Schiff碱,咪唑金属配合物的合成与抗癌活性

报道一类新的Ｓｃｈｉｆｆ碱和咪唑的混合型金属配合物，即水杨醛缩甘氨酸，咪唑金属配合物和２，４－二羟基苯甲醛缩丙氨酸，咪唑金属配合物的合成，用溴化乙锭荧光分析法研究了这类配合物与ＤＮＡ的相互作用，其中镍配合物与ＤＮＡ的作用明显。     

Schiff碱,咪唑金属配合物合成及抗癌活性的荧光筛选研究

本文报道了一类新的Ｓｃｈｉｆｆ碱和唑的混合型金属配合物（即水杨醛缩甘氨酸，咪唑金属配合物和２．４－二羟基苯甲醛缩丙氨酸，咪唑金属配合物）的合成，以及用溴化乙锭荧光分析法对这类配合物与ＤＮＡ相互作用的研究。结果表明，其中金属镍配合物与ＤＮＡ的作用效明显，可作为具有抗癌作用的药物进行深入研究。     

荧光法研究手性金属配合物与DNA的作用机理

以溴化乙锭为荧光探针，研究手性金属配合物［Ｎｉ（ｐｈｅｎ）３］＾＋和［Ｆｅ（ｐｈｅｎ）３］＾２＋与ＤＮＡ的反应机理。结果表明，配合物与ＤＮＡ作用存在插入和静电结合两种模式，即部分菲咯啉配体插入ＤＮＡ双螺旋碱基对中，同时带正电荷的配合物与ＤＮＡ的磷酸基团发生静电结合。     

丙二胺缩乙酰丙酮单席夫碱、咪唑金属配合物的XPS与电子结构分析

对6个丙二胺缩乙酰丙酮单席夫碱、咪唑（苯并咪唑）金属配合物进行了XPS分析，得到了配合物在生成过程中金属离子M(Cu^2 、Ni^2 、Co^2 ）的2p轨道、配位体N原子的1s轨道能级的变化道；观察到咪唑或苯并咪唑配位后，其环上另一个非配位的胺N原子向亚胺型N原子状态过渡。     

三菲咯啉合铁手性配合物键合DNA的立体选择性

应用光谱法研究了手性金属配合物［Ｆｅ（ｐｈｅｎ）３］＾２＋与小牛胸腺ＤＮＡ的作用，确定了△型异构体对Ｂ型右手螺旋ＤＮＡ有优先键合的立体选择性。     

[Cu(HIm)_2(PPh_3)_2](BF_4)的合成与晶体结构

铜?配合物以结构多样化、生物和医药活性和独特的光谱性能而成为活跃的研究领域,其合成、结构以及性能的研究已受到日益广泛的重视,它们与普通配体的分子设计和结构测定涉及生物无机化学,无机合成和金属基药物设计等内容犤１,２犦。咪唑衍生物是常见的生物配体,对生物功能起重要的作用,咪唑氮原子与金属离子配位成键,形成各种金属生物分子的活性中心,通过了解金属与咪唑氮原子配位的结构特点,建立生物活性结构模型配合物,可以达到研究金属酶活性中心结构与物性关系的目的犤３,４犦。生物体中大部分铜与两种以上配体形成混配配合…     

多咪唑盐合成的N-杂环卡宾金属配合物研究进展

N-杂环卡宾金属配合物具有良好的化学稳定性和催化活性,一直是有机化学研究领域中的热点.咪唑盐作为N-杂环卡宾的前体,其制备容易,结构多样的特点为构建拓扑结构的N-杂环卡宾金属配合物提供了基础.主要针对近年来由环状多咪唑盐、非环状多咪唑盐为配体与金属进行组装,或以咪唑盐与P/N配体与金属共同组装,或经过异腈分布合成法形成的具有特殊柱状、笼状、环状、"分子方"和"分子矩形"等结构的多N-杂环卡宾金属配合物的合成,结构及物理化学性质进行归纳总结,并对其研究前景进行了展望.     

过渡金属配合物断裂双链DNA及其机理

本文讨论了过渡金属配合物导致ＤＮＡ双链断裂的各种攫氢反应及碱基氧化机理,对由水解过程促进ＤＮＡ断裂的过渡金属配合物也作了介绍。     

微量热法研究[Cu（phen）2]^2＋、[Cu（bpy）2]^2＋与ＤＮＡ的作用

用微量热法对菲洛合铜[Cu(phen)2]2^2 和联吡合铜[Cu(bpy)2]^2 与小牛胸腺ＤＮＡ的相互作用进行了研究,依据ＭcGhee-Von Hippel邻近排斥方程确定了结合反应的平衡常数K、结合位点距离n及热力学参数 △rHm,△rGm和△rSm。结果表明这两种铜的配合物与ＤＮＡ之间均可 形成稳定的三元配合物,且反应为熵驱动过程,ＤＮＡ与这些配合物的刍合过程中同时存在插入和静电作用两种模式,插入作用的强弱与金属配合物中配体的平面性质有关。     

Schiff碱类芳香性金属配合物的合成及XPS研究

用乙二胺（或丙二胺）缩乙酰丙酮Ｓｃｈｉｆｆ碱三齿配体与咪唑（或苯并咪唑）及金属离子Ｍ（Ⅱ）配位，合成了１２种Ｓｃｈｉｆｆ碱类类芳香金属配合物，对这类配合物的Ｘ射线光电子能谱研究结果表明，配位后，金属离子的２ｐ电子结合能降低，配位Ｎ原子的１ｓ电子结合能增大；这类配全哦分子中的电荷移行径是以Ｌ→Ｍ为主，其配位键以σ键为主。     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.