研究合成具有抗肿瘤活性新型化合物

<正>记者从华南农业大学获悉,该校理学院设计、合成了两个具有抗肿瘤活性的新型化合物。相关成果近期在线发表于英国皇家化学会期刊《道尔顿无机化学》。据了解,关于金属配合物型抗肿瘤化合物的抗肿瘤活性及其作用机理方面的研究已经成为当今抗肿瘤药物研究开发的重要方向。其中,靶向DNA小沟特异碱基系列的金属配合物作为抗肿瘤试剂的研     

质谱在金属抗肿瘤化合物分子作用机理研究中的应用

软电离质谱,包括电喷雾质谱(ESI-MS)和基质辅助激光解吸电离质谱(MALDI-MS)已成为研究金属抗肿瘤药物与蛋白质、DNA等生物大分子相互作用最强有力的工具.质谱成像技术在组织、细胞水平上探索金属抗肿瘤化合物作用机理研究上的应用也方兴未艾.本文基于在金属抗肿瘤配合物分子作用机理研究中的工作进展,系统地总结、评述质谱在铂基和钌基金属抗肿瘤配合物分子作用机理研究中的应用,介绍质谱研究金属抗肿瘤配合物与蛋白质和DNA相互作用及作用位点的最新研究成果,并展望质谱在这一前沿交叉领域的应用前景和趋势.     

单羟基咔咯锰（III）配合物的合成及其与DNA的相互作用

以五氟苯基二吡咯烷烃为原料,与对羟基苯甲醛经缩合反应合成了单羟基自由咔咯（1）; 1与醋酸锰反应合成了一种单羟基咔咯锰配合物--10-(4-羟基苯基)-5,15-二(2,3,4,5,6-五氟苯基)咔咯锰(III)配合物,其结构经UV-Vis和HR-MS（ESI）表征。通过紫外滴定、荧光滴定、圆二色谱和琼脂糖凝胶电泳实验探讨了其催化氧化DNA的活性。     

单羟基咔咯锰(Ⅲ)配合物的合成及其与DNA的相互作用

以五氟苯基二吡咯烷烃为原料,与对羟基苯甲醛经缩合反应合成了单羟基自由咔咯(1);1与醋酸锰反应合成了一种单羟基咔咯锰配合物——10-(4-羟基苯基)-5,15-二(2,3,4,5,6-五氟苯基)咔咯锰(Ⅲ)配合物,其结构经UV-Vis和HR-MS(ESI)表征。通过紫外滴定、荧光滴定、圆二色谱和琼脂糖凝胶电泳实验探讨了其催化氧化DNA的活性。     

新型吩噻嗪-咔咯锰（III）配合物的合成及其催化氧化DNA断裂的活性

以单羟基自由咔咯为起始原料,与吩噻嗪-10-碳酰氯（PTZ）反应制得吩噻嗪 咔咯二元化合物(2）; 2与醋酸锰反应合成了一种新型5,15-二（2,3,4,5,6)-五氟苯基-10-(4-吩噻嗪苯基)咔咯锰（Ⅲ）配合物(3),收率80.0%,其结构经UV-Vis和HR-MS（ESI）表征。通过琼脂糖凝胶电泳实验探讨了其催化氧化DNA的活性。结果表明：在过氧化氢存在下,3能有效引起超螺旋pBR322 DNA发生氧化断裂,3浓度为250 μmol·L^-1时,氧化断裂DNA的活性达34%。通过紫外滴定、荧光滴定、圆二色谱推断3与小牛胸腺(ct-DNA）的结合模式为外部结合。     

新型吩噻嗪-咔咯锰(Ⅲ)配合物的合成及其催化氧化DNA断裂的活性

以单羟基自由咔咯为起始原料,与吩噻嗪-10-碳酰氯(PTZ)反应制得吩噻嗪-咔咯二元化合物(2);2与醋酸锰反应合成了一种新型5,15-二(2,3,4,5,6)-五氟苯基-10-(4-吩噻嗪苯基)咔咯锰(Ⅲ)配合物(3),收率80.0%,其结构经UV-Vis和HR-MS(ESI)表征。通过琼脂糖凝胶电泳实验探讨了其催化氧化DNA的活性。结果表明:在过氧化氢存在下,3能有效引起超螺旋p BR322 DNA发生氧化断裂,3浓度为250μmol·L~(-1)时,氧化断裂DNA的活性达34%。通过紫外滴定、荧光滴定、圆二色谱推断3与小牛胸腺(ct-DNA)的结合模式为外部结合。     

钴（III）咔咯合成与应用研究进展

综述了不同类型咔咯自由碱及其金属钴（III）配合物的合成方法，并分类探讨了不同类型的金属钴（III）咔咯在能源化学与环境化学领域的应用，包括（1）电化学催化氧气还原；（2）分子传感器；（3）有机氯污染物降解；（4）烯烃催化氧化。同时，对钴（III）咔咯化学未来的发展方向进行了展望。     

苯基桥联双咔咯镓配合物的合成与发光性质

合成了苯基桥联双咔咯(1)及其镓配合物(2),利用紫外-可见光谱(UV-Vis),核磁共振波谱(1H NMR,19F NMR)及质谱(MS)对它们进行了表征.采用稳态和时间分辨荧光光谱对化合物1和2的发光性质进行了研究.实验结果表明,双咔咯1及其镓配合物2的荧光量子产率分别为0.142和0.473,荧光寿命相应为5.2与3.2 ns,且配合物2的荧光光谱显著蓝移.瞬态吸收光谱显示,在无氧条件下双咔咯1和配合物2的三重激发态(T1)寿命分别为58与34μs,其T1态的量子产率则分别为0.47和0.63.     

桑色素及其配合物与DNA作用的研究

桑色素 (Morin)是黄酮类化合物 ,具有一定的抗肿瘤活性 [1] .前文 [2 ] 以桑色素为配体合成了 6种过渡金属的配合物 ,并研究了这些配合物与配体对超氧阴离子自由基的清除作用和抗肿瘤活性 .研究表明 ,配合物对超氧阴离子自由基的清除作用明显高于配体 ,桑色素合铜 ( )和桑色素合锌 ( )配合物对 Hep- 2 ,BHK- 2 1和 HL - 6 0癌细胞瘤株的抑制作用强于配体 .配合物具有比单一有效成分更显著的药效 [3 ,4 ] .本文采用荧光方法和电化学方法研究了桑色素和抗肿瘤活性较强的桑色素合铜 ( )、桑色素合锌 ( )与 DNA在生理条件下的相互作用 ,试图…     

铝镓咔咯配合物的发光性质、堆积效应与轴向配位作用

本文合成了2种第三主族金属铝和镓咔咯配合物Al(tpfc)、Ga(tpfc)、Al(tpfc)(Py)2、Ga(tpfc)(Py)。测定了在甲苯溶液中,铝和镓咔咯的电子光谱、荧光光谱、荧光量子产率及荧光寿命。在不同溶剂作用下,铝和镓咔咯的电子吸收光谱和荧光光谱的峰位置和强度存在差异。在二氯甲烷溶液中,轴向配体吡啶能促进铝和镓咔咯的π-π堆积。不同轴向配体与金属咔咯的结合能力为:咪唑>4-甲基咪唑>吡啶,铝比镓的咔咯配合物有更强的结合轴向配体的能力。     

多环芳二酐型聚酯亚胺膜的透气性能

多环芳二酐型聚酯亚胺膜的透气性能李悦生，丁孟贤，徐纪平（浙江大学高分子科学与工程研究所，杭州，３１００２７）（中国科学院长春应用化学研究所）关键词聚醚酰亚胺，聚酯酰亚胺，膜，透气性通常的聚酰亚胺加工性能较差，在芳环二酐的苯环间引入醚键等柔性基团后，其...     

Determination and study on residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) method for the determination of benazolin-ethyl and quizalofop-p-ethyl in rape and soil by high-performance liquid chromatography-tandem mass spectrometry has been developed in this study. The residue and dissipation of benazolin-ethyl and quizalofop-p-ethyl in rape and soil were determined with the developed method. The half-lives of benazolin-ethyl in rape straw and soil were 3.7–5.1 days and 14.3–26.3 days, respectively. The half-lives of quizalofop-p-ethyl in rape straw and soil were 5.0-6.1 days and 0.3–9.7 days, respectively. The residue of benazolin-ethyl and quizalofop-p-ethyl in rapeseed and soil were below the detection limit (i.e., 0.5?mg?kg^?1, the maximum residue level of European Union for quizalofop-p-ethyl).     

微量元素与疾病诊断治疗的研究现状及展望

对国内外微量元素与疾病的关系及其诊断治疗的研究现状及研究动向进行了综述，包括：微量元素与地方病、癌肿、心血管病、糖尿病、眼病、神经系统病等。参考文献72篇。     

Conformations and steric and stacking interactions of trisubstituted ureas and thioureas with alkyl and phenyl groups

The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R₂UPh type and -thioureas of the R₂TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments.     

Synthesis and Optical and Redox Properties of Symmetric and Asymmetric BODIPYs

Herein, we present the synthetic route and the photophysical, electrochemical as well as laser properties of novel red‐emitting boron‐dipyrromethenes (BODIPYs) bearing arylethyne moieties. Such functionality is added along the main axis of the chromophore leading to single‐ and double‐substituted derivatives. The relationship between the dye structure and the lasing properties is studied in detail with the help of the photophysical and electrochemical properties as well as quantum mechanical simulations. The asymmetric substitution of the parent dye induces inhomogeneities in the charge distribution, which leads to an overall loss of the fluorescence capacity, mainly in polar media. Such non‐radiative deactivation processes can be softened by decreasing the electron‐donor ability of the substituent or even avoided by symmetrical substitution. Thus, grafting of the arylethyne moieties at the longitudinal axis of the indacene core results in an effective strategy to develop red‐edge BODIPYs with highly efficient and photostable laser emission.     

Ti-V基储氢合金及其氢化物的物相结构与组分优化设计

Ti-V基储氢合金在室温、常压下即可表现出良好的储氢特性,且质量储氢容量明显高于传统AB₅型储氢合金,从而在氢气的精制和回收、运输和储存及热泵等方面有较早的应用。 此外,在混合气体分离、核反应堆中处理氢的同位素、镍氢电池及燃料电池负极材料等方面也得到了广泛的研究与关注。 基于目前Ti-V基储氢合金的研究现状,概述了该类合金的优势、限制性因素(包括成因)及改性手段。 此外,为了进一步理解Ti-V基合金储氢机理、构建合金组分与储氢特性之间的对应关系,本工作重点围绕Ti-V基储氢合金及其氢化物的结构、组分优化设计展开综述,并对其未来研究方向做出展望。     

钒与糖代谢及糖尿病

微量元素钒作为生物体内必需元素，经证实有很重要的生理学功能，与机体糖代谢有十分密切的关系，且能降低糖尿病动物模型的高血糖，极有可能被开发为治疗糖尿病的药物。     

Ferrocene and ferrocenium modified clays and their styrene and EVA composites

In this work, ferrocene- and ferrocenium-containing salts were employed to modify montmorillonite. X-ray measurements show an increase in the interlayer spacing upon clay modification, which means that the larger and more organophilic cations were inserted into the gallery space of montmorillonite. Attempts to prepare nanocomposites of polystyrene and ethylene vinyl acetate copolymers lead to immiscible systems; the morphology of these systems was elucidated with TEM, XRD and cone calorimetry. The thermal stability of the composites is greater than that of the virgin polymer.     

Homo- and copolymerizaton of norbornene and norbornene derivative with Ni- and Pd-based β-ketoiminato complexes and MAO

Neutral nickel(II) and palladium(II) complexes bearing β-ketoiminato ligand have been synthesized. The two complexes have been investigated as catalyst for the polymerization. Using methylaluminoxane (MAO) as a cocatalyst, both complexes produce vinyl-addition polynorbornenes, but palladium(II) complex displays much higher activity up to 8.0 × 10⁷ g/(molPd h). Furthermore, both Ni(II) and Pd(II)/MAO system can efficiently copolymerize norbornene and 5-norbornene-2-yl acetate (NB-OCOMe) in moderate yields and in relatively high molecular weights. The analyses of the product by FTIR, ¹H NMR and ¹³C NMR spectra give the verification of vinyl addition copolymer. The copolymers show narrow molecular weight distribution and good solubility in common organic solvents.