三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz^*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu₂(mpz^*eaT-EtO)₂(N₃)₂Cl₂(1)和Cu₂(mpz^*eaT-MeO)₂(N₃)₄(2)(mpz^*eaT-EtO：2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz^*eaT-MeO：2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.9949(2)nm,b=1.0216(2)nm,c=1.1480(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.9460(3)nm³,Z=1;配合物2属于单斜晶系,P2₁/c空间群,a=1.5464(5)nm,b=1.4008(5)nm,c=0.8905(3)nm,β=103.227(5)°,V=1.8779(10)nm³,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

两个基于2-氨基-5-巯基-1,3,4-噻二唑乙酸的稀土配合物的合成、晶体结构和性质研究

用2-氨基-5-巯基-1,3,4-噻二唑乙酸(Hatma)为配体合成出2种新型同构的稀土配合物[Ln(atma)₃(H₂O)₂]_n(Ln=La(1),Nd(2))。配体和2个配合物的结构均由X-射线单晶衍射法确定,同时对配合物进行了IR,TGA及元素分析。单晶结构表明,配体属单斜晶系,C2/c空间群,晶胞参数为a=2.1419(9)nm,b=0.40076(17)nm,c=1.7500(8)nm,V=1.4950(11)nm³,Z=4;配合物1和2的晶体都属于三斜晶系,空间群为P1,配合物1的晶胞参数为a=0.8820(3)nm,b=1.2306(4)nm,c=1.2586(4)nm,V=1.2913(7)nm³,Z=2;配合物2的晶胞参数为a=0.8834(4)nm,b=1.2283(5)nm,c=1.2510(5)nm,V=1.2821(9)nm³,Z=2。2个配合物均形成一维链状空间结构,通过丰富的氢键连接形成三维超分子结构。抗菌试验表明,配合物比配体表现出更好的生物活性。初步的植物生长实验表明,配合物对油菜和小麦的生长具有一定的促进作用。     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。     

镍(II)的两种配位聚合物的合成、晶体结构和性质

分别用水热法和溶液法合成了镍的两种配位聚合物[2{Ni(HO-BDC)(bpe)H₂O}]_n·n(py)·nH₂O (1) (HO-H₂BDC=5-羟基-1,3-苯二甲酸，bpe=1,2-二(4-吡啶)乙烷，py=吡啶)和[Ni(HO-BDC)(bipy)]_n·nH₂O (2) (bipy=2,2’-联吡啶)，并对它们进行了元素分析、红外光谱等表征，并用X-射线单晶衍射测定了配合物的单晶结构。配位聚合物1晶体属三斜晶系,P1空间群,晶体学数据为：a= 1.019 2(2) nm, b=1.145 5(3) nm, c=1.246 0(3) nm, α=68.377(5)°, β=67.275(12)°, γ=71.821(7)°,V=1.222 7(5) nm³, Z=1, M_r=979.26, D_c=1.330 g·cm^-3, F(000)=508, μ=0.835, R₁=0.049 4, wR₂=0.112 1；配位聚合物2晶体属单斜晶系, P2/c空间群,晶体学数据为：a= 0.861 1(2) nm, b=1.106 8(3) nm, c=1.839 4(4) nm, β=104.267(9), V=1.699 0(7) nm³, Z=4, M_r=413.00, D_c=1.615 g·cm^-3, F(000)=848, μ=1.182, R₁=0.063 5, wR₂=0.196 9。配合物1中形成了具有纳米孔的2D结构，而配合物2则是一个1D链状结构，它们分别通过氢键和π-π堆积效应形成3D结构。     

二维网状Pb(Ⅱ)配合物的合成、晶体结构及荧光性质

利用4-吡啶-3-苯甲酸(4,3-pybz)和醋酸铅在水热条件下合成了一种新型金属配合物[Pb(4,3-pybz)2]_n(1),并对其进行了元素分析、红外光谱、热重表征、X 射线单晶衍射测定。该配合物为正交晶系,Pccn空间群,a=1.070 74(7) nm,b=2.138 03(13) nm, c=0.865 65(5) nm,V=1.981 7(2) nm³,Z=4,D_c=2.023 Mg·m^-3,F(000)=1 152,GOF=1.050,μ=8.549 mm^-1,残差因子R₁=0.013 9,wR₂=0.032 4。该配合物展现了一个具有(4,4)拓扑二维波浪状网络结构,进而通过弱的π-π相互作用拓展为三维超分子体系。此外,室温下配合物1展现了弱的荧光性质。     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

一个不常见的Ni(Ⅱ)的戊三酮二水杨酰腙配合物的合成和晶体结构

合成了镍的戊三酮二水杨酰腙配合物Ni(C₁₉H₁₆N₄O₅)的两个同质异晶,测定其晶体结构。该配合物的两个晶体均属单斜晶系,空间群为C2/c,晶体1晶胞参数为:a=1.03076(9)nm,b=1.9105(1)nm,c=0.93305(8)nm,β=101.490(4)°,Z=4,μ=1.119mm^-1,R=0.0370;晶体2晶胞参数为:a=2.1949(3)nm,b=0.9901(2)nm,c=0.8568(1)nm,β=92.799(6)°,Z=4,μ=1.084mm^-1,R=0.0440。两个晶体中镍原子由多啮配体的二个酰氧原子和二个肼氮原子形成平面正方形配位。对配合物的红外光谱进行归属。     

2-[(2-溴苯胺基)甲基]-4-氯苯酚Schiff碱及其铜配合物的合成及晶体结构

以5-氯水杨醛和邻溴苯胺为原料合成了一种新的Schiff碱配体2-[(2-溴苯胺基)甲基]-4-氯苯酚(1)(C₁₃H₉BrClNO,H₂L),继而与过渡金属铜离子配合,得到其配合物2 ([Cu(C₁₃H₈BrClNO)₂],CuL₂)。通过X-射线衍射法对配体及其配合物进行了结构表征。化合物1属正交晶系,Pbca空间群,晶胞参数a=0.710 19(12) nm,b=1.308 2(2) nm,c=2.533 3(5) nm,M_r=310.57,V=2.353 6(7) nm³,D_c=1.753 g·cm^-3,Z=8,μ=3.700 mm^-1,Z=8,F(000)=1 232,R=0.025 0,wR=0.055 5;化合物1依靠分子间的C-H…N,C-H…O,C-H…Cl 氢键及π-π堆积作用进一步联结成二维网状结构。化合物2属单斜晶系,P2₁/c空间群,晶胞参数a=0.956 8(2) nm,b= 1.085 3(3) nm,c=1.204 7(3) nm,β=105.965(7)°,M_r=682.67,V=1.202 8(6) nm³,D_c=1.885 g·cm^-3,Z=2,μ=4.481 mm^-1,F(000)=670,R=0.045 0,wR=0.122 5。2依靠分子间C-H…π作用及卤素…卤素作用进一步联结成三维网状结构。     

基于1，2，4-苯三酸与[2，3-f]吡嗪并[1，10]菲咯啉配体的钴(Ⅱ)及镉(Ⅱ)配合物的水热合成与晶体结构

利用水热技术,合成了2个新的配合物{[Co(Hbtc)(Pyphen)(H₂O)]·H₂O}_n (1)和{[Cd₂(btc)(Pyphen)₂Cl]·2H₂O}_n(2) (H₃btc=1,2,4-苯三酸,Pyphen=[2,3-f]吡嗪并[1,10]-菲咯啉),并通过X-射线单晶衍射、元素分析、热重分析和荧光进行了表征。配合物1属三斜晶系,空间群P1,a=0.643 44(13) nm,b=1.202 9(2) nm,c=1.371 6(3) nm,α=95.03(3)°,β=90.46(3)°,γ=103.54(3)°,V=1.027 7(4) nm³,Z=2,CoC₂₃H₁₆N₄O₈,M_r=535.31,D_c=1.730 g·cm^-3,μ(MoKα)=0.900 mm^-1,F(000)=546,GOOF=1.089,R=0.099 2,wR=0.249 0;配合物2属三斜晶系,空间群P1,a=0.968 93(8) nm,b=1.223 82(10) nm,c=1.592 21(14) nm,α=67.486 0(10)°,β=73.158 0(10)°,γ=78.468 0(10)°,V=1.660 9(2) nm³,Z=2,Cd₂C₃₇H₂₃N₈O₈Cl,M_r=967.88,D_c=1.935 g·cm^-3,μ(MoKα)=1.432 mm^-1,F(000)=956,GOOF=1.051,R=0.077 9,wR=0.141 2。结构分析表明：配合物1为无限一维双链结构,配合物2为二维层状结构。此外,氢键和π-π相互作用在加固配合物的结构中起到重要作用。     

2-甲基-2,5′-(乙烯基)-二-8-羟基喹啉锌配合物的合成与荧光特性

设计合成了8-羟基喹啉衍生物3和4以及它们的金属锌配合物5和6,化合物3和4经质谱(MS)、元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱( ¹H NMR)进行表征,并测定了它们的荧光性质,与2-甲基-8-羟基喹啉(λ_max=390 nm)比较表明,化合物3和4的荧光红移80～150 nm;用X射线单晶衍射仪测定了化合物3的晶体结构,晶体属于三斜晶系,空间群P1,a=0.706 87(5) nm,b=0.962 03(6) nm,c=1.221 09(8) nm,α=86.735(4)°,β=87.840(4)°,γ=74.333(4)°,V=0.798 01(9) nm³,Z=2,D_c=1.367 Mg·m^-3,μ=0.089 mm^-1,F(000)=344,wR₁=0.055 2,wR₂=0.158 1。化合物3的晶体结构确认了2-甲基-8-羟基喹啉甲酰化是在5位。测定了化合物5和6的荧光光谱及其荧光寿命,结果表明,化合物5和6发光的峰值为620 nm 和623nm,能够发出橙色的荧光,与2-甲基-8-羟基喹啉锌(λ_max=515 nm)比较,发生了明显的红移。化合物5和6的寿命分别为1.57 ns和1.77 ns,呈单指数衰减。     

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.     

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.     

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.