固体六氰合铁酸钴微粒在聚电解质中的现场显微红外光谱电化学

报道了六氰合铁酸钴（COHCF）微粒在聚电解质中的光谱电化学及电催化行为．CoHCF的循环伏安呈现一对可逆氧化还原峰，电位扫速在100mV／s范围内，峰电流与扫速成正比．现场红外光谱表明，氧化还原属于CoHCF中的Fe（Ⅱ／Ⅲ）的转化CoHCF微粒可以催化抗坏血酸的氧化，使氧化电位负移，氧化电流增大．根据现场红外光谱推测，催化作用是通过抗坏血酸的烯酸基与CoHCF相互作用实现的．     

生物分子电催化的研究：V.邻菲绕啉电化学聚合修饰电极的性质

本文用恒电位，恒电流，循环扫描等电化学方法，首次制备了邻菲绕啉（０－ｐｈｅｎ）聚合膜修饰电极，在０．０１ｍｏｌ／ＬＫＣｌＯ４水溶液中，其氧化与还原过程的峰电位分别为＋０．０４Ｖ和－０．５３Ｖ（ｖｓ．ＳＣＥ），该修饰电极在酸性，中性，碱性条件下均具有良好的稳定性，能较好地改善Ｋ３Ｆｅ（ＣＮ）６和Ｖｋ３在电极上的氧化还原性质，对维生素Ｃ和肼的氧化有很好的催化作用，其氧化峰电位分别降低２２０ｍＶ和５６２     

非水溶剂中铁酞菁的“in—situ”可见紫外光谱电化学

用循环伏安与现场可见紫外光谱电化学方法研究了氯化４－特丁基苯氧基铁酞菁［（ＴｂＰｃ）Ｆｅ（Ⅲ）Ｃｌ］电化学行为．结果表明，在四氢呋喃溶剂中其正电位区经历了两步氧化过程，对应于Ｆｅ（Ⅲ）／Ｆｅ（Ⅳ）以及Ｆｅ（Ⅳ）／阳离子自由基的生成反应，负电位区还原过程经历了Ｆｅ（Ⅲ）／Ｆｅ（Ⅱ），Ｆｅ（Ⅱ）／Ｆｅ（Ⅰ）和Ｆｅ（Ⅰ）／阴离子自由基生成的３个步骤，阐述了配位效应对氧化还原机理的影响．指出Ｆｅ（Ⅳ）不寻常价态的出现，是阴离子Ｃｌ－的轴向配位对超常价态起到稳定作用的结果．     

玻碳电极上六氰亚铁酸钯膜的现场FTIR光谱电化学研究

本文报道六氰亚铁酸钯膜修饰电极在ＨＣｌ,ＫＣｌ和ＮａＣｌ溶液中的现场反射ＦＴＩＲ光谱电化学研究,结果表明该修饰膜具有内外两层结构,分别为Ｐｄ２Ｆｅ（ＣＮ）６和Ｍ２ＰｄＦｅ（ＣＮ）６,其中Ｍ为支持电解质一价阳离子．在１ｍｏｌ／ＬＮａＣｌ中,内层的氧化电位Ｅｍ＝０．８７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）,外层为０．７７Ｖ．在１ｍｏｌ／ＬＨＣｌ或ＫＣｌ中两层的氧化还原波重叠为一个大ＣＶ波峰而难以分辨,然而现场ＦＴＩＲ光谱电化学清晰地分辨出这两种结构在所有３种溶液中ＣＮ的不同振动频率,发现Ｈ＋离子是最佳的支持电解质,能使这两种结构同时发生氧化反应     

芳香烃异构体的毛细管柱气相色谱－傅里叶变换红外光谱联用技术分析

采用国产色谱仪与进口红外光谱仪及接口组成的气相色谱－傅里叶变换红外光谱（ＧＣ／ＦＴＩＲ）分析仪，使用大口径毛细管柱，分析了乙苯与苯乙烯固相催化反应液的复杂芳香烃异构体组成，讨论了ＧＣ／ＦＴＩＲ分析中随机噪声和基线漂移的去除方法。采用等高线图（ＣＴＤ）分析技术得到了混合液中各组分的纯气相红外光谱图，最后鉴定了１４个气相色谱峰中的９个，占整个色谱峰面积９９％以上。     

芳香烃异构体的毛细管柱气相色谱—傅里叶变换红外光谱联用技术分析

采用国产色谱仪与进口红外光谱仪及接口组成的气相色谱－傅里叶变换红外光谱（ＧＣ／ＦＴＩＲ）分析仪，使用大口径毛细管柱，分析了乙苯与苯乙烯固相催化反应液的复杂芳香烃异构体组成，讨论了ＧＣ／ＦＴＩＲ分析中随机噪声和基线漂的去除方法。采用等高线图９ＣＴＤ）分析技术得混合液中各组分的纯气相红外光谱图，最后了１４个气相色谱峰中的９个，占整个色谱峰面积９９５以上。     

四核钼簇合物Mo_4S_4（μ－OAc）_2（dtp）_4在一些非水溶剂中的电化

利用循环伏安法测定了四核钼簇合物Ｍｏ_４Ｓ_４（μ－ＯＡｃ）_２（ｄｔｐ）_４在ＣＨ_３ＣＮ，ＤＭＦ，ＤＭＳＯ等溶剂中的氧化还原半波电位（Ｅ_（１／２）），对其氧化还原峰进行了归属，结果表明在ＣＨ_３ＣＮ中存在一个单电子的氧化过程和二个单电子的还原过程，而在ＤＭＦ和ＤＭＳＯ中只存在二个单电子的还原过程。同时还探讨了溶剂的ＤＮ数对该簇合物电化学性质的影响。     

镓—茜素紫极谱络合吸附波的研究

在含有０．０５ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ５．６）、０．１ｍｏｌ／Ｌ ＫＣＬ和１．５×１０＾－５ｍｏｌ／Ｌ茜素紫的溶液中，镓（Ⅲ）－茜素紫络合物在单扫示波极谱仪上产生一灵敏的导数极谱波，峰电位在－１．１１Ｖ（ｖｓ．ＳＣＥ），峰电流与镓（Ⅲ）浓度在２．０×１０＾－８ｍｏｌ／Ｌ。机理研究表明，峰电流是由吸附在电极表面的络合物中的中心离子和配位体同时还原而产生的。方法已应用于铝合金中镓的测定，结果     

纤维蛋白原在Pt电极上的界面电化学研究

应用电化学方法和电化学原位红外反射光谱(electrochemical in-situ FTIR)等研究了纤维蛋白原在Pt电极上的界面电化学行为.结果表明:纤维蛋白原在Pt电极上的吸附使电极的析氢与氧脱附过程减弱,影响程度随扫速的增加而增强;同样纤维蛋白原的吸附会降低亚铁氰化钾-铁氰化钾电对的氧化还原反应可逆性和电流;在-0.1~0.6V(vs.SCE)扫描范围内没有出现纤维蛋白原的特征"氧化还原"峰.电化学原位红外反射光谱测试表明纤维蛋白原在0.3~0.5V(vs.SCE)间发生化学反应,有新的产物生成.     

CoTPP电化学催化原溴代环己烷的机理

以电化学循环伏安、现场ＥＳＲ电化学以及现场薄层电化学方法研究了电生Ｃｏ（Ｉ）ＴＰＰ与溴代五己烷的反机制。在ＤＭＦ中，Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）的氧化还原有明显的催化溴代环己烷还原的特片，反现场有自由基生成，反应产物之一是Ｃｏ－Ｃ键化合物，可以在１．３０Ｖ（ＳＣＥ）－电子还原，当存在ＣＨ２－ＣＨＣＮ时，。生成另一种Ｃｏ－Ｃ键化合物，该化合物在－１．１０Ｖ（ＳＣＥ）处一电子还原，证明溴代环己烷与Ｃｏ（Ｉ）     

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.