检测有机磷神经毒剂及模拟物的荧光探针

有机磷神经毒剂是一类具有极大杀伤力的化学毒剂,这类有机磷酸盐通过破坏人体内的神经递质乙酰胆碱酯酶麻痹人的中枢神经,很小的剂量就可致人死亡,因此对有机磷神经毒剂进行快速简便地检测具有重要意义。荧光化学传感具有灵敏度高、选择性好和响应时间短等优点,近些年来应用荧光传感方法对有机磷神经毒剂及其模拟物的检测越来越受到研究人员的关注。本篇综述对荧光传感的原理做了简要介绍,综述了近年来国内外研究者开发的各种用于有机磷神经毒剂及其模拟物检测的荧光新材料与新方法,并对荧光传感方法应用于有机磷神经毒剂检测的未来进行了展望。     

检测活性氮/活性氧的分子荧光探针

活性氮和活性氧是具有强生物活性的化学物质.在人体细胞中,由于酶促或非酶促过程均可生成过氧化物,该物种的异常水平会引起氧化损伤与衰老和各种疾病,如心血管疾病、神经性疾病、阿尔茨海默病、帕金森病甚至癌症.因此,发展选择性识别和高灵敏度的分子荧光探针,实现活性氮或活性氧的有效检测具有重要意义.分子荧光探针检测法与成像技术具有灵敏度高、选择性强、损伤性小和细胞相容性好等优点,并在阐述活性氮和活性氧的病理生理过程中起到重要作用,在生物和医学等领域应用广泛.然而,由于活性氮和活性氧自身的特殊性而存在许多难题,例如反应活性高、存在周期短等一直困扰研究人员.着重综述了近年来发展的分子荧光探针用于活性氮和活性氧的检测及细胞成像工作的研究进展,提出进一步构建新型分子荧光探针用于活性氮和活性氧检测面临的挑战、未来发展方向及展望.     

香豆素衍生物荧光探针研究进展

对近5年来设计合成的新型香豆素荧光探针研究进展进行综述。系统阐述合成新型香豆素荧光探针在生物学领域的应用,主要包括检测内源性物质、监测细胞结构形态、对重金属离子的定性定量分析等。香豆素母核的活性位点多样,适于结构修饰,基于香豆素荧光探针对7、8位的活性位点进行改造,得到一系列新型香豆素衍生物荧光探针。通过对此类荧光传感器相关技术进展进行综述,为寻找新的荧光结合位点以及合成新型香豆素衍生物传感器提供参考。     

萘酰亚胺类荧光分子探针的研究进展

荧光分子探针作为一种有效的金属离子检测手段,不仅使用方便,而且具有高灵敏度,高选择性等突出的优点.作者综述了萘酰亚胺类荧光分子探针的最新研究进展;指出萘酰亚胺化合物具有独特的荧光化学性质(如荧光量子产率高、荧光发射波长适中、斯托克斯位移大、光稳定性好、结构易于修饰等),因此被广泛应用于荧光探针研究领域,并且在合成、离子识别、检测及细胞成像等方面不断取得新的应用.     

核酸功能化稀土基纳米材料在生物检测中的应用

体内一些生物分子和离子的水平通常与细胞、组织、器官等结构和功能的变化相关,从而直接影响到疾病的预防、诊断和治疗,因此对体内这些物质的生物检测在医疗和健康领域具有重要的意义.基于稀土基纳米材料构建的纳米荧光探针具有灵敏度高、简单高效、抗干扰能力强等优点,在生物检测方面具有巨大的潜力.对稀土基纳米材料的核酸功能化能够进一步为纳米荧光探针提供更好的特异性识别能力和生物相容性,从而增强其在复杂样品中的生物检测能力.本综述总结了核酸功能化的稀土基纳米材料作为纳米荧光探针在生物检测领域的研究进展,简要介绍了其主要种类和性能、检测机理及检测物质,最后对该领域面临的挑战及未来的发展方向进行了展望.     

基于硅杂蒽类染料的荧光探针及其应用

近年来,荧光成像技术为人们研究活体细胞及组织内的化学生物学过程提供了有效的研究工具,可以无损、实时、原位地以高时空分辨率实现对目标物进行生物荧光成像与分析。荧光成像技术在生物学、环境监测、临床诊断和药物发现等诸多研究领域发挥着越来越重要的作用。生物荧光成像技术的最新进展对发展新型小分子荧光染料及探针提出了更高的要求。激发和发射波长位于近红外光区（600~900 nm）的荧光染料及探针由于具有光毒性低、生物分子自发荧光干扰小、光散射低、组织穿透能力强等优点,非常适合用于生物荧光成像领域。通过将罗丹明分子中O桥原子用Si代替,得到了一类新型的探针分子--硅杂蒽类荧光探针。这类染料分子在保留了氧杂蒽荧光染料优越的光学性质的同时,光谱发生明显红移,满足了近红外荧光检测的要求,具有良好的生物相容性。本文综述了近年来基于硅杂蒽及其衍生物荧光探针的合成及在金属离子、pH值、小分子、生物酶等检测方面的研究进展,并且简要阐述了基于硅杂蒽类探针分子的识别检测机理以及其在生物成像等方面的应用。     

近红外荧光探针检测金属离子、小分子和生物大分子

荧光探针技术是近年来发展迅速的一种荧光分析方法,具有灵敏度高、选择性好、操作简便和响应迅速等特点,受到环境及生命科学领域的青睐。随着荧光探针技术的发展,近红外一区荧光探针由于具有发射波长长(600~900 nm)、对细胞损伤小、组织穿透性强和自发荧光背景低等优点,被广泛应用于细胞、组织等复杂生物体系中生物分子的检测、示踪及成像。本文评述了近年来(2016~2020年)近红外荧光探针对金属离子(Hg²⁺、Cu²⁺、Zn²⁺、Al³⁺、Fe³⁺)、生物小分子(Cys、N₂H₄、H₂S、H₂O₂)与生物大分子(亮氨酸氨基肽酶、β-半乳糖苷酶)等重要生物分子的检测及成像的研究进展,讨论了该类探针在细胞及活体的分析应用,并对近红外荧光探针的前景进行了展望。     

荧光探针在氰化物分析中的研究进展

氰化物极易与细胞色素氧化酶键合,抑制电子转移、导致组织缺氧,从而显示较强的毒性。荧光化学传感器作为简易、灵敏且可视化的方法广泛应用于氰化物的检测。本文对荧光探针在氰化物检测中的应用进行综述,概述了氰化物的毒性机制和荧光探针对氰化物的响应机理。同时,本文总结了荧光探针在水体、食品和生物组织中对氰化物的检测及生物成像中的应用,并对荧光探针在结构设计中如何提高生物兼容性和靶向性等进行了展望,以期为光化学探针分子的设计及应用提供理论与研究依据。     

亚铁离子荧光探针的研究进展

铁作为生命系统中最丰富的过渡金属元素,在许多生理和病理过程中发挥着无可替代的作用.铁平衡失调不仅会导致诸如癌症、心血管疾病、神经退行性疾病等的发生和发展,而且还会造成细胞铁死亡.尽管细胞中的铁有Fe~(2+)和Fe~(3+)两种形式,但细胞还原性微环境使其主要以Fe~(2+)形式存在.因此,开发一种对Fe~(2+)的特异性检测技术有助于深入了解Fe~(2+)与人类健康和疾病的关系.随着荧光成像技术的发展,近年来特异性检测Fe~(2+)的荧光探针引起学者们的极大关注.对近10年来报道的Fe~(2+)荧光探针,根据探针的设计思路、与Fe~(2+)的作用机理、光学特性以及其生物应用等方面进行了总结,并对Fe~(2+)荧光探针的发展前景进行了展望.     

有机双光子线粒体内活性小分子荧光探针研究进展

线粒体在细胞的能量代谢中发挥着关键作用,其内部环境的微小变化会影响细胞的正常生命活动。同时线粒体内许多活性小分子在细胞的许多生理过程中也起着关键作用。因此,可视化监测线粒体自身及内部微环境的变化对于生命现象的研究和疾病的诊断与治疗具有非常重要的意义。荧光分析法因具有操作简便、灵敏度高、选择性好、实时检测以及损伤小等优点而得到了广泛的研究和应用。双光子荧光探针技术相对于单光子荧光技术具有长波吸收短波发射、高度的三维空间选择性、大的穿透深度、避免荧光漂白和光致毒以及降低组织自发荧光干扰等特点,在生命科学领域具有广阔的应用前景。该文介绍了有机双光子吸收基本原理以及有机双光子线粒体内活性小分子荧光探针的研究现状,同时对有机线粒体内活性小分子荧光探针今后的发展趋势进行了展望。     

A Fluorescent Sensor for Dual‐Channel Discrimination between Phosgene and a Nerve‐Gas Mimic

The ability to analyze highly toxic chemical warfare agents (CWAs) and related chemicals in a rapid and precise manner is essential in order to alleviate serious threats to humankind and public security caused by unexpected terrorist attacks and industrial accidents. In this investigation, we designed a o‐phenylenediamine‐pyronin linked dye that is capable of both fluorogenic and colorimetric discrimination between phosgene and the prototypical nerve‐agent mimic, diethyl chlorophosphate (DCP) in the solution or gas phase. Moreover, this dye has been used to construct a portable kit that can be employed for real‐time monitoring of DCP and phosgene in the field, both in a discriminatory manner, and in a simple and safe way.     

Sensitive and Visual Detection of Phosgene by a TICT-Based BODIPY Dye with 8-(o-Hydroxy)aniline as the Active Site

Phosgene and its substitutes (diphosgene and triphosgene) are widely utilized as chemical industrial materials and chemical warfare agents and pose a threat to public health and environmental safety due to their extreme toxicity. Research efforts have been directed to develop selective and sensitive detection methods for phosgene and its substitutes. In this paper, we have prepared two BODIPY-based fluorescent probes, o-Pah and o-Pha, which are two isomers with different active sites, ortho-aminohydroxy (3′,4′ or 4′,3′) phenyls at meso position of BODIPY, and compared their sensing performance toward triphosgene. The probe with o-(4′-amino-3′-hydroxyl), o-Pha, exhibits better sensing performance over the o-(3′-amino-4′-hydroxyl), o-Pah, for instance, a lower limit of detection (LOD) (0.34 nm vs. 1.2 nm ), and more rapid response (10 s vs. 200 s). Furthermore, based on the above comparative studies, a red-fluorescence probe o-Phae has been constructed through extending 3,5-conjugation of o-Pha. The probe o-Phae displays rapid response (60 s), high sensitivity to triphosgene (LOD=0.88 nm ), and high selectivity for triphosgene over relevant analytes including nitric oxide. Finally, a facile test strip for phosgene was fabricated by immobilizing o-Phae in a polyethylene oxide membrane for sensitive (<2 ppm) and selective detection of phosgene in the gas phase.     

Phosgene as a derivatizing reagent prior to gas and liquid chromatography

The use of phosgene as a derivatizing agent for bifunctional compounds prior to gas and liquid chromatographic analysis is reviewed. Applications include gas chromatographic determinations of metoprolol and its metabolites in biological fluids, enantiomeric separations of beta-blocking drugs and sympathomimetic agents on a chiral stationary phase and liquid chromatographic enantiomer separations.     

Purity analysis of hydrogen cyanide, cyanogen chloride and phosgene by quantitative (13)C NMR spectroscopy

Hydrogen cyanide, cyanogen chloride and phosgene are produced in tremendously large quantities today by the chemical industry. The compounds are also particularly attractive to foreign states and terrorists seeking an inexpensive mass-destruction capability. Along with contemporary warfare agents, therefore, the US Army evaluates protective equipment used by warfighters and domestic emergency responders against the compounds, and requires their certification at > or = 95 carbon atom % before use. We have investigated the (13)C spin-lattice relaxation behavior of the compounds to develop a quantitative NMR method for characterizing chemical lots supplied to the Army. Behavior was assessed at 75 and 126 MHz for temperatures between 5 and 15 degrees C to hold the compounds in their liquid states, dramatically improving detection sensitivity. T(1) values for cyanogen chloride and phosgene were somewhat comparable, ranging between 20 and 31 s. Hydrogen cyanide values were significantly shorter at 10-18 s, most likely because of a (1)H--(13)C dipolar contribution to relaxation not possible for the other compounds. The T(1) measurements were used to derive relaxation delays for collecting the quantitative (13)C data sets. At 126 MHz, only a single data acquisition with a cryogenic probehead gave a signal-to-noise ratio exceeding that necessary for certifying the compounds at > or = 95 carbon atom % and 99% confidence. Data acquired at 75 MHz with a conventional probehead, however, required > or = 5 acquisitions to reach this certifying signal-to-noise ratio for phosgene, and >/= 12 acquisitions were required for the other compounds under these same conditions. In terms of accuracy and execution time, the NMR method rivals typical chromatographic methods.     

光气法制备酰氯的催化剂研究进展

酰氯是一类用途非常广泛的重要有机合成中间体,在工业上制备酰氯主要使用的氯化剂包括PCl3、PCl5、SOCl2、光气等,充分反应后通过过滤、蒸馏等工艺进行脱色提纯制得酰氯。光气法由于对环境污染较低,是目前最常用的方法。三光气可以分解成光气,其优良的物理、化学性质以及便捷的储存和运输条件是光气的最佳替代化学品。但由于光气活性较低,在使用过程中添加催化剂必不可少,本文将重点介绍目前光气法制备酰氯时所使用的各种催化剂及其性能。     

Reactivity difference between diphosgene and phosgene in reaction with (2,3-anti)-3-amino-1,2-diols

In reactions of (2,3-anti)-3-amino-1,2-diols with diphosgene and phosgene and their conversion into 1,3-oxazolidin-2-ones, some differences in the stereochemistry of the reactions have been found with these two reagents. The reactions with phosgene afforded the expected cis-oxazolidinones, and in the reaction with diphosgene under the same reaction conditions, the trans-oxazolidinones were also obtained.     

A HTS Assay for the Detection of Organophosphorus Nerve Agent Scavengers

A new pro‐fluorescent probe aimed at a HTS assay of scavengers is able to selectively and efficiently cleave the P? S bond of organophosphorus nerve agents and by this provides non‐toxic phosphonic acid has been designed and synthesised. The previously described pro‐fluorescent probes were based on a conventional activated P? Oaryl bond cleavage, whereas our approach uses a self‐immolative linker strategy that allows the detection of phosphonothioase activity with respect to a non‐activated P? Salkyl bond. Further, we have also developed and optimised a high‐throughput screening assay for the selection of decontaminants (chemical or biochemical scavengers) that could efficiently hydrolyse highly toxic V ‐type nerve agents. A preliminary screening, realised on a small α‐nucleophile library, allowed us to identify some preliminary “hits”, among which pyridinealdoximes, α‐oxo oximes, hydroxamic acids and, less active but more original, amidoximes were the most promising. Their selective phosphonothioase activity has been further confirmed by using PhX as the substrate, and thus they offer new perspectives for the synthesis of more potent V nerve agent scavengers.     

Development of BINOL-Si complexes with large stokes shifts and their application as chemodosimeters for nerve agent

Three fluorescent BINOL-Si complexes (FS1, FS2 and FS3) were rationally designed and synthesized to detect diethyl chlorophosphate (DCP), a mimic of lethal nerve agents. These three fluorescent probes showed green, yellow and orange fluorescence, respectively. Moreover, the series of fluorescent probes has the characteristics of fast response time (≤ 4 s), low detection limit (0.0097 μmol/L), high sensitivity and naked eye detection. More important, a fiber optic sensor capable of detecting DCP vapor in real time was also prepared for the first time, the lowest detection limits (down to 4.4 ppb) were all lower than that of the IDLH (immediately dangerous to life or health) concentration of Sarin (7.0 ppb).     

Development of BINOL-Si complexes with large stokes shifts and their application as chemodosimeters for nerve agent

Three fluorescent BINOL-Si complexes (FS1, FS2 and FS3) were rationally designed and synthesized to detect diethyl chlorophosphate (DCP), a mimic of lethal nerve agents. These three fluorescent probes showed green, yellow and orange fluorescence, respectively. Moreover, the series of fluorescent probes has the characteristics of fast response time (≤4 s), low detection limit (0.0097 μmol/L), high sensitivity and naked eye detection. More important, a fiber optic sensor capable of detecting DCP vapor in real time was also prepared for the first time, the lowest detection limits (down to 4.4 ppb) were all lower than that of the IDLH (immediately dangerous to life or health) concentration of Sarin (7.0 ppb).     

Analysis of nerve agents using capillary electrophoresis and laboratory-on-a-chip technology

The nerve agents belong among the most toxic compounds produced by human kind. While they have been used very sporadically until now, typically in local conflicts or by local terrorists groups, the global increase in terrorist activity in the recent years has generated tremendous demand for innovative tools capable of detecting nerve agents. Fast, sensitive and reliable detection of nerve agents in the field is very important issue in present days. Capillary electrophoresis (CE) offers great possibilities for sensitive detection of these harmful compounds as well as incorporation in mobile laboratory and it proved to have capability to detect nerve agent breakdown products in real environmental samples. Laboratory-on-a-chip format offers great possibilities to create portable, field deployable, rapidly responding and potentially disposable device, allowing security forces to make the important decision regarding the safety of civilians. This article overviews the conventional capillary electrophoretic and laboratory-on-a-chip techniques for analysis of degradation products of G-type and V-type nerve agents. It discusses diverse strategies of detection of different nerve agents breakdown products, which are corresponding to their parental nerve agents. It also overviews possibilities and challenges for analysis of the real samples.