AgNDs) for the electrochemical detection and degradation of CWA sulphur mustard (HD). The AgNDs/APTES‐GO hybrid material was characterized by SEM, EDX, BET, TGA, Raman, UV‐Vis, XPS and XRD techniques. The AgNDs/APTES‐GO modified GC electrode was also characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Electrochemical studies indicated presence of electrocatalysis owing to the synergistic effect of AgNDs and GO for sensing CWA HD via reductive dehalogenation. The AgNDs/APTES‐GO modified GC electrode exhibited linearity for CWA HD from 5.3 μM to 42.4 μM. Constant potential electrolysis was performed with modified electrode and degradation products were analysed using GC‐MS, highlighting the great potential of graphene based hybrid material. This new strategy provides an opportunity for the development of “detect and destroy” system for the CWAs and other environmental toxic pollutant, which could help in mitigation of on‐ site events for first responders.     

压电晶体传感器阵列在补体系统免疫分析中的应用

将压电石英晶体阵列应用于补体系统免疫分析中,从而发展了一种新型的同步免疫分析方法,并对补体系统的四种成分（C4,C5,C1q,B因子）进行了分析测试。通过对不同条件（即抗体效价不同）下的多组分分析物进行同步检测,研究了补体系统免疫反应的特性和该传感器阵列的响应特性。差频信号的测量消除了粘度、温度和电导率的影响,同时对该传感器阵列晶体间的干扰进行了测试。该方法操作简单、准确、灵敏度较高。