电化学分析的发展及应用

评述了从2001年1月-2002年12月间我国电化学分析发展的概况。内容分极谱与伏安法，微电极、超微电极和修饰电极，离子选择性电极与传感器，示波分析法，电泳及色谱电化学，光谱电化学、电致发光，扫描电化学显微镜及石英晶体微天平，化学计量学方法，电位分析及其它和仪器装置及实验技术等。引用文献591篇。     

电化学分析

本文是《分析试验室》定期评述中电化学分析第六篇评述文章。它评述了从１９９７年１月至１９９８年１０月期间我国电化学分析的进展。内容分基础理论与应用研究两大部分。前者包括电化学分析理论研究、电分析化学中的化学计量学方法,后者包括极谱与伏安法,络合吸附波与催化波,线性扫描伏安法,示差脉冲伏安法,吸附溶出分析法,示波分析法,微电极、超微电极与化学修饰电极,离子选择电极与各类传感器,光谱电化学,扫描隧道显微法和液／液界面电化学分析,电化学检测／电泳、色谱技术,电化学免疫法,电位分析法及其它等。共引用文献４８３篇。     

电化学分析

本文是《分析试验室》定期评述中“电化学分析”第二篇和“离子选择电极”第三篇评述文章,它第一次将上述两课题合并为“电化学分析”课题。它对1987～1990年间(其中离子选择电极为1989～1990年)国内电化学分析的进展作了全面评述。内容包括:基础理论研究、极谱与伏安分析、溶出分析、化学修饰电极、液-液界面电化学、色谱电化学与流动注射分析检测、光谱电化学、离子选择电极、库伦分析及其他分析方法     

电化学分析的进展及应用

本文对2005年1月～2007年3月间我国电化学分析的发展进行了评述.文章按照电化学分析的不同领域分为极谱与伏安法,微电极、超微电极和修饰电极,离子选择性电极与传感器,示波分析法,电泳及色谱电化学,光谱电化学、电致发光法,石英晶体微天平,化学计量学方法,其他分析方法和仪器装置及实验技术等几部分.引用文献561篇.     

甲醛极谱吸附波的研究及分析应用

本文对甲醛在醋酸-醋酸铵-乙酰丙酮底液中的极谱行为和电极反应机理进行了探讨,提出了用示波极谱法测定痕量甲醛的一种新方法。在上述底液中,于70℃恒温水浴中加热10min,甲醛与试剂的反应产物在单扫描示波极谱仪上产生一灵敏的吸附波,峰电位为-0.96V(vs.sCE)。在0.002～1.0μg/ml的范围内,峰电流与甲醛浓度呈线性关系,检测下限为0.002μg/ml。     

钙—芦丁极谱络合吸附波的研究

在０．０１ｍｏｌ／ＬＫＯＨ底液中，用单扫示波极谱法可获得钙－芦丁络合吸附波，检出限为８．０＊１０＾－７ｍｏｌ／Ｌ．电极表面反应速率常数为ｋｓ＝ｄ１．２７ｓ＾－１。     

示波极谱滴定的研究(ⅩⅩⅧ)——单微铂电极上的示波极谱络合滴定法

示波极谱滴定中使用一个微铂电极和一个大面积电极者称为单微铂电极示波极谱滴定法,本文研究了单微铂电极示波极谱络合滴定法,取得了较好的结果。     

用电化学方法研究邻苯三酚的自氧化机理

利用单扫示波极谱法研究了邻苯三酚的自氧化机理，依据多种电化学参数和紫外可见吸收光谱对主要极谱峰和吸收峰的变化规律作出合理解释，指出邻苯三酚自氧化过程存在多种电子转移历程，单扫示波极谱法可直接监测半醌和醌等中间和最终产物的变化。     

甘草酸的电化学行为研究

用循环伏安法、单扫描示波极谱法研究了甘草酸（ｇｌｙｃｙｒｒｈｉｚｉｃ，ＧＡ）在汞电极上的电化学行为及反应机理．证明甘草酸在ｐＨ＝４～１２的缓冲溶液（Ｈ３ＢＯ３＋Ｈ３ＰＯ４＋乙酸＋ＮａＯＨ）中有吸附峰，且示波极谱导数峰值与甘草酸浓度在８．３×１０－５～１．２×１０－６ｍｏｌ／Ｌ范围内成正比，使用悬汞电极（ＨＭＤＥ）线性扫描伏安法可使检测下限达２．４×１０－６ｍｏｌ／Ｌ．根据实验结果首次提出了甘草酸在汞电极上的反应机理．该机理同时被紫外光谱证明，得到合理解释     

电化学分析法测定硒的研究进展

本文综述了国内外电化学分析(极谱和溶出伏安法)测定痕量硒的研究进展,主要包括极谱催化波、吸附波以及阴极溶出伏安法,阳极溶出伏安法,并从反应体系、催化波类型、检出限和电极反应机理等方面进行归纳与评述,展望了硒分析方法的研究方向和发展前景,对进一步研究硒的电化学性质和探索测定硒的新体系有重要参考价值。     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.