儿茶酚胺类药物的流动注射化学发光分析

观察到雷盐（ＮＨ４「Ｃｒ（ＮＨ３）２」（ＳＣＮ）４」。Ｈ２Ｏ）对鲁米诺－Ｈ２Ｏ２化学发光反应的催化作用。根据儿茶酚胺类物质可与雷氏盐发生沉积反应而导致鲁米诺－Ｈ２Ｏ－２雷氏盐体系化学发光强度降低的性质，建立了儿茶酚胺类物质多巴胺，肾上腺素和异丙肾上腺素的流动注射化学发光分析法。     

四元体系CsCl—PrCl3—13%HCl—H2O（25℃）和CsCl—PrCl3—42%H…

测定了四元体系ＣｓＣｌ－ＰｒＣｌ３－１３％ＨＣｌ－Ｈ２Ｏ（２５℃）和ＣｓＣｌ－ＰｒＣｌ３－４２％ＨＡｃ－Ｈ２Ｏ（３０℃）的稳定平衡态的溶液数据，绘制了相应的溶度图，两个体系的皆中有４种固相，ＣｓＣｌ，ＰｒＣｌ３．６Ｈ２Ｏ２种原始盐和ＣｓＣｌ．ＰｒＣｌ３．６Ｈ２Ｏ，３ＣｓＣｌ．ＰｒＣｌ３．７Ｈ２Ｏ２种复盐，证实了文献中对Ｍｅｙｅｒ反应１机理的解释，并对新相进行了热分析，Ｘ射线粉末衍射及偏光显微镜测定     

邻硝基苯基荧光酮化学发光性能和机理研究

研究了在碱性介质中金属离子催化邻硝基苯基荧光酮（ｏ－ＮＰＦ）－Ｈ２Ｏ２体系的化学发光行为。结果表明，在研究的２０多种金属离子中，只有Ｃｏ２＋离子对ｏ－ＮＰＦ－Ｈ２Ｏ２体系有较强的催化发光作用，Ｃｏ２＋的浓度与发光强度在２．５×１０－９～３．０×１０－６ｇ／ｍＬ范围内呈良好的线性关系。通过对化学发光光谱、荧光光谱的研究以及用Ｈｕｃｋｅｌ分子轨道法（ＨＭＯ）计算了ｏ－ＮＰＦ的π电子分布和键级，提出了ｏ－ＮＰＦ可能的化学发光机理．     

N—（β—羧丙酰基）异鲁米诺的电致化学发光行为及其机理探讨

本进行了Ｎ－（β－羧丙酰基）异鲁米诺的电致化学发光行为的研究。采用正矩形液脉冲电压，在ＫＯＨ－ＫＣｌ－Ｈ２Ｏ２－（ｐＨ１１．６）介质中，Ｎ－（β－羧丙酰基）异鲁米诺测定的线性范围为４．０×１０＾－１０￣７．０×１０＾－８ｍｏｌ／Ｌ，检出限为２．０×１０＾－１０ｍｏｌ／Ｌ。本对此体系的电致化学发光机理进行了探讨。     

三元体系MgCl2—CO（NH2）2—H2O在25℃时的等温溶度与新相 …

测定了２５℃时三元体系ＭｇＣｌ２－ＣＯ（ＮＨ２）２－Ｈ２Ｏ的等温溶度及饱和溶液的折光率和密度，且绘制成溶度图和性质，组成图，在三元体系内形成２个三元化合物新相，ＭｇＣｌ２．ＣＯ（ＮＨ２）２．４Ｈ２Ｏ（记作Ａ）和ＭｇＣｌ２．４ＣＯ（ＮＨ２）．２Ｈ２Ｏ（记作Ｂ），Ｂ为新化合物，三元体系的溶度图由４支单饱和线（对应单饱和因相为ＭｇＣｌ２．６Ｈ２Ｏ，三元化合物Ａ和Ｂ，ＣＯ（ＮＨ２）２）组成，这４支单饱和线     

4—氨基—3,5—二甲基—1,2,4—三唑水杨亚胺合铜[Ⅱ]配合物合成及其单…

４－氨基－３，５－二甲基－１，２，４－三唑与水杨醛缩合形成４－（邻羟苯基亚甲基）－亚胺－０３，５－二甲基－１，２，４－三唑Ｓｃｈｉｆｆ碱（ＳＡＴＺ），该Ｓｃｈｉｆｆ碱与Ｃｕ（ＣｌＯ４）２．６Ｈ２Ｏ形成配合物Ｃｕ（ｓａｔｚ）２．６Ｈ２Ｏ，分子式为Ｃ２２Ｈ２２ＣｕＮ８Ｏ２．６Ｈ２Ｏ。     

稀土Yb(Ⅲ)对Luminol-H2O2-Cr(Ⅲ)体系的化学发光熄灭效应

研究了稀土Ｙｂ（Ⅲ）对Ｌｕｍｉｎｏｌ－Ｈ２Ｏ２－Ｃｒ（Ⅲ）体系化学发光的熄灭效应，在此基础上建立了稀土Ｙｂ的流动注射化学发光分析法。该法灵敏度高，线性范围宽，仪器设备简单，操作方便     

三元体系Y(ClO4)3·3H2O—B15C5—CH3OH(25℃)的半微量相平衡研究

采用半微量相平衡方法研究了三元体系Ｙ（ＣｌＯ４）３．３Ｈ２Ｏ－Ｂ１５Ｃ５－ＣＨ３ＯＨ在２５℃的溶解度，测定了各饱和溶液的折光率。该体系在２５℃生成三种化学计量的配合物，其组成分别为：４Ｙ（ＣｌＯ４）３．３Ｂ１５Ｃ５．１２Ｈ２Ｏ．１２Ｃｈ３ＯＨ（Ｉ），Ｙ（ＣｌＯ４）３．２Ｂ１２Ｃ５．３Ｈ２Ｏ．Ｃｈ３ＯＨ（Ⅲ），其中配合物（Ｉ）和（Ⅱ）是溶解不一致化合物。在甲醇溶剂中，分离制备了配合物（Ⅲ），在６９－     

金属键有机化合物的研究—非对称型η^5—取代环戊二烯…

通过η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３ＭＨａ与η＾５－Ｒ＾２Ｃ５Ｈ４（ＣＯ）２ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３ＭｏＮａ与η＾５－Ｒ＾２Ｃ５Ｈ４（ＣＯ）３ＷＮａ在Ｆｅ２（ＳＯ４）３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η＾５－Ｒ＾１Ｃ５Ｈ４（ＣＯ）３Ｍｏ－Ｍｏ（ＣＯ）３Ｃ５Ｈ４Ｒ＾２－η＾５（Ｒ＾１，Ｒ＾２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η＾５     

[Cu2（Gly—GlyO）2（4,4‘—bpy）（OH）2].10H2O配合物的合成,晶 …

合成了以４，４－ｂｐｙ为中继基，Ｇｌｙ，ＧｌｙＯ为螯环的新型双核铜配合物。经Ｘ射线单昌结构分析确定该配合化合物的化学式为「（Ｈ２ＣＣＨ２ＣＯＮＨＣＨ２ＣＯＯ）Ｃｕ（ＯＨ）Ｃｕ（ＯＨ）（Ｃ１０Ｈ８Ｎ２０Ｃｕ（ＯＨ）－（Ｈ２ＮＣＨ２ＣＯＮＨＨＣＨ２ＯＯ）．」１０Ｈ２Ｏ。     

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.