毒剂的生化分析技术

本文论述了酶法分析、核酸探针、免疫分析法特别是生物传感器在毒剂检测中的应用，提出了毒剂生化分析的发展方向。     

水和粮食中化学战剂的分析

建立了水和粮食中７种化学战剂沙林、棱曼、塔崩、甲氟膦酸环已酯、Ｓ－（２＝－二惜内基氨乙基）甲基硫直膦酸乙酯（ＶＸ）、俄罗期ＶＸ和芥子气的ＧＣ、璃子选择＿分析方法。染毒水样经二氯甲烷提取,提取液在氮气流下浓缩至１ｍＬ;染毒粮样用蒸馏水提取,提取液离心后过Ｃ１８固相柱,乙腈洗脱,然后用ＧＣ－ＭＳ－ＳＩＭ测定。该法前处理较简便,净化效果好,方法灵敏,适用于军粮、饮水中微量化学战剂的分析。     

Detection of Chemical Warfare Nerve Agents via a Beckmann Fragmentation of Aldoxime

Abstract

A new (E)-pyrene-1-carbaldehyde O-tert-butyldimethylsilyl oxime 3 was synthesized for the detection of chemical warfare nerve agents, O-isopropyl methylphosphonofluoridate (GB) and O-pinacolyl methylphosphonofluoridate (GD). ¹H NMR spectrum showed that the tert-butyldimethylsilyl (TBDMS) group was deprotected using TBAF and the oximate supernucleophile was made. Upon addition of chemical warfare agents (GB and GD) (50 mol%), the reaction was completely finished within 5 min and also the color change of reaction mixture was observed under a hand-held UV lamp with the naked eye.     

Electrochemical Biosensors for Detection of Biological Warfare Agents

This review discusses current development in electrochemical biosensors for detection of biological warfare agents. This could include bacteria, viruses and toxins that are aerosoled deliberately in air, food or water to spread terrorism and cause disease or death to humans, animals or plants. The rapid and unequivocal detection and identification of biological warfare agents is a major challenge for any government including military, health and other government agents. Reliable, specific characterization and identification of the microorganism from sampling location, either air, water, soil or others is required. This review will survey different types of electrochemical biosensors has been developed based on the following: i) Immunosensors ii) PCR (DNA base Sensor) iii) Bacteria or whole cell sensor and iv) Enzyme sensor. This article gives an overview of electrochemical biosensor for detection of biological warfare agents. Electrochemical biosensors have the advantages of sensitivity, selectivity, to operate in turbid media, and amenable to miniaturization. Recent developments in immunofiltration, flow injection, and flow‐through electrochemical biosensors for bacteria, viruses, and toxin detection are reviewed. The current research and development in biosensors for biological warfare agents detection is of interest to the public as well as to the defense is also discussed.     

Monitoring Chemical Warfare Agents: A New Method for the Detection of Methylphosphonic Acid

Methylphosphonic acid (MPA) is the degradation product of many chemical warfare agents. The convenient detection of this substance would aid in field testing to confirm illicit manufacture and use of banned chemical weapons. Efficient functionalization of MPA with an aromatic diazo compound allowed binding by monoclonal antibodies elicited by using an analogous hapten (see scheme). An ELISA assay was rapid, sensitive, and specific.     

化学毒剂探测技术发展现状

化学毒剂(CWAs)作为一种大规模杀伤性武器,具有杀伤力强、影响范围广、防护困难、易于制作施放等特征,从诞生之初即常被用于战争冲突,在现代非对称战争、恐怖袭击中也造成了巨大威胁.因此如何及时地探测化学毒剂成为世界各国国土安全的重点研究方向.该文聚焦于化学毒剂现有主流及具有潜力的各类探测技术,对各种检测技术的基本原理及其...     

Supramolecular Sensing of a Chemical Warfare Agents Simulant by Functionalized Carbon Nanoparticles

Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits noncovalent interactions, in particular hydrogen bonds, to detect DMMP, a simulant of nerve agents. The nanostructure of the sensor combined with the supramolecular sensing approach leads to high binding constant affinity, high selectivity and the possibility to reuse the sensor.     

染毒粮食中7种化学战剂的气相色谱分析方法

为了研究染毒粮食（大米、面粉）中７种化学战剂的检测方法,建立了相应的气相色谱分析方法。该法采用火焰光度检测器检测,ＢＰ－１０毛细管色谱柱分离,二氯甲烷萃取。模拟染毒大米、面粉中化学战剂测定相对误差为２．０％～１２．０％、８．１０％～２７．３％。相对标准偏差分别为０．９％～６．１０％、３．９５％～１６．８％。方法的最低检出浓度为０．０１～２μｇ／ｇ。所建方法操作简便,灵敏度高。     

Decontamination of Chemical Warfare Agents by Novel Oximated Acrylate Copolymer

A novel acrylate copolymer, polymethylacrylate-β-(bromoacetyl ethyl)ester-co-N,N-dimethylacrylamide[P(MABE-co-DMAA)] was synthesized by the copolymerization of N,N-dimethylacrylamide and methylacrylate-β-(bromoacetyl ethyl)ester. Subsequently, the copolymer was oximated by 4-pyridinium aldoxime(4-PAM), and was abbreviated as PAM-P(MABE-co-DMAA). A maximum oxime conversion of 53.7% was obtained. The as-prepared oximated copolymer PAM-P(MABE-co-DMAA) effectively decontaminated chemical warfare agents(CWAs) including methylphosphonofluoridate(sarin or GB), S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate (VX), and 2,2'-dichloroethyl sulfide(sulfur mustard, or HD). The detoxification rates were 90.6% for GB, 85.7% for VX, and 90.5% for HD. Chromogenic analysis, high performance liquid chromatography-mass spectrometry (HPLC/MS) and gas chromatography-mass spectrometry(GC/MS) were used to identify the decontamination products, and the decontamination mechanism was concluded to be a combination of nucleophilic substitution and a second order Beckmann rearrangement. Furthermore, the active decontamination materials, such as decontamination cloths and covers could be made from the oximated copolymer by virtue of its processability, as well as its strong ability to degrade CWA.     

Niobium(V) Saponite Clay for the Catalytic Oxidative Abatement of Chemical Warfare Agents

A Nb^V‐containing saponite clay was designed to selectively transform toxic organosulfur chemical warfare agents (CWAs) under extremely mild conditions into nontoxic products with reduced environmental impact. Thanks to the insertion of Nb^V sites within the saponite framework, a bifunctional catalyst with strong oxidizing and acid properties was obtained. Remarkable activity and high selectivity were observed for the oxidative abatement of (2‐chloroethyl)ethyl sulfide (CEES), a simulant of sulfur mustard, at room temperature with aqueous hydrogen peroxide. This performance was significantly better compared to a conventional commercial decontamination powder.     

Mechanistic Insights into the Luminescent Sensing of Organophosphorus Chemical Warfare Agents and Simulants Using Trivalent Lanthanide Complexes

Organophosphorus chemical warfare agents (OP CWAs) are potent acetylcholinesterase inhibitors that can cause incapacitation and death within minutes of exposure, and furthermore are largely undetectable by the human senses. Fast, efficient, sensitive and selective detection of these compounds is therefore critical to minimise exposure. Traditional molecular‐based sensing approaches have exploited the chemical reactivity of the OP CWAs, whereas more recently supramolecular‐based approaches using non‐covalent interactions have gained momentum. This is due, in part, to the potential development of sensors with second‐generation properties, such as reversibility and multifunction capabilities. Supramolecular sensors also offer opportunities for incorporation of metal ions allowing for the exploitation of their unique properties. In particular, trivalent lanthanide ions are being increasingly used in the OP CWA sensing event and their use in supramolecular sensors is discussed in this Minireview. We focus on the fundamental interactions of simple lanthanide systems with OP CWAs and simulants, along with the development of more elaborate and complex systems including those containing nanotubes, polymers and gold nanoparticles. Whilst literature investigations into lanthanide‐based OP CWA detection systems are relatively scarce, their unique and versatile properties provide a promising platform for the development of more efficient and complex sensing systems into the future.     

压电晶体微天平阵列传感器识别毒剂的研究

压电晶体微天平(QCM)阵列传感器在毒剂侦检领域具有广泛的应用前景。本研究建立了QCM阵列传感器毒剂检测系统,以氢键酸性共聚硅氧烷(BSP3)、聚表氯醇(PECH)和乙基纤维素(ECEL)为膜材料制备了对毒剂敏感的QCM阵列传感器,对沙林、芥子气、甲基膦酸二甲酯进行了定量检测,并结合模式识别方法对检测结果进行了分析处理,识别率达到98%以上,为探索QCM阵列传感器对毒剂的定性定量分析提供了方法依据。     

应用热脱附-气相色谱质谱法测定空气中化学毒剂模拟剂

采用Tenax-TA热脱附采样管(Tube)主动采样,以热脱附仪结合气相色谱质谱(GC-MS)联用仪为分析手段,建立了空气中4种化学毒剂模拟剂(1,2-二氯乙烷、N,N-二甲基乙酰胺、磷酸三甲酯和甲基磷酸二甲酯)的快速分析方法。结果表明,4种模拟剂在1～100 ng/tube范围内线性关系良好,相关系数均大于0.99,平均加标回收率为82%～112%,检出限为0.13～0.26 ng/tube,相对标准偏差小于15%。     

Ionic Liquid as an Alternative Greener Sensing Medium for the Chemical Warfare Agent

Greener electrochemical detection method developed for chemical warfare agent (CWA) nitrogen mustard‐2 (NM‐2) using room temperature ionic liquid (RTIL). The diffusion coefficient calculated for NM‐2 in acetonitrile and RTIL was 1.57×10^?4 cm²/s and 1.82×10^?10 cm²/s, respectively. NM‐2 addition to RTIL enhanced RTIL conductivity. Moreover, heterogeneous rate constant (0.192 s^?1), transfer coefficient (0.231) and the number of electron involved (1.0) were deduced for NM‐2 in RTIL. The calibration plot showed linearity between 2.94×10^?5 and 1.17×10^?3 M with detection limit 1.47 ×10^?5 M (S/N=3). The large number of available RTIL can be used for greener detection of toxic CWAs.     

含磷毒剂及其降解产物的气相色谱-质谱测定方法研究

研究了用台式气相色谱-质谱仪分析测定含磷毒剂及其降解产物,并对降解产物的衍生化方法及它们的色谱行为进行了研究,总结分析了它们的质谱裂解特点及规律,测定了水样中的含磷毒剂及降解产物。     

Broad‐Spectrum Liquid‐ and Gas‐Phase Decontamination of Chemical Warfare Agents by One‐Dimensional Heteropolyniobates

A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one‐dimensional polymeric polyniobate (P‐PONb), K₁₂[Ti₂O₂][GeNb₁₂O₄₀]?19 H₂O ( KGeNb ) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H₂O)/k(D₂O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P‐PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P‐PONbs themselves, a critical control experiment.     

Bifunctional Europium(III) and Niobium(V)-Containing Saponite Clays for the Simultaneous Optical Detection and Catalytic Oxidative Abatement of Blister Chemical Warfare Agents

For the first time, the co-presence in the saponite structure of luminescent Eu^III and catalytic Nb^V metal sites was exploited for the simultaneous detection and catalytic abatement of sulfur-containing blister chemical warfare agents. Metal centers were introduced in structural positions of the saponite (in the interlayer space or inside the inorganic framework) following two different synthetic methodologies. The functionalized saponites were able to reveal the presence of a sulfur mustard simulant (2-chloroethyl)ethyl sulfide (CEES) after few seconds of contact time and more than 80 % of the substrate was catalytically decomposed after 24 h in the presence of aqueous hydrogen peroxide.     

Ultra‐Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal–organic frame‐works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF–nanofiber kebab structures for fast degradation of CWAs. We found TiO₂ coatings deposited via atomic layer deposition (ALD) onto polyamide‐6 nanofibers enable the formation of conformal Zr‐based MOF thin films including UiO‐66, UiO‐66‐NH₂, and UiO‐67. Cross‐sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF‐functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half‐lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF–nanofiber textile composites capable of ultra‐fast degradation of CWAs.     

Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products

The analysis of chemical warfare agents and their degradation products is an important component of verification of compliance with the Chemical Weapons Convention. Gas and liquid chromatography, particularly combined with mass spectrometry, are the major techniques used to detect and identify chemicals of concern to the Convention. The more polar analytes, and some of the more reactive or highly volatile agents, are usually derivatised to facilitate chromatography, and to impart properties beneficial for detection. This review focuses on derivatisation reactions used in the chromatographic analysis of chemical warfare agents, their degradation products and metabolites.     

Application of Impedimetric and Voltammetric Genosensor for Detection of a Biological Warfare: Anthrax

A strategy for the detection of anthrax, which is a potential biological weapon by using an electrochemical genosensing technology, is investigated. An alkanathiol‐linked or unlabeled capture probe related to B. anthracis is immobilized onto gold or graphite electrode surface. A 101‐mer anthrax target is used for hybridization. The extent of hybridization between probe and target sequences is determined by using differential pulse voltammetry (DPV) and electrochemical impedance spectrometry (EIS). EIS analysis are based on electron transfer resistance (R_ct) in the presence of [Fe(CN)₆]^3?/4? and DPV measurements are based on transduction of both guanine oxidation and Meldola's blue (MDB) reduction signal as hybridization indicator. The response of the probe‐modified electrodes which was interacted with a noncomplementary sequence was the same as the responses of probe‐modified surface and proved the specifity of the hybridization with the target. According to these results the developed genosensors based on EIS and DPV techniques can be employed for rapid and selective detection of B. anthracis.