过氧化爆炸物研究进展

爆炸恐怖袭击是恐怖分子首选的作案手段,对国家安全和社会稳定造成严重威胁。三过氧化三丙酮(TATP)、二丙酮二过氧化物(DADP)、六亚甲基三过氧化二胺(HMTD)等过氧化爆炸物因其制作工艺简单、制作原料易得、常规安检手段难以检测、爆炸威力大等特点,成为恐怖分子实施爆炸恐怖袭击的重要工具。本文从过氧化爆炸物的合成、性能、检测、销毁四个方面综述了目前国内外关于过氧化爆炸物的研究进展,包括合成方法和机理,热力学性质和感度等,质谱及其联用技术、表面增强拉曼光谱、比色传感器及其阵列检测在过氧化爆炸物检测中的应用等,可为提高办案人员现场处置的安全意识,提取、检测及销毁过氧化爆炸物提供参考依据。     

过氧化氢荧光探针的研究进展

过氧化氢(H2 O2)与生命系统中的许多生理和病理过程有关.但是,过量的H2 O2会导致一系列生理疾病,因此,有效地识别和检测H2 O2非常重要.近年来已经报道了许多用于检测生物体系中H2 O2的荧光探针,与传统的检测方法相比,其具有灵敏度高、无创检测及实时成像等优点.本文根据不同的荧光团,评述了近五年H2 O2荧光探...     

次氯酸比色荧光探针的研究进展

次氯酸(HClO)和次氯酸钠(NaClO)广泛存在于生命体和环境中,并与生命体的健康或疾病密切相关.近年来,为揭示HClO对生物体的作用及作用机制,已经设计出许多HClO比色荧光探针,这些次氯酸比色荧光探针由于具有灵敏、快速、高选择性、可视化和实时监测等优点而被用于环境或生物体中HClO或ClO-的检测.根据探针对HClO识别机制的不同,将HClO比色荧光探针分为五大类,总结评价近五年来次氯酸比色荧光探针的设计、特征及实际应用.     

静电纺荧光纳米纤维膜在痕量爆炸物检测中的应用

爆炸物检测作为打击爆炸恐怖主义的重要措施之一,正日益彰显出广阔的应用前景.其中,静电纺荧光纳米纤维膜在爆炸物检测领域已展现出其独特的优点,可满足爆炸物检测所需的检测速度快、检测灵敏度高等要求.本文总结了近年来静电纺荧光纳米纤维膜在爆炸物检测中的代表性成果,简要介绍了爆炸物荧光传感机理、静电纺丝技术原理、静电纺荧光纳米纤维膜的制备方法及其爆炸物检测性能的影响因素;系统、重点梳理了有机小分子体系、共轭聚合物体系、聚集诱导发光体系及其他荧光材料体系的静电纺荧光纳米纤维膜在爆炸物检测中的应用,并针对该领域尚未解决的问题和未来可能的发展方向进行了展望,可为实际爆炸物检测中静电纺荧光纳米纤维膜的设计提供指导.     

化学比色法检测爆炸物的研究进展

综述了以化学比色法为原理的比色检测方法在爆炸物检测方面的应用现状以及研究进展。主要介绍了比色传感器、比色传感器阵列以及基于新型材料基底的化学比色传感器。展望了化学比色方法在爆炸物检测领域的应用前景。     

荧光传感方法检测爆炸物的研究进展

爆炸物检测是当前国际安全中迫切关注的问题之一。在过去的几十年中,大量的荧光传感材料用于荧光传感检测气态、液态和固态爆炸物见诸于报道。近年来,为了实现爆炸物的快速响应、高灵敏和高选择性的检测,研究工作者大力开发了各种新型荧光材料。这篇综述总结了近年来用于爆炸物检测的先进荧光材料,详尽、系统、重点地介绍了共轭聚合物、荧光小分子、超分子体系、具有聚集诱导发光效应的活性材料及静电纺丝纳米材料等各种荧光材料在爆炸物检测中的应用,展望了荧光传感方法在爆炸物检测领域的应用前景。     

比色法在爆炸物检测中的研究进展

爆炸物杀伤力大、隐蔽性强,被广泛应用于军事战争,也是恐怖分子施暴方式的首选。基于保护人民生命和财产安全的迫切需求,爆炸物检测技术受到世界公共安全领域的高度重视。相比于其它分析方法,比色法因操作简便、抗干扰性强,不依赖分析设备的优势成为最适用于现场快速检测爆炸物的方法之一。该文主要综述了比色法在爆炸物探测领域的研究进展,包括对比色探针和比色阵列研究进展的总结与前景分析,并重点讨论了比色人工嗅觉系统及其在爆炸物检测中的应用,展望了其未来的发展趋势和应用前景。     

基于对Fe~(3+)-H_2O_2-OPD体系荧光和比色信号的增强检测多巴胺

利用多巴胺对Fe~(3+)-H_2O_2-OPD体系荧光和比色信号的增强,建立了一种荧光和比色双模检测的多巴胺传感方法。Fe~(3+)催化H_2O_2氧化无色的邻苯二胺(OPD),生成黄色且具有荧光信号的二氨基吩嗪(DAP),但是该反应很慢。多巴胺通过引发芬顿反应,促进Fe~(3+)-H_2O_2体系持续产生强氧化性的羟基自由基(·OH),从而加快了OPD转化成DAP的速率,使体系溶液颜色加深,荧光增强。基于此原理,通过测量Fe~(3+)-H_2O_2-OPD体系荧光和比色信号随多巴胺浓度的变化,可以实现多巴胺的双模检测。本方法荧光和比色检测多巴胺的线性范围分别为0.05~20#mol/L和0.10~18#mol/L,检出限分别为15 nmol/L和65 nmol/L(S/N=3)。荧光和比色双模式检测方法操作简单、灵敏度高、结果可视化,并增加了检测的准确度。将本方法应用于人尿液中多巴胺的检测,结果良好。     

分子印迹技术和荧光分析技术在爆炸物检测中的应用*

爆炸品危害社会安定、国家安全,引起国际社会的关注。开发爆炸品的在线监测技术成为当今热点研究领域之一。爆炸物的种类多种多样,它们的检测方法也各不相同。本文简要地回顾了爆炸物的常规检测方法,介绍了爆炸物的新颖检测技术,重点介绍了分子印迹技术和荧光分析技术在爆炸物检测中的应用,总结了分子印迹聚合物和荧光共轭聚合物检测爆炸物的特点,并对它们的发展趋势进行了展望。     

基于磺酸酯的荧光探针用于活细胞内过氧化氢的成像检测

基于过氧化氢（H2O2）特异性催化水解磺酸酯,设计合成了新型绿色荧光探针：荧光素二磺酸酯（FS—1）和二氯荧光素二磺酸酯（FS-2）两种螺环内酯型化合物,用于活细胞内过氧化氢的检测．探针结构由元素分析、IR、^1H NMR及^13C NMR表征．实验表明：探针FS-1和FS-2在模拟生物体系中检测过氧化氢具有良好的选择性和灵敏度,且线性范围较宽．细胞成像显示：探针FS-1和FS-2用于PMA刺激或外加不同浓度H2O2孵育的小鼠腹膜巨噬细胞均呈现明亮的绿色荧光,且能对细胞内H2O2微摩尔级浓度变化产生响应,证明两探针均具有良好的膜渗透性、高的选择性及良好的灵敏度．该方法的建立对研究生物体内H2O2的产生,H2O2导致的各种疾病机制及H2O2介导的信号转导途径具有重要的理论及实际意义．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.