基于双氢青蒿素-巯基化合物电化学探针对巯基化合物的检测

在20%乙醇+B-R缓冲溶液(pH7.2)介质中,利用双氢青蒿素与谷胱甘肽、6-巯基嘌呤及L-半胱氨酸作用,分别于-1.05,-1.20和-1.10V处获得双氢青蒿素-巯基化合物复合物灵敏的还原峰,该还原峰在一定浓度范围内随着巯基化合物以及双氢青蒿素浓度的增加而增大,因此可将其作为电化学探针应用于上述3种巯基化合物以及双氢青蒿素的检测,为检测巯基化合物提供了一种新方法;探讨了复合物形成的电极反应机理,利用纳米金与巯基的共价作用阻断巯基参与形成复合物,证实了复合物是由双氢青蒿素中的碳自由基与巯基化合物巯基中的硫原子通过SC键结合形成。     

浅议基于《有机化合物命名原则2017》的复杂有机化合物

In order to promote and keep pace with the teaching of new nomenclature of organic compounds, some important revisions about teaching organic nomenclature suggested in Nomenclature of Organic Compounds 2017 were summarized. We proposed some concrete suggestions for using the new principles of the Nomenclature of Organic Compounds 2017 to name the complex organic compounds.     

Mesomorphic Complex Compounds

This paper presents a review of liquid crystalline complexes whose central atoms are d elements (Group IB, IIB, IIIB, or VB atoms), f elements (lanthanides), and s or p elements. The possibilities of constructing coordination compounds with mesomorphic properties are discussed in view of the central atom coordination number and the nature of the ligand.     

基于DNA-甲苯胺蓝生物聚合离子膜的多环有机物电化学传感器的研究

利用DNA与小分子之间的相互作用,以DNA/壳聚糖生物聚合离子膜固定电活性小分子,制备了DNA-甲苯胺蓝/壳聚糖聚合离子复合膜修饰电极,并利用多环有机物与染料分子对DNA特异结合的竞争关系,构筑了多环有机物非试剂添加型DNA电化学生物传感器。以盐酸四环素为模式分子,利用循环伏安法和方波伏安法研究了该修饰电极的电化学特性以及该电极对盐酸四环素的电化学响应,结果表明,DNA和甲苯胺蓝成功地固定在电极表面,电极表面的甲苯胺蓝保持了很好的电化学活性。利用紫外-可见分光光度法研究了电极对盐酸四环素响应的作用机理。该传感器的线性范围为2.5~100μmol·L-1。     

Phosphorus-Nitrogen Compounds as Complex Ligands

Abstract

Amino(imino)phosphanes(σ²-phosphazenes) of the type N[sbnd]P[dbnd]N- are useful complex ligands.     

Crystal Chemistry of Complex Carbides and Related Compounds

Numerous metal carbides can be discussed in a rather uniform way by means of structural features, mainly characterized by the mode of linking of octahedral and occasionally trigonal prismatic [M₆C] groups (M = transition element). From this point of view perovskite carbides (M₃M′C, M′ = another transition or A-group element) and derivatives, β-Mn carbides (M₃M′₂C), κ-carbides, carbides with V₃AsC- and Cr₂AlC type structures and derivatives, η-carbides (M₃M′₃C) and carbides having the filled Mn₅Si₃ type structure will be treated. The high stability of these complex carbides is due to the strong bonding M? C and additional bonding of M? M′ atoms forming an ordered parent lattice. Besides the interstitial principle of filling of lattice holes (by isolated carbon atoms), substitution with A-group elements may also take place. Thus in borocarbides extended structural elements occur.     

基于昆虫气味结合蛋白的新型酰基哌啶类化合物的构效关系

利用Sybyl7.3软件对29个具有驱避活性的新型酰基哌啶类化合物与气味结合蛋白AgamOBP1的结合模式进行研究,发现二者之间的结合以疏水作用和水桥作用为主. 其中酰基哌啶类化合物末端的疏水片段可与AgamOBP1结合腔内狭长的疏水通道产生相互作用. 同时,其关键药效基团——酰基氧可通过HOH153与AgamOBP1中的关键残基Trp114和Gly92或Cys95形成多重氢键作用. 利用比较分子力场分析法（CoMFA）和比较分子相似性指数分析法（CoMSIA）构建了新型酰基哌啶类化合物的三维定量构效关系（3D-QSAR）模型,其交叉验证系数r_cv²分别为0.650和0.587. 研究表明,在CoMSIA模型中,疏水场、静电场和立体场组合所得的三维构效关系模型最佳,其中尤以疏水场对这类酰基哌啶类化合物的驱避活性最为重要. 基于AgamOBP1靶标结合口袋特征和酰基哌啶类化合物的3D-QSAR模型得出具有驱避活性的酰基哌啶类化合物的构效关系如下：在酰基C上引入一定碳链长度的疏水基团可使化合物表现出驱避活性,其中又以含9~10个C的化合物的驱避活性最佳,这与AgamOBP1结合口袋的疏水性质密不可分;当酰基端碳链长度一定时,在哌啶环上不宜引入立体效应过大的取代基,这是由AgamOBP1结合口袋的大小决定的;与哌啶N相连的酰基作为氢键受体基团,对于化合物识别与结合AgamOBP1蛋白至关重要.     

The Distribution of Charge in Complex Compounds

The charges on metal atoms and ligands in complex compounds of transition metals may be calculated theoretically or measured empirically, but there is no reliable method of doing either. This review is concerned mainly with two experimental methods, dipole moment measurement and X-ray photoelectron spectroscopy, applied to tertiary phosphate and such complexes of the heavier transition metals. It is concluded that the charge is rarely greater than ±0.3e and that some so-called neutral or positive ligands, e.g. N₂ or NO⁺, may carry more negative charge in a complex than formally anionic ligands such as H^?. Small ligands of high formal charge, e.g. O^2?, NR^2?, and N^3?, appear to carry no more negative charge than Cl^?, but monoanionic ligands vary greatly in their capacity to contribute to the dipole moments. The ligands NO, CO, PF₃, CH, and H^? are all nearly neutral to slightly negative, whereas pyridines, tertiary phosphanes, etc. are the most strongly positively charged.     

Spiroheterocyclic Compounds Based on 2-Bromobutanolides

Bromination of ethyl 5-alkoxymethyl-2-oxotetrahydrofuran-3-carboxylates afforded ethyl 5-alkoxymethyl-3-bromo-2-oxotetrahydrofuran-3-carboxylates which reacted with thiourea, substituted thioureas, benzimidazole-2-thiol, and benzothiazole-2-thiol to give new heterocyclic compounds.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 590–593.Original Russian Text Copyright © 2005 by Kochikyan.     

基于有机硼化合物的氟离子化学探针

本文综述了有机硼化合物在氟离子探针领域的研究进展.介绍了基于三芳基硼化合物、硼酸和硼酸酯的有机硼化合物在氟离子检测中的应用,评述了这些化合物的结构和检测性能之间的关系,讨论了检测机理,即有机硼化合物中硼原子空的pπ轨道使其作为路易斯酸能够选择性地结合氟离子,硼原子与氟离子的结合破坏了硼中心与芳香取代基的pπ-π共轭,引起有机硼化合物光物理性质的变化,从而实现对氟离子的高选择性检测.最后提出了有机硼化合物作为氟离子探针存在的一些问题,并展望了有机硼化合物在氟离子探针领域的研究和发展方向.     

掺Pb对Bi系超导体性能影响的研究

在使用聚合物-金属复合物(PMC)新型合成工艺制备出性能优良的BiSrCaCuO超导体的基础上,利用PMC法易于掺杂的特点,合成了Bi2-x(Pb)xSr2Ca2Cu2Oy超导体,实验结果表明,掺Pb后,合成时间进一步缩短,高Tc相的形成速率是不掺Pb的4~6倍,所得超导体为单相,掺Pb不影响体系的微观均匀性。     

用聚合物-金属复合物法合成BiSrCaCuO超导体的研究

通过使用聚合物-金属复合物的新型合成工艺,制备出性能优良的BiSrCaCuO超导体,超导体内高Tc和低Tc相并存,其Tce为114.7 K,Tco为84.0 K。探索了各金属离子的配比、聚合物与无机离子的质量比,以及各种不同的热处理条件对超导体中高Tc相和低Tc相的比例的影响。对聚合物-金属混合物的前体液进行了结构分析。实验结果表明,聚合物与金属离子形成了复合结构,聚合物-复合物合成工艺具有微观均匀性的特点。     

Reactions of divalent transition metal halides with 3,5-dimethyl-1-(hydroxymethyl)-pyrazole

Factors determining the complex formation reaction of copper(II), nickel(II) and cobalt(II) chloride and copper(II) bromide with 3,5-dimethyl-1-(hydroxymethyl)-pyrazole (HL) has been studied. Depending on experimental conditions, complexes with different composition were obtained: [CuCl₂(dmp)]₂ (I), [CuCl₂(dmp)₂]₂ (II), [CoCl₂(dmp)₂] (III) (dmp=3,5-dimethylpyrazole), [CuBr(L)]₂ (IV), [CoCl(L)(EtOH)]₄ (V) and [NiCl(L)(EtOH)]₄ (VI). The compounds were characterized by FTIR spectroscopy, solution conductivity and magnetic measurements. The crystal structure of [CoCl(L)(EtOH)]₄ has been determined by single crystal X-ray diffraction. The thermal decomposition of the compounds was studied and found to be continuous for all of the compounds. The desolvation mechanism of [MCl(L)(EtOH)]₄ (M=Co(II), Ni(II)) is explained on the basis of the route of complex formation of CoCl₂ with HL.     

A 1D Double Stranded Chain Complex Based on Barium Ion and 1,3,5-Triazine

A new coordination compound [Ba(OBPT)2(H2O)2]·H2O was obtained at room temperature by the reaction of 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol(HOBPT) with BaCl2.It was characterized by elemental analysis,FTIR,TG analysis,powder X-ray diffraction analysis and single-crystal X-ray diffraction analysis.The complex crystallizes in the monoclinic P21/n space group,with a = 16.325(1),b = 6.7977(5),c = 24.164(2) ,β = 104.009(1),V = 2601.8(3) 3,Z =4,C26H22BaN10O5,Mr = 691.88,Dc = 1.766 g/cm3,F(000) = 1376 and μ(MoKα) = 1.587 mm-1.The final R = 0.0282 and wR = 0.0724 for 5095 observed reflections with I > 2σ(I) and R = 0.0312 and wR = 0.0744 for all data.In the complex,the barium ion is ten-coordinated with six nitrogen atoms from two ligands,two deprotonated hydroxyl oxygen atoms from another two ligands and two coordinated water molecules to form a double stranded chain.The extensive supramolecular interac-tions lead to the formation of an infinite 2D framework.     

Synthesis of Functionalized Bicyclic Compounds Based on 2-(1-Arylethylidene)malononitriles

Russian Journal of Organic Chemistry - New tetrahydroisoquinoline-5,7-dicarbonitrile derivatives have been synthesized by piperazine hydrate-catalyzed reaction of acetoacetanilide with...     

基于磷杂菲基团化合物的构建与性能*

由于磷杂菲基团具有杂环含磷特性、非共平面性、与分子内或分子间基团的相互作用性、分子极性等特点,能够作为改性基团引入到化合物中用于构建具有新结构和新性能的材料。本文综述了磷杂菲基团衍生物的构建方法和含有磷杂菲基团功能材料的性能以及磷杂菲基团对材料性能的影响规律。介绍了利用9,10-二氢-9-氧杂-10-磷杂菲 10-氧化物（DOPO）的P-H键与不饱和基团醌、醛、酮、碳碳双键、碳氮双键、碳氮三键等进行加成反应获得磷杂菲衍生物的方法和原理。重点总结了含磷杂菲基团的环氧树脂、聚酯、涂料和助剂等化合物的阻燃性能以及磷杂菲基团提高材料阻燃性能的原理;介绍了磷杂菲基团易于与分子内和分子间基团相互作用的性质以及对热致液晶高分子材料液晶性质的影响规律,这一性质也导致了一些磷杂菲化合物的聚集诱导发光现象的发生。此外,磷杂菲基团的极性提高了聚酯和聚酰胺等化合物的分子极性,使这类化合物获得了良好的有机溶解性。     

基于阴离子-石墨嵌层化合物的电化学电容器

石墨可以在高电势下电化学可逆存储阴离子,有望在高电压储能器件中担当正极材料.本文介绍了基于阴离子-石墨嵌层化合物型正极材料的高比能电容器的研究进展,剖析了影响电容器性能的各方面因素,探讨了一系列表征相关电极材料储能机制的方法和手段,揭示了溶剂化效应对阴离子插嵌石墨正极电化学行为的关键性作用.并进一步概述了该种正极材料近年来在新型储能器件-双离子电池中的发展态势,展望了其应用前景和即将面临的潜在问题.