基于[1，2，4]-三唑衍生物的两个镉（Ⅱ）配合物的结构与光谱学表征

合成了2个新的镉（Ⅱ）合物{[Cd（Htta）₂（H₂O）₂]·2H₂O}_n（1）和[Cd（tba）₂（H₂O）₄]（2）（H₂tta=2-[1,2,4]-三唑对苯二甲酸,Htba=3-[1,2,4]-三唑苯甲酸）,配合物分子结构经X射线单晶衍射分析确认。对配合物1和2进行了X射线粉末衍射、红外光谱、紫外光谱和固体荧光光谱表征。X射线单晶衍射测试表明,配合物1为一维双链高分子聚合物,2为单核零维配合物,中心镉（Ⅱ）离子均采取六配位八面体配位构型。配合物1通过分子间丰富的氢键作用进一步组装成三维超分子结构,配合物2则通过分子间氢键和π-π堆积作用组装成三维超分子结构。固体荧光光谱显示,配合物1和2分别在437和357 nm处有强的荧光发射峰。     

由2-甲基-4-噻唑甲酸构筑的过渡金属配合物的合成、晶体结构及与DNA作用

以2-甲基-4-噻唑甲酸（HMTZA,C₅H₅NO₂S）为配体合成了3种新型过渡金属配合物[Co（MTZA）₂（H₂O）₂]·3H₂O（1）,[Cu（MTZA）₂（H₂O）]·2H₂O（2）和[Zn（MTZA）₂（H₂O）₂]·3H₂O（3）。对配合物进行了元素分析、红外光谱和热重分析表征,用单晶X射线衍射方法测定了配合物的晶体结构。结果表明,配合物1属于单斜晶系,空间群为P2₁/n,中心金属Co（Ⅱ）离子的配位数为6,配位构型为略为变形的八面体;配合物2属于三斜晶系,空间群为P1,Cu（Ⅱ）离子的配位构型是一个畸变的四方锥;配合物3属单斜晶系,空间群为P2₁/n,中心金属Zn（Ⅱ）离子的配位构型为畸变的八面体。用溴化乙锭荧光探针法测定了配体和配合物与DNA作用的荧光光谱,结果显示无论配体还是配合物均能使EB-DNA复合体系发生不同程度的荧光猝灭,且配合物的作用强度远大于配体。     

由4-甲基-1，2，3-噻二唑-5-甲酸构筑的过渡金属配合物的合成、晶体结构及与DNA作用

以4-甲基-1,2,3-噻二唑-5-甲酸（C₄H₄N₂O₂S, HL）分别与硫酸钴（CoSO₄·7H₂O）、氯化铜（CuCl₂·2H₂O）、硝酸银（AgNO₃）反应合成了3个配合物[Co（L）₂（H₂O）₄] ·2H₂O （1）、[CuNa（L）₃] _n （2）和[AgL] _n （3）,用元素分析、红外光谱、热重分析进行表征,用单晶X射线衍射测定了产物的结构。配合物1属于三斜晶系,空间群P1,Co²⁺的配位数为6,形成一个略为拉长的CoN₂O₄八面体,与理想的正八面体非常接近。配合物2属于三斜晶系,空间群P1。Cu²⁺离子的配位数为4,构成变形的平面四边形结构,Na⁺离子的配位数为6,构成一个略微变形的八面体结构,最终形成三维网状结构。配合物3属于单斜晶系,空间群P2₁/c,银离子为三配位,构成变形的平面三角形构型,具有二维网状结构。用溴化乙锭荧光探针法测定了配体和配合物与DNA作用的荧光光谱。     

基于2-氨基-3-羟基-吡啶Schiff碱的双核Ni(Ⅱ)和Zn(Ⅱ)配合物:合成、超分子结构和光谱性质

合成了2个2-氨基-3-羟基-吡啶Schiff碱双核Ni（Ⅱ）和Zn（Ⅱ）配合物,[Ni（L¹）（DMF）]₂（1）（H₂L¹=4-羟基-3-（（3-羟基-吡啶-2-亚氨基））-苯并吡喃-2-酮）和[Zn（L²）（H₂O）]₂·2DMF（2）（H₂L²=2-（（3,5-二溴-2-羟基）-氨基）-吡啶-3-醇）,并通过元素分析、红外光谱、紫外-可见吸收光谱、荧光光谱及X射线单晶衍射分析等手段进行了表征。X射线单晶衍射分析结果表明：配合物1和2均具有双核结构,均由2个金属离子和2个配体单元以及2个配位的溶剂分子组成,不同的是配合物2含有2个溶剂分子。配合物1和2都是单斜晶系、P2₁/c空间群,且中心金属Ni（Ⅱ）和Zn（Ⅱ）离子的空间构型均为五配位的扭曲的四方锥。此外,配合物1和2通过分子间氢键、C-H…π及π…π作用形成3D超分子结构。此外,讨论了H₂L¹,H₂L²及其相应的Ni（Ⅱ）和Zn（Ⅱ）配合物的荧光性质。配体H₂L¹和H₂L²呈现蓝色发射,最大发射波长λ_em分别为457和473 nm,而配合物1和2显示绿色发射,λ_em分别为543和538 nm。     

混合配体构筑的配位聚合物的合成、结构与荧光性质

在溶剂热条件下,利用Cd（Ⅱ）、Co（Ⅱ）在混配体体系下合成出3个结构新颖的配位聚合物[Cd₃（pic）₄（H₂bmimb）]_n（1）,[Co₃（pic）₄（H₂bmimb）]_n（2）和[Cd₂（1,2-mbix）（pic）₂（H₂O）₂]_n（3）（pic=5-苯基间苯二甲酸;H₂bmimb=1,4-二（（2-甲基咪唑）亚甲基）苯;1,2-mbix=1,2-二（（2-甲基咪唑）亚甲基）苯）,并通过单晶X射线衍射、红外光谱、热重分析、元素分析、粉末X射线衍射和荧光光谱等对配合物进行了表征。配合物1和2中金属离子Cd²⁺、Co²⁺均与pic配体形成了三维阴离子骨架,双质子化的双咪唑配体位于骨架中平衡骨架电荷。配合物3中,Cd²⁺金属中心与pic、1,2-mbix配体配位形成一维链,链与链之间通过苯环间的π…π堆积形成二维层,进而通过氢键形成三维超分子结构。配合物1和3表现出良好的荧光性质。     

联苯-2,4,4',6-四甲酸银、咪唑-菲啰啉-苯氧乙酸镉配位聚合物的合成、结构及与DNA的相互作用

由联苯-2,4,4'',6-四甲酸（H₄BPTC,C₁₆H₁₀O₈）和2-4-（1H-咪唑-2-[4,5-f] [1,10]菲啰啉基）苯氧乙酸（HPIMPHC,C₂₁H₁₄N₄O₃）,水热合成了2种新型配位聚合物[Ag₄（BPTC）]_n（1）,[Cd（PIMPHC）₂]_n（2）。用元素分析、红外光谱、热重分析和X射线单晶衍射对配合物进行了表征和结构分析。配合物 1 属三斜晶系,空间群为P1;Ag（Ⅰ）的配位数分别为4、3、2,配位构型为变形四面体、平面三角形和V型。配合物2属正交晶系,空间群为Pbcn;Cd（Ⅱ）的配位数为6,配位构型为变形的八面体,Cd（Ⅱ）离子间通过三齿配体 PIMPHC^-桥连,形成2D网状结构。用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

基于三唑配体的金属锰（Ⅱ）、锌（Ⅱ）配合物的合成、晶体结构与性质研究

在不同反应条件下,采用三唑衍生物作为配体与乙酸锰和硝酸锌反应,合成了2个具有三维结构的配位化合物{Mn（pytyba）（H₂O）₃]·2H₂O}_n（1）和{[Zn（pytyba）（H₂O）₃]·4H₂O}_n（2）,并通过元素分析、热重分析、荧光性、X射线单晶衍射对化合物进行分析。结构分析表明1和2有许多共同特征：两个聚合物的晶体均属于单斜晶系,C2/c空间群,Mn²⁺和Zn²⁺均为六配位畸变八面体配位结构,具有相似的热稳定性、荧光性以及相近的孔隙率。配体中的氧原子与金属离子配位形成一维链状结构,然后又通过O-H…N、O-H…O氢键作用和π…π芳香堆积形成超分子结构。此外,通过测定化合物抗氧化活性（SOD）的经典方法-Marklund法对配合物1和2的抗氧化活性进行了研究。     

以9，10-双(咪唑基)蒽为配体的锌配合物的合成、晶体结构和荧光性质

以9,10-双（咪唑基）蒽（DIA）和硝酸锌为原料,分别与对苯二甲酸（H₂bdc）、二苯甲酮-4,4''-二羧酸（H₂cdc）、反式-1,4-环己二甲酸（H₂chdc）在溶剂热条件下反应,得到3个结构不同的配位聚合物[Zn₂（DIA）（bdc）₂]_n（1）、{[Zn（DIA）（cdc）]·H₂O}_n（2）和[Zn（DIA）（chdc）]_n（3）。对它们进行了X射线单晶衍射分析、元素分析、红外光谱分析和热重分析。单晶结构分析显示,配合物1是第一例拥有三维（4,7）-连接的{3².4.5².6}{3².4⁸.5⁴.6⁵.7²}₂拓扑结构;配合物2具有二维格子状结构,层与层之间通过O-H…O和π…π弱相互作用形成三维超分子结构;而配合物3具有二维两重贯穿的层状结构。结果说明有机羧酸的长度和刚柔性在配合物组装过程中起着非常重要的作用。此外,在室温下对3个配合物进行了荧光性质分析。     

基于2-氨基-3-羟基-吡啶Schiff碱的双核Ni(Ⅱ)和Zn(Ⅱ)配合物:合成、超分子结构和光谱性质

合成了2个2-氨基-3-羟基-吡啶Schiff碱双核Ni（Ⅱ）和Zn（Ⅱ）配合物,[Ni（L¹）（DMF）]₂（1）（H₂L¹=4-羟基-3-（（3-羟基-吡啶-2-亚氨基））-苯并吡喃-2-酮）和[Zn（L²）（H₂O）]2·2DMF（2）（H₂L²=2-（（3,5-二溴-2-羟基）-氨基）-吡啶-3-醇）,并通过元素分析、红外光谱、紫外-可见吸收光谱、荧光光谱及X射线单晶衍射分析等手段进行了表征。X射线单晶衍射分析结果表明：配合物1和2均具有双核结构,均由2个金属离子和2个配体单元以及2个配位的溶剂分子组成,不同的是配合物2含有2个溶剂分子。配合物1和2都是单斜晶系、P2₁/c空间群,且中心金属Ni（Ⅱ）和Zn（Ⅱ）离子的空间构型均为五配位的扭曲的四方锥。此外,配合物1和2通过分子间氢键、C-H…π及π…π作用形成3D超分子结构。此外,讨论了H₂L¹,H₂L²及其相应的Ni（Ⅱ）和Zn（Ⅱ）配合物的荧光性质。配体H₂L¹和H₂L²呈现蓝色发射,最大发射波长λ_em分别为457和473 nm,而配合物1和2显示绿色发射,λ_em分别为543和538 nm。     

2,5-噻吩二甲酸与菲咯啉构筑的稀土配合物:晶体结构，荧光性质和对Cu2+离子的荧光传感

稀土硝酸盐和2,5-噻吩二甲酸与菲咯啉在水热反应条件下合成了3个新的配合物,[Ln（2,5-tdc）_1.5（phen）（H₂O）]_n（Ln=Gd（1）,Tb（2）,Dy（3）;2,5-tdc=2,5-噻吩二甲酸根,phen=菲咯啉）。通过X射线单晶衍射确定了它们的晶体结构。配合物1~3为同构的2D网络结构。配合物1在340 nm激发下出现最大发射中心位于366和387 nm的宽峰,可归属于配体的π^*-π跃迁发射。配合物2在365 nm紫外灯照射下发绿光,其荧光发射光谱中出现了4个尖峰,位于491、545、588和620 nm处,对应于Tb³⁺的⁵D₄→⁷F_J（J=6~3）跃迁。配合物2的荧光寿命显示为单指数衰减,其值为（0.123±0.005）ms。配合物3的发射光谱中出现了2个尖峰,位于482和575 nm处,分别对应于Dy³⁺的⁴F_5/2→⁶H_15/2和⁴F_5/2→⁶H_13/2跃迁。另外,研究了配合物2的荧光传感能力,该配合物可作为荧光探针检测水溶液中的Cu²⁺离子。     

3-Ferrocenyl-3-(1-naphthyl)cyclopropene. Synthesis, structure, and chemical transformations

Crystalline 3-ferrocenyl-3-(1-naphthyl)cyclopropene was prepared by dehydrobromination ofZ- andE-2-bromo-1-ferrocenyl-1-(1-naphthyl)-cyclopropanes by Bu^tOK in DMSO. The resulting compound and the startingZ-monobromocyclopropane were characterized by X-ray diffraction analysis. The obtained cyclopropene reacts with 1,3-diphenylisobenzofuran to give a [4+2]-cycloadduct. The small ring opens upon treatment with HBF₄ etherate to afford isomericZ- andE-prop-1-enes and 1-ferrocenyl-3H-benzo[e]indene. Thermolysis of this cyclopropene results in the formation of 1-ferrocenyl-9bH-benzo[e]indene. In all cases, opening of the small ring is accompanied by exclusive alkylation of the naphthalene moiety. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 499–506, March, 1998.     

有机物3,4,5,6-四氯-N-羟基邻苯二甲酰亚胺和1,4-二氨基-2,3-二氯蒽醌催化乙苯的分子氧氧化

合成了3,4,5,6-四氯-N-羟基邻苯二甲酰亚胺并与1,4-二氨基-2,3-二氯蒽醌组合成有机催化体系.在无溶剂条件下,该体系能够有效催化乙苯的分子氧氧化.     

Beneficial Effects of Epigallocatechin-3-O-Gallate,Chlorogenic Acid,Resveratrol, and Curcumin on Neurodegenerative Diseases

Many observational and clinical studies have shown that consumption of diets rich in plant polyphenols have beneficial effects on various diseases such as cancer, obesity, diabetes, cardiovascular diseases, and neurodegenerative diseases (NDDs). Animal and cellular studies have indicated that these polyphenolic compounds contribute to such effects. The representative polyphenols are epigallocatechin-3-O-gallate in tea, chlorogenic acids in coffee, resveratrol in wine, and curcumin in curry. The results of human studies have suggested the beneficial effects of consumption of these foods on NDDs including Alzheimer’s and Parkinson’s diseases, and cellular animal experiments have provided molecular basis to indicate contribution of these representative polyphenols to these effects. This article provides updated information on the effects of these foods and their polyphenols on NDDs with discussions on mechanistic aspects of their actions mainly based on the findings derived from basic experiments.     

Charge‐Transfer Complexes Between the Sulfur Molecules SO2, S2O,S3, SONH,and SOCl2 and the Amine Donors NH3 and NMe3 — A theoretical Study

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Conformational analysis and steric effects of substituents in derivatives of 3-oxo-, 3-imino-, and 3-methylenecyclohexene

The equilibrium conformations and the inversion barriers of the rings in 3-oxo-, 3-imino-, 3-methylenecyclohexenes and in their methyl,tert-butyl, and phenyl derivatives were calculated by molecular mechanics. The unsubstituted molecules adopt a sofa conformation. The nonbonded interactions between substituents at positions 2 and 4 and the exocyclic double bond lead to a change in the conformation of the ring to a half-chair. The effect is enhanced as the volume of the substituent increases in the series of the oxo, imino, and methylene derivatives. Substituents at other positions of the ring affect only slightly the equilibrium conformation. The results of calculations were confirmed by X-ray structural analysis of 2-(4-benzoyloxybenzyl)-6-isopropyl-3-methylcyclohex-2-enone. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1995–2000, November, 1997.     

Die Perthioborate RbBS3, TIBS3 und TI3B3S10

The Perthioborates RbBS₃, TIBS₃, and Tl₃B₃S₁₀ . RbBS₃ (P2₁/c, a=7.082(2) Å, b=11.863(4) Å, c=5.794(2) Å, β=106.54(2)°) was prepared as colourless, plate-shaped crystals by reaction of stoichiometric amounts of rubidium sulfide, boron, and sulfur at 600°C and subsequent annealing. TlBS₃ (P2₁/c, a=6.874(3) Å, b=11.739(3) Å, c=5.775(2) Å, β=113.08(2)°) which is isotypic with RbBS₃ was synthesized from a sample of the composition Tl₂S · 2 B₂S₃. The glassy product which was obtained after 7 h at 850°C was annealed in a two zone furnace for 400 h at 400→350°C. Yellow crystals of TlBS₃ formed at the warmer side of the furnace. Tl₃B₃S₁₀ (P1 , a=6.828(2) Å, b=7.713(2) Å, c=13.769(5) Å, α=104.32(2)°, β=94.03(3)°, γ=94.69(2)°) was prepared as yellow plates from stoichiometric amounts of thallium sulfide, boron, and sulfur at 850°C and subsequent annealing. All compounds contain tetrahedrally coordinated boron. The crystal structures consist of polymeric anion chains. In the case of RbBS₃ and TlBS₃ nonplanar five-membered B₂S₃ rings are spirocyclically connected via the boron atoms. To obtain the anionic structure of Tl₃B₃S₁₀ every third B₂S₃ ring of the polymeric chains of MBS₃ is to be substituted by a six-membered B(S₂)₂B ring.     

Synthesis,Antifungal Activity,and 3D-QSAR Study of Novel Nopol-Derived 1,3,4-Thiadiazole-Thiourea Compounds

A series of novel nopol derivatives bearing the 1,3,4-thiadiazole-thiourea moiety were designed and synthesized by multi-step reactions in search of potent natural product-based antifungal agents. Their structures were confirmed by FT-IR, NMR, ESI-MS, and elemental analysis. Antifungal activity of the target compounds was preliminarily evaluated by in vitro methods against Fusarium oxysporum f. sp. cucumerinum, Cercospora arachidicola, Physalospora piricola, Alternaria solani, Gibberella zeae, Rhizoeotnia solani, Bipolaris maydis, and Colleterichum orbicalare at 50 µg/mL. All the target compounds exhibited better antifungal activity against P. piricola, C. arachidicola, and A. solani. Compound 6j (R = m, p-Cl Ph) showed the best broad-spectrum antifungal activity against all the tested fungi. Compounds 6c (R = m-Me Ph), 6q (R = i-Pr), and 6i (R = p-Cl Ph) had inhibition rates of 86.1%, 86.1%, and 80.2%, respectively, against P. piricola, much better than that of the positive control chlorothalonil. Moreover, compounds 6h (R = m-Cl Ph) and 6n (R = o-CF₃ Ph) held inhibition rates of 80.6% and 79.0% against C. arachidicola and G. zeae, respectively, much better than that of the commercial fungicide chlorothalonil. In order to design more effective antifungal compounds against A. solani, analysis of the three-dimensional quantitative structure–activity relationship (3D-QSAR) was carried out using the CoMFA method, and a reasonable and effective 3D-QSAR model (r² = 0.992, q² = 0.753) has been established. Furthermore, some intriguing structure–activity relationships were found and are discussed by theoretical calculation.     

ChemInform Abstract: [Ta3O3]A (A: Li,Na, K) and [Ta3O3]B[Ta3O3] (B: Ca,Sr, Ba): Sandwich‐Type Complexes Containing Ta3O3‐ δ and π Double Aromatic Ligands.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

1,3-二苯基-5-吡唑啉酮三种异构体的结构及其发光性能

本文以1,3-二苯基-5-吡唑啉酮(DPP)为研究对象,采用不同溶剂对其进行重结晶,得到了3种不同颜色和不同构型的异构体。通过XRD粉末衍射、IR、1H NMR等确定了3种异构体的组成和结构,通过荧光光谱研究了它们的发光行为。结果表明这类化合物具有聚集诱导发光性能和光异构化性能,而且溶剂对产物的构型及发光性能均有明显的影响。此外,将该化合物与无规聚苯乙烯复合制备的薄膜也具有很好的荧光性能,在防伪领域具有潜在的应用。