新型含氮配体钴配合物的水热合成、晶体结构及荧光性质

以4,5-二羟基苯-1,3-二磺酸钠（Na₂H₂L）和4,4′-bipy为原料,采用水热法与Co(NO₃)₂反应合成了新的含氮配体钴配合物[Co(4,4′-bipy)(H₂O)₄]·H₂L·2H₂O（1）（H₂L^2-=4,5-二羟基苯-1,3-二磺酸根离子,4,4′-bipy=4,4′-联吡啶）,其结构和组成经X-射线单晶衍射、红外光谱、元素分析和热重分析表征。晶体结构解析表明：钴离子与4,4′-bipy和水分子配位,形成扭曲的八面体配位构型。H₂L^2-配体没有配位,仅起平衡电荷作用。在结构单元中,[Co(4,4′-bipy)(H₂O)₄]²⁺, H₂L^2-和自由水分子之间通过氢键相连。配合物的荧光发射峰与配体相比发生了蓝移,最大发射峰位于357 nm。     

新型离子型配合物的合成、晶体结构及性质

利用水热法合成了4-(N,N′-双(4-羧基苄基)氨基)苯磺酸（H₃L）的两个离子型配合物：[Mn(phen)₂(H₂O)₂]?(HL)?(H₂O)₄（1）和[Zn(phen)₂(H₂O)₂]?(HL)?(H₂O)₆（2, phen =邻菲罗啉）,其结构经FL、 IR、元素分析、X-射线单晶衍射、 X-射线粉末衍射和TG表征。结果表明：化合物1属于单斜晶体,P2₁/c空间群,晶胞参数a=11.997(1) Å, b=22.978(1) Å, c=18.093(1) Å, β=92.749(3)°, V=4981.8(3) ų, Z=4。化合物2属于单斜晶体,P2₁/c空间群,晶胞参数a=11.861(1) Å, b=22.816(1) Å, c=18.251(1) Å, β=92.832(5)°, V=4932.8(5) ų,Z=4。化合物2有较好的荧光性质;初始分解温度为80 ℃。      

系列Sm3+配合物的合成、结构及光物理性能

采用水热方法合成了4种Sm³⁺配合物, 即{[SmZn(2,5-pdc)₂(tp)_0.5(H₂O)]·2H₂O}_n(1), [Sm₂Zn₂(C₆H₅COO)₁₀(Imh)₂(H₂O)₂](2), {[Sm₂(NO₂C₆H₄COO)₆(H₂O)₄]·H₂O}_n(3)和{[SmN(CH₂COO)₃(H₂O)₂]·H₂O}_n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C₆H₅COO=苯甲酸根, Imh=咪唑, NO₂C₆H₄COO=对硝基苯甲酸根, N(CH₂COO)₃=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm³⁺离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm³⁺离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm³⁺离子发光的影响, 并分析了配合物中Sm³⁺离子的近红外发射带位移、 劈裂和加宽的原因.     

Zn(Ⅱ)与5-氨基四氮唑和1,4-对苯二甲酸配位聚合物的溶剂可控合成

以5-氨基四氮唑（HATz）、1,4-对苯二甲酸（H₂BDC）和Zn（NO₃）₂为反应物,在水热条件下得到了1个二维层结构的Zn（Ⅱ）配位聚合物{[Zn₂（ATz）₂（BDC）（H₂O）₂] ·H₂O}_n（1）,而在N,N’-二甲基甲酰胺（DMF）溶剂热条件下得到了1个三维结构的Zn（Ⅱ）配位聚合物{[Zn₂（ATz）₂（BDC）（DMF）₂] }_n（2）. 通过元素分析、红外光谱、单晶X射线衍射和粉末X射线衍射等对它们的组成和结构进行了表征. 单晶结构分析结果表明,配合物1是以Zn（Ⅱ）离子作连接点、μ₂-ATz^-和μ₂-BDC^2-作连接子形成的3-连接（6,3）蜂窝型二维层结构,二维层之间再通过氢键作用形成三维超分子结构. 配合物2是以两羧基桥连的双核Zn（Ⅱ）单元[Zn₂（CO）₂] 作连接点、μ₂-ATz^-和μ₄-BDC^2-作连接子形成的6-连接简单立方格子的三维金属-有机框架结构. 室温固体荧光实验表明,在350 nm的光激发下,配合物1和2分别在451和466 nm处出现强烈的荧光发射.     

基于锌(Ⅱ)Schiff碱构筑模块和6-羧基吡啶-2-甲醇的3d-4f异金属四核簇合物的荧光和磁弛豫性质

用溶剂热方法合成了2个新的3d-4f异金属四核簇合物：[Zn₂Ln₂（salen）₂（CO₂PyCH₂O）₂（MeOH）2]（ClO₄）₂·2MeOH（Ln=Dy（1）,Tb（2）;H₂salen=N,N'-双（3-甲氧基水杨基）-1,3-二氨基丙烷;HCO₂PyCH₂OH=6-羧基吡啶-2-甲醇）。它们是由锌（Ⅱ）Schiff碱构筑模块和6-羧基吡啶-2-甲醇辅助配体组装而成的Zn-Ln₂-Zn型簇合物。磁性测量表明稀土离子间存在铁磁性相互作用。Zn₂Dy₂配合物1在2 000 Oe直流磁场下显示出磁弛豫行为;而Zn₂Tb₂配合物2不但有磁场导致的磁弛豫行为,而且还具有荧光性质。     

DABT含能化合物的合成,结构及性质研究

利用水热法制备了一个单核含能配合物[Ni(DABT)(H₂O)₄] SO₄·H₂O(1)(DABT=3,3’-二氨基-5,5’-二(1H-1,2,4-三唑))和一个含能离子盐DABT·SO₄(2)。结构分析表明,1和2均通过三唑环的π-π堆积作用及其氢键相互作用形成了三维超分子结构。研究了1和2的红外光谱,紫外可见光谱;运用TG-DSC热分析仪研究了1的热分解行为,结果表明1在失去水分子后可以稳定到350℃才放热分解;探究了2对推进剂主要组分的热分解行为,结果表明2对AP具有一定的燃烧催化作用。     

以4,4'-联苯二甲酸和咪唑基化合物为配体的钴配合物的合成和晶体结构

以4,4′-联苯二甲酸（H₂BPDC）和4,4′-二咪唑基二苯醚（BIDPE）为原料,与硝酸钴在不同温度下反应,得到2个结构不同的配位聚合物{[Co₂（BPDC）₂（BIDPE）₂（H₂O）]·2H₂O}_n（1）和{[Co（BPDC）（BIDPE）]·H₂O}_n（2）。对它们进行了元素分析、红外光谱分析,并利用X射线衍射测定了它们的单晶结构。配合物1属于单斜晶系,C2/c空间群,a=1.456 02（15）nm,b=1.557 51（16）nm,c=2.522 6（3）nm,β=90.834 0（10）°,V=5.720 2（10）nm3,Z=4,Mr=1 256.98,Dc=1.460 g·cm-3,μ=0.655,F（000）=2 592,R1=0.036 7,w R2=0.087 5（I>2σ（I））。配合物2属于三斜晶系,P1空间群,a=1.061 92（10）nm,b=1.098 51（11）nm,c=1.324 51（13）nm,α=112.725 0（10）nm,β=92.112 0（10）°,γ=96.574 0（10）°,V=1.410 2（2）nm3,Z=2,Mr=619.48,Dc=1.459 g·cm-3,μ=0.662,F（000）=638,R1=0.047 4,w R2=0.116 5（I>2σ（I））。单晶结构分析显示,配合物1拥有一维链状结构,而配合物2具有二维两重贯穿结构,并表现出聚轮烷的结构特征。结果说明了反应温度在配合物组装过程中起着非常重要的作用。     

多苯并咪唑锰( Ⅱ )配合物的合成及对DNA凝聚的促进作用

以多苯并咪唑配体1,1,4,7,7-五(2-苯并咪唑甲基)-二乙基三胺(DTPB)为主配体, 合成了锰(Ⅱ)配合物[Mn(DTPB)Ac]Ac·8H₂O(1)和[Mn₂(DTPB)(NO₃)₂(H₂O)₂][Mn₂(DTPB)(NO₃)₂(H₂O)(CH₃OH)]·(NO₃)₄·5CH₃OH·H₂O(2), 并对其进行了表征. 利用紫外-可见吸收光谱和黏度实验研究了配合物1和2与DNA的相互作用, 发现这2个配合物均能与DNA结合, 并对配合物与DNA作用的机理进行了探讨. 利用琼脂糖凝胶电泳和直角光散射(RALS)技术研究了配合物1和2促进DNA凝聚的性质. 结果表明, 在近中性条件下2个配合物都能促使DNA凝聚. 利用透射电子显微镜(TEM)观察了不同凝聚体的形态.     

新型含磺酸基配体锰配合物的水热合成及其性能

采用水热法合成了单核锰配合物[Mn(H₂L)(phen)₂(H₂O)]（1, H₂L_2-=4,5-二羟基苯-1,3-二磺酸根离子,phen=1,10-邻菲罗啉）,其结构和性能经X-射线单晶衍射、红外光谱、荧光光谱、元素分析和热重分析表征。研究表明,配合物中锰离子是六配位的,与两个phen配体的四个氮原子配位以及水分子和磺酸基氧原子配位,形成扭曲的八面体配位构型。1的荧光发射峰与配体相比发生了蓝移,最大发射峰位于390 nm。     

刚性4-取代双三唑配体构筑的三个锌配合物的合成和荧光

在室温下合成了3个新的配位聚合物{[Zn(4?Nbdc)(btx)]·2H₂O}_n(1·2H₂O)、[Zn(btx)_1.5(1,3?bdac)]n(2)和{[Zn(mbtx)(1,3?bdc)(H₂O)₂]·H₂O}_n(3)(btx=1,4?二(4H?1,2,4?三唑)苯,mbtx=1,3?二(4H?1,2,4?三唑)苯,4?Nbdc=4?硝基邻苯二甲酸根,1,3?bdac=间苯二乙酸根,1,3?bdc=间苯二甲酸根),测试了配合物的单晶结构,并从元素分析、红外和粉末衍射等方面进行表征。单晶X射线衍射表明,配合物1是二维(4,4)网格结构,配合物2和3都是一维链状结构。配合物2中的π?π作用将一维链连接成三维网格结构。在配合物3中,分子间氢键将一维链连接成二维网格,2套二维网格在分子间氢键的作用下相互穿插得到2D+2D→2D的网格结构。同时,还研究了3个配位聚合物的荧光和热稳定性。     

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.