阿霉素在钴离子注入修饰电极上的电化学行为及其应用

阿霉素在０．１ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．６２）缓冲溶液中用注入钴的修饰玻碳电极为工作电极进行伏安测定,得到一良好的还原峰;Ｅｐ＝－０．５２２Ｖ（ｖｓ．ＳＣＥ）。峰电流与阿霉素浓度在１．４×１０＾－６－１．４×１０＾－６ｍｏｌ／Ｌ和１．４×１０＾－６－５．６×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系,。     

用8—氨基喹啉高选择性分光光度法测定痕量锇的研究

研究了用８－氨基喹啉在ｐＨ３．６２的ＨＡｃ－ＮａＡｃ缓冲溶液中测定痕量Ｏｓ（Ⅳ）的分光光度法。常用的非贵金属和贵金属离子不干扰测定，并且选择性较好。Ｏｓ（Ⅳ）与８－氨基喹啉的组成比为１：３，表观摩尔吸光系数ε６００＝１．３×１０＾５Ｌ／ｍｏｌ·ｃｍ。在０～１０μｇ／１０ｍＬ范围内符合比耳定律。合成样品分析结果良好。     

吸附络合物体系的示波分析

Ｉｎ（Ⅲ）在ｐＨ４５７ＨＡｃＮａＡｃ０．１％ＶＣ０．０６％ＨＣｕＰ溶液中，用示波计时电位法可获得良好示波图，其切口电位为Ｅ＝０９０（Ｖｓ．ＳＣＥ），切口高度与Ｉｎ（Ⅲ）浓度在８００×１０－７～１４×１０－５ｍｏｌ／Ｌ范围内成正比，检出限可达５０×１０－７ｍｏｌ／Ｌ吸附络合物组成为Ｉｎ（Ⅲ）：铜铁试剂（ＨＣｕｐ）＝１∶１，条件稳定常数为５９×１０３     

新显色剂邻羧基苯基偶氮桑色素褪色光度法测定微量铁的研究

本文研究了新显色剂基苯偶氮桑色素与铁（Ⅲ）在ｐＨ５．６的缓冲溶液中的褪色反应，实验结果表明，利用此褪色反应测定铁（Ⅲ）其灵敏度高，表观摩尔吸光系数达３．１５×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，线性范围０～０．１μｇ／２５ｍＬ，检测限为：１．８×１０＾－１０ｇ／ｍＬ。应用于黑色食品中微量铁的测定，获是了满意的结果。     

淋必治的极谱研究

在０．１ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．５０）支持电解质中，淋必治（ＳＰＥ）有一灵敏的示波极谱导数还原峰，峰电位Ｅｐ＝－０．９８Ｖ（ｖｓ．ＳＣＥ）。峰电流与ＳＰＥ的浓度在２．０×１０＾－７￣８．０×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系，最低检出限为５．０×１０＾－８ｍｏｌ／Ｌ。该法用于注射针剂中ＳＰＥ含量的测定。，结果良好。文中对ＳＰＥ的极谱行为、电极过程及反应机理进行了探讨。     

用银和铅标记人白蛋白的离子选择电极电位法研究

用离子选择电极电位法研究了银和铅与人白蛋白（ＨＳＡ）的配合平衡。明确证实银和铅都与ＨＳＡ形成了单核配合物ＭＡ和ＭＡ２．Ａｇ－ＨＳＡ配合物的稳定性积β１１＝４．４×１０＾７，β１２＝１．０×１０＾１２；Ｐｂ＝ＨＳＡ配合物的β１１＝３．１×１０＾５，β１２＝２．０×１０＾９。根据ＨＳ与人白蛋白羊抗血清（ＧＡＨＡ）的免疫反应，用银和铅分别标记ＨＳＡ时，测定ＧＡＨＡ（效价１：４０）的线性范围是０．２～２．     

铜—腺嘌呤络合物吸附波的研究

了在０．０８ｍｏｌ／ＬＮａＡｃ～０．０２ｍｏｌ／ＬＨＡｃ缓冲溶液铜与腺嘌呤（Ａｄｅ）络合物的极谱行为，结果表明，扫描电压为－０．２Ｖ～－０．７Ｖ时铜－腺嘌呤络合物在单扫示波极谱上有一络合物吸附波，其一阶导数峰电位主－０．４Ｖ（ｖｓ．ＳＣＥ），腺嘌呤浓度在１．０×１０＾－６～１．０×１０＾－５ｍｏｌ／Ｌ范围内与一阶导数波高呈良好的线性关系，检出限为１．０×１０＾－７ｍｏｌ／Ｌ，实验证明，该峰具有吸附     

安力农的极谱测定及其电化学行为

在ｐＨ５．６，０．１５ｍｏｌ／Ｌ磷酸盐缓冲溶液（ＰＢＳ）中，得到了安力农的灵敏极谱吸附波，波的二阶导波高在２×１０＾－８～８×１０＾－６ｍｏｌ／Ｌ范围内与安力农的浓度成直线关系，检测下限为１×１０＾－８ｍｏｌ／Ｌ，测定出电极过程的电子传递系数ａ＝０．４３，表面电极反尖速率常数ｋｓ＝３．３ｓ＾－１，安力农在汞电极上的吸附遵从Ｌａｎｇｍｕｉｒ等温式，测得其吸附系数β＝８．１×１０＾５。     

氧氟沙星—镁络合吸附波的研究

本文用多种电化学方法研究了氧氟沙星与镁离子的相互作用及其极谱伏安行为，在０．０１ｍｏ１／Ｌ的ＮＨ３－ＮＨ４Ｃ１缓冲溶液中（ｐＨ＝９．２），氧氟沙星与镁离子络合，产生一灵敏的还原峰，峰电位ＥＰ＝－１．７０Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）．该峰为不可逆的络合吸附峰，还原峰电流与镁离子浓度在４×１０－６～２×１０－５ｍｏｌ／Ｌ范围内呈良好的线性关系，可望用于镁离子的分析测定．本文还测定了该络合物的络合比，探讨了电极反应机理与络合物结构．     

显色剂N—烯丙基—N‘—（氨基对苯磺酸钠）硫脲与钯（Ⅱ）显色反应的研究和…

本报道了极易溶于水的显色剂Ｎ－烯丙基－Ｎ＇－（氨基对苯磺酸钠）硫脲光度法测定钯的条件，：在ＰＨ４．０－５．５缓冲介质中，ＡＳＡＴｕ与钯生成易溶于水的、稳定的黄色络合物，组成比为：Ｐｄ（Ⅲ）：ＡＳＡＴｕ＝１：４；络合物的最大吸收波长为２９６．０ｎｍ表观摩尔吸光系数ε２９６＝１．３３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１；钯（Ⅱ）在０－２０嗳μｇ／２５ｍＬ呈线性，相关系数γ＝０．９９９５。该法灵敏度     

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.