铜-(N-正十二碳酰双甘肽)配合物模拟SOD研究

合成一种新的SOD模拟物－带功能基的长链铜（II）氨基酸配合物N－正十二碳酰双甘肽合铜[Cu(C12-Gly-Gly]和二－（Ｎ－正十二碳酰双甘肽合铜）[Cu(C12-Gly-Gly)2],用脉冲辐解法测定了其ＳＯＤ样活性,发现Ｃu(C12-Gly-Gly）２的ＳＯＤ样活性基本接近于天然ＳＯＤ,达到了整体模拟ＳＯＤ的效果。     

水溶性铑膦配合物HRh(CO)(TPPTS)_3及其相关体系的~1H-NMR研究

在液体高分辨ＮＭＲ谱仪上, 测定并比较了具有高效烯烃氢甲酰化活性的水溶性铑膦配合物ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３ 及与此有关的配体ＴＰＰＴＳ和ＯＴＰＰＴＳ分别在Ｄ２Ｏ、混合溶剂Ｄ２Ｏ－ＴＨＦ（ｄ８）－ＣＤ３ＯＤ中的１Ｈ－ＮＭＲ谱图, 并借助１Ｈ－１Ｈ ＣＯＳＹ谱对上述３ 种化合物的１Ｈ－ＮＭＲ谱峰进行了指认; 讨论了影响化学位移和偶合常数的因素, 为水溶性铑膦配合物催化剂的结构与催化性能的关联及新催化剂设计研究提供了基础数据．     

D—葡萄糖与氯化稀土配合物的合成及红外光谱研究

以非水溶剂为介质合成了Ｄ－葡萄糖，氯化稀土，吡啶的混配多元配合物，并进行了元素分析和红外光谱测定。研究结果表明，Ｄ－葡萄糖和溶剂吡啶同时参与了配位，该配合物的组成为：Ｌｎ（Ｃ６Ｈ１２Ｏ６）（Ｃ５Ｈ５Ｎ）Ｃｌ３（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ等）。本文还对配合物的可能结构进行了讨论。     

D－葡萄糖与氯化稀土配合物的合成及红外光谱研究

以非水溶剂为介质合成了Ｄ－葡萄糖、氯化稀土、吡啶的混配多元配合物，并进行了元素分析和红外光谱测定。研究结果表明，Ｄ－葡萄糖和溶剂吡啶同时参与了配位，该配合物的组成为：Ｌｎ（Ｃ_６Ｈ_（１２）Ｏ_６）（Ｃ_５Ｈ_５Ｎ）Ｃｌ_３（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ等）．本文还对配合物的可能结构进行了讨论．     

超氧化物歧化酶与过氧化氢酶的缀合物的制备与性质研究

我们用戊二醛制备了超氧化物歧化酶（ＳＯＤ）和过氧化氢酶（ＣＡＴ）的缀合物，ＳＯＤ和ＣＡＴ都是抗氧化应激酶系的成员，缀合物兼具两个酶的功能，具有很强的Ｈ＿２Ｏ＿２抑制作用，从而能更有效地清除活性氧，使之更适合于医用。     

吡啶—2,6—二甲醇配合物[Sc＊HDPA）（DPA）（H2O）2].5H2O的合成及其晶体结构

在水溶液 中合成了吡啶－２，６－二甲酸钪配合物的晶体，元素分析结果表明，可用Ｓｃ（ＨＤＰＡ）（ＤＰＡ）．７Ｈ２Ｏ表示。用Ｘ射线衍射方法测定了配合物的单晶结构，其结构式为［Ｓｃ（ＨＤＰＡ）（ＤＰＡ）（Ｈ２Ｏ２）］５Ｈ２Ｏ。晶体属正交晶系，空间群为Ｐｎ２ｌａ。     

POM／EVA共混物的研究

用力学测试、扫描电镜（ＳＥＭ）、热分析（ＤＳＣ）等手段研究了聚甲醛（ＰＯＭ）与乙烯－醋酸乙烯酯共聚物（ＥＶＡ）共混物（ＰＯＭ／ＥＶＡ）的力学性能及其微同形态；用聚甲醛与马来酸二丁酯（ＤＢＭ）的接枝物（ＰＯＭ－ｇ－ＤＢＭ）作相溶剂，能改变共的两相间的粘结力，从而提出了共混物的力学性能，ＳＥＭ观察表明接枝物的加入改变了ＰＯＭ／ＥＶＡ共混物的断裂方式，微观形态及结晶性能，对其热性能影响不大；通过改变ＰＯ     

双环氮杂锡氧烷配合物与醛的缩合反应的研究

含席夫碱双环氮杂锡氧烷配合物的结构与ＶＢ６酶体系结构相似。以含席夫碱二苯基锡配合物（ＰｈＳｎＬ１Ｈ）为研究对象，测定了二苯基锡配合物（ＰｈＳｎＬ１Ｈ）在ＤＭＳＯ中的ｐＫａ（１７．６０），同时研究了该配合物与醛的缩合反应，合成了７种新的含β－羟基－α－氨基酸配体的有机锡配合物（ＰｈＳｎＬ１ＣＨＯＨＲⅠ～Ⅶ），并由ＩＲ、１ＨＮＭＲ、１１９ＳｎＮＭＲ及元素分析等确定了配合物的结构。     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成,表征以…

合成了通式为Ｋ１５Ｈ３〔Ｃｅ（Ｐ２Ｗ１６ＶＯ６１）２〕．６１Ｈ２Ｏ、Ｋ１５Ｈ４〔Ｌｎ（Ｐ２Ｗ１６ＶＯ６１）２〕．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋，Ｐｒ＾３＋，Ｎｄ＾３＋，Ｓｍ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋）的９种镧系元素Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物，并用ＩＲ、ＵＶ、ＮＭＲ、ＥＳＲ、ＸＲＤ、ＴＧ－ＤＴＡ等对其结构和性质进行子研究。该类配合物具有与Ｋ１６〔Ｃｅ（Ｐ２Ｗ１７Ｏ     

聚二甲基硅氧烷／聚氨酯共混体系的增容作用（I）

采用二甲基硅氧烷－ｂ－乙二醇嵌段共聚物（ＤＭＳ－ｂ－ＯＥ）对聚二甲基硅氧烷／聚氨酯（ＰＤＭＳ／ＰＵ）共混体系的增容，重点研究了增容共混体系的微观形态结构和软科学性能之间的关系。扫描电子显微镜、动态力学分析和力学性能测试结果表明：ＤＭＳ－ｂ－ＯＥ对ＰＤＭＳ／ＰＵ具有优良的增容作用，改善了ＰＤＭＳ／ＰＵ共混体系的相容性，提高了该共混物的力学性能。其抗张强度由３．４ＭＰａ提高到７．６ＭＰａ。     

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.     

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.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.