新型不对称三齿多吡啶配体及其混配钌(Ⅱ)配合物的合成、表征及与DNA相互作用研究

合成了两个新型不对称三齿多吡啶配体,3-(1,10-菲咯啉基-2)-1,2,4-三唑(PHT), 3-(1,10-菲咯啉基-2)-5-甲基-1,2,4-三唑(PHMT),及其混配配合物[Ru(tpy)(PHT)]2+ (Ru1)和[Ru(tpy)(PHMT)]²⁺ (Ru2),通过元素分析、FAB-MS, ES-MS, ¹H NMR, IR, UV-vis,发射光谱和电化学对它们进行了表征.运用电子吸收光谱、竞争性结合实验和粘度测试等方法研究了配合物与DNA的作用机理,结果显示它们均是通过静电作用与DNA结合,且Ru2与DNA的作用比Ru1与DNA的作用更强.     

配体的空间构型及疏水性对钌（Ⅱ）多吡啶配合物与DNA作用的影响

合成了4－氰基苯基咪唑并[5,6-f]邻菲咯啉（CYIP）和2－羧基苯基咪唑并[5, 6-f]邻菲咯啉（COIP）两种新配体及它们的钌混配配合物[Ru(bpy)2CYIP](ClO4)2 ·H2O（Rul）（bpy=2,2′-联吡啶），[Ru(phen)2CYIP](ClO4)2·H2O(Ru2) (phen=1,10-邻菲咯啉），[Ru(bpy)2COIP](ClO4)2·3H2O(Ru3)和[Ru(phen)2COIP] (ClO4)2·H2O(Ru4)，并用红外光谱、紫外光谱、核磁和质谱对它们进行了表征。 通过循环伏安法研究了这些配合物的电化学性质。采用电子吸收光谱、稳态荧光、 圆二色谱和粘度测定研究了配合物与小牛胸腺DNA的相互作用。结果表明配合物 Rul和Ru2通过CYIP配体以插入的方式与DNA结合，而配合物Ru3和Ru4则通过COIP配 体以部分插入的方式与DNA结合。     

新型双核配合物的形成及荧光性质研究

利用光谱学方法研究了[Ru(bpy)2TPPHZ]2+(TPPHZ=四吡啶[3,2-a: 2',3'-c: 3",2"-h: 2'",3'"-j]吩嗪)和[Ru(bpy)2ODHIP]2+(ODHIP=3,4-二羟基-咪唑并[4,5-f][1,10]邻菲咯啉)与Ni2+的配位情况及配位后的荧光性质变化, 探讨了配合物与Ni2+配位形成双核配合物后与DNA的作用机制变化. 结果表明, [Ru(bpy)2TPPHZ]2+和[Ru(bpy)2ODHIP]2+均可与Ni2+配位, 形成双核配合物[Ru(bpy)2(TPPHZ)Ni]4+和[Ru(bpy)2(ODHIP)Ni]4+, 配合物的荧光强度随着Ni2+浓度的增加而减弱. 与DNA作用后, 配合物仍可与Ni2+配位形成双核配合物, [Ru(bpy)2(TPPHZ)Ni]4+的荧光几乎完全消失, 同时配合物与DNA保持插入模式作用, 而配合物[Ru(bpy)2(ODHIP)Ni]4+与DNA的作用则由沟面结合改为插入结合, 同时配合物的荧光减弱.     

噻吩基钌配合物与酵母RNA的相互作用研究

通过紫外-可见吸收光谱和荧光光谱滴定、稳态荧光猝灭以及盐效应实验研究了噻吩基钌配合物[Ru(bpy)2(Htip)]Cl2(1)、[Ru(Htip)2(dppz)]Cl2(2)、[Ru(Htip)3]Cl2(3)和[Ru2(bpy)4(H2bipt)]Cl4(4){bpy=2,2'-联吡啶;Htip=2-噻吩咪唑[4,5-f][1,10]邻菲咯啉;H2bipt=2,5-二(2-咪唑[4,5-f][1,10]邻菲咯啉)噻吩;dppz=二吡啶并[3,2-a:2',3'-c]吩嗪}与酵母RNA(yeast-RNA)的相互作用,并比较了该类配合物与yeast-RNA和小牛胸腺DNA(ct-DNA)的键合性质。结果表明,该类噻吩基钌配合物是较强的RNA嵌入试剂,其中配合物2和3的RNA键合强度大于其DNA键合强度;此系列配合物在低盐和高盐浓度时均能与RNA较强地结合,即使在100 mmol/L Na Cl条件下仍具有较大的RNA键合常数;配合物1与RNA键合时荧光强度下降,配合物2在水溶液中以及与RNA键合时几乎无荧光,而它们与DNA作用时荧光强度明显增大,显示出良好的区分RNA和DNA的荧光特性。     

钌(Ⅱ)多吡啶配合物的合成、荧光性质及与脱氧核糖核酸DNA的作用机制研究

设计合成含多个配位中心的多吡啶配体ODCIP(3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(Ⅱ)多吡啶配合物[Ru(bpy)2ODCIP]2 .运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征.利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2 与DNA(脱氧核糖核酸)的作用机制、与Co2 配位后与DNA的作用机制及其荧光变化情况.结果表明[Ru(bpy)2ODCIP]2 与DNA通过部分插入模式作用,[Ru(bpy)2ODCIP]2 与Co2 配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4 也能与DNA插入结合.进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2 和双核配合物[Ru(bpy)2(ODCIP)Co]4 的荧光性质.     

{2-(2-噻吩基)-1H-咪唑[4,5-f][1,10]菲咯啉-κN~7,κN~8}双(1,10-菲咯啉-κN~1,κN~(10))镍(Ⅱ)配合物的合成

以1,10-菲咯啉为原料,经氧化、缩合和络合反应合成了一种新的核酸荧光探针--{2-(2-噻吩基)-1H-咪唑[4,5-f][1,10]菲咯啉-κN7,κN8}双(1,10-菲咯啉-κN1,κN10)镍(Ⅱ)配合物,总收率38.2%,其结构经MS和元素分析表征.     

钌(II)多吡啶配合物的合成、荧光性质及与脱氧核糖核酸DNA的 作用机制研究

设计合成含多个配位中心的多吡啶配体ODCIP (3,4-二氯基苯并咪唑并[4,5-f][1,10]邻菲咯啉)及其钌(II)多吡啶配合物[Ru(bpy)2ODCIP]2＋. 运用元素分析、红外光谱、核磁谱和质谱对配体及配合物进行结构表征. 利用紫外吸收光谱、荧光光谱和粘度法研究了[Ru(bpy)2ODCIP]2＋与DNA(脱氧核糖核酸)的作用机制、与Co2＋配位后与DNA的作用机制及其荧光变化情况. 结果表明[Ru(bpy)2ODCIP]2＋与DNA通过部分插入模式作用, [Ru(bpy)2ODCIP]2＋与Co2＋配位形成的双核配合物[Ru(bpy)2(ODCIP)Co]4＋也能与DNA插入结合. 进一步利用稳态荧光发射光谱、荧光淬灭实验等方法研究了单核配合物[Ru(bpy)2ODCIP]2＋和双核配合物[Ru(bpy)2(ODCIP)Co]4＋的荧光性质.     

钌(Ⅱ)多吡啶配合物与DNA相互作用的光切割与荧光性质研究

利用琼脂糖凝胶电泳法研究了钌(Ⅱ)多吡啶配位物[Ru(bpy)2(ODCIP)]2+(bpy:2,2'-联吡啶,ODCIP:含多个配位中心的多吡啶配体,3,4-二氯基-咪唑并[4,5-f][1,10]邻菲咯啉)对pBR322质粒DNA的光切割作用及其可能机理,并运用紫外可见吸收光谱、荧光光谱和琼脂糖凝胶电泳法研究了[Ru(bpy)2(ODCIP)]2+与Zn2+配位后与DNA的光谱性质和光切割作用.结果表明[Ru(bpy)2(ODCIP)]2+对DNA有较好的光切割作用,其机理可能是产生了超氧阴离子自由基和单线态氧.[Ru(bpy)2(ODCIP)]2+与Zn2+配位可能形成的双核配位物[Ru(bpy)2(ODCIP)Zn]4+与DNA也能进行插入结合,对DNA的光切割效果并没有明显增强。     

钌多吡啶配合物与DNA作用及抗肿瘤活性

应用电子吸收光谱、荧光光谱和粘度测定等方法研究钌多吡啶配合物[Ru(phen)2(Hecip)]2(phen=1,10-邻菲啰啉,Hecip=2(9-乙基-9H-咔唑-3-基)-1H-咪唑并[4,5-f][1,10]菲啰啉)与DNA相互作用。结果表明配合物与DNA键合计量比为2∶1,键合常数超过105mol-1.L,配合物以插入方式与DNA结合。运用琼脂糖凝胶电泳实验研究配合物诱导pBR322DNA断裂及断裂机理。体外抗肿瘤活性结果表明配合物能有效抑制肿瘤细胞增殖,进一步研究表明配合物可以将细胞周期阻滞在S期。     

新型2-取代苯基-1H-咪唑[4,5-f][1,10]邻菲啰啉基Ru(II)配合物的光电性质

为获取具有活性官能团的接枝型、高性能荧光传感配合物,合成了2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NH2)、2-(4-羟基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-OH)、2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-COOH)和2-(4-硝基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉(CImPB-NO2)四种配体,借助紫外-可见(UV-Vis)吸收光谱、荧光(PL)光谱、循环伏安法(CV)和含时密度泛函理论(TD-DFT)对上述四种配体与过渡金属元素钌(Ru)所形成的配合物的光电性能进行研究.结果表明:四种配合物均在可见光区域有较强吸收,发光范围覆盖绿色到红色光波段.在极性溶剂N,N-二甲基甲酰胺(DMF)中,以2-(4-氨基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉为配体所构建的钌配合物([Ru(CImPB-NH2)(bpy)2]2+的荧光量子产率(Φ)较不含咪唑环的5-氨基邻菲啰啉合钌([Ru(phen-NH2)(bpy)2]2+)的提高了67%,以2-(4-羧基苯基)-1H-咪唑[4,5-f][1,10]邻菲啰啉所构建的钌配合物([Ru(CImPB-COOH)(bpy)2]2+)的Φ可达29.8%,是[Ru(phen-NH2)(bpy)2]2+的18倍.理论计算表明:配体中取代苯环、咪唑环和邻菲啰啉的稠环共平面,形成共价大π体系,其有效共轭长度较邻菲啰啉母体有显著增加,配合物是以Ru为中心的近似八面体构型,理论计算的电子吸收光谱和跃迁性质与实验结果相一致.上述研究有可能为接枝型、高性能荧光传感配合物的设计和筛选提供实验依据.     

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...     

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。     

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).     

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。     

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 of Tyrosol and Hydroxytyrosol Glycofuranosides and Their Biochemical and Biological Activities in Cell-Free and Cellular Assays

Tyrosol (T) and hydroxytyrosol (HOT) and their glycosides are promising candidates for applications in functional food products or in complementary therapy. A series of phenylethanoid glycofuranosides (PEGFs) were synthesized to compare some of their biochemical and biological activities with T and HOT. The optimization of glycosylation promoted by environmentally benign basic zinc carbonate was performed to prepare HOT α-L-arabino-, β-D-apio-, and β-D-ribofuranosides. T and HOT β-D-fructofuranosides, prepared by enzymatic transfructosylation of T and HOT, were also included in the comparative study. The antioxidant capacity and DNA-protective potential of T, HOT, and PEGFs on plasmid DNA were determined using cell-free assays. The DNA-damaging potential of the studied compounds for human hepatoma HepG2 cells and their DNA-protective potential on HepG2 cells against hydrogen peroxide were evaluated using the comet assay. Experiments revealed a spectrum of different activities of the studied compounds. HOT and HOT β-D-fructofuranoside appear to be the best-performing scavengers and protectants of plasmid DNA and HepG2 cells. T and T β-D-fructofuranoside display almost zero or low scavenging/antioxidant activity and protective effects on plasmid DNA or HepG2 cells. The results imply that especially HOT β-D-fructofuranoside and β-D-apiofuranoside could be considered as prospective molecules for the subsequent design of supplements with potential in food and health protection.     

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.