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1.
合成并结构表征了一种新型的线性三核锌(II)配合物,{[ZnL(OAc)]2Zn}∙CH3COCH3(H2L:乙二氧双(5-溴-2-羟基苯亚甲基胺))。X-射线结构表明配合物中三个锌(II)离子配位到了两个四齿的L2-单元和两个桥联的的乙酸根基团。围绕两端的Zn(1) 或 Zn(1)#1原子形成了扭曲的四方锥配位几何体,围绕中心Zn(2) 原子构成了一个稍微扭曲的八面体配位结构。同时,观察到锌(II)配合物能发出蓝绿色荧光,其最大发射波长为464 nm。 相似文献
2.
该文以三种母体环糊精(CD),即α-、β-和γ-CD为修饰模板,将功能性基团有机碲引入到环糊精次面的2位羟基上,制备得到了三种具有谷胱甘肽过氧化物酶(GPX)活性的GPX模拟物。采用元素分析、红外光谱、核磁共振等手段对三种环糊精衍生物的结构进行了表征。运用GPX经典双酶体系法测定了三种环糊精衍生物的GPX活性,实验结果表明三者均具有很高的催化活性,其中2-位碲桥联γ-环糊精(2-Te-γ-CD)具有最高的GPX活性,其催化谷胱甘肽(GSH)还原过氧化氢(H2O2),叔丁基过氧化氢(t-BuOOH)和枯烯过氧化氢(CuOOH)的活力分别是传统"小分子硒酶"Ebselen的80.5,333.3和118.3倍。 相似文献
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《高等学校化学学报》2018,(11)
选用2-(3'-羧基苯氧基)苯甲酸(2,3'-H2oba)、1,3-双(4-吡啶基)-丙烷(DPP)和1,4-二(1,2,4-三氮唑-1-)丁烷(BTB)为配体,采用水热法得到了过渡金属配合物Cd (2,3'-oba)(DPP)(1)和Zn(2,3'-oba)(BTB)0. 5(2).配合物1为二维网状结构,中心Cd~(2+)的配位环境为{Cd O4N2},双齿螯合配位的2,3'-oba和单齿桥联配位的DPP将Cd~(2+)连接成Cd~(2+)-2,3'-oba-Cd~(2+)-DPP两条螺旋链.配合物1由分子间氢键连接并自组装为三维超分子结构.配合物2为三维框架结构,中心Zn~(2+)采取五配位的畸变四方锥构型{Zn O4N}. 2,3'-oba配体以双齿螯合与双齿桥联的配位方式连接相邻Zn~(2+)并形成二维网层,BTB分子桥联Zn~(2+)并连接相邻网层进而形成三维结构.荧光光谱表明配合物1和2分别在437和359 nm存在最大发射,均来源于配体的π*-π跃迁.广谱型农药甲基磺草酮对配合物2的荧光强度具有明显的猝灭作用,据此配合物2可作为荧光探针检测甲基磺草酮. 相似文献
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以易得的1-金刚烷甲酸为原料, 合成了一系列对称桥头二取代金刚烷衍生物. 由1-金刚烷甲酸经Koch-Haaf羰基化反应得到1,3-金刚烷二甲酸(1); 化合物1经还原得到1,3-金刚烷二甲醇(2); 化合物2在HBr-ZnBr2体系中经溴代反应得1,3-二(溴甲基)金刚烷(3); 同时经Apple-Lee反应将化合物2转化得到1,3-二(氯甲基)金刚烷(4). 采用红外光谱和核磁共振氢谱等手段表征了产物的结构, 提出了可能的反应机理, 并对合成条件进行了优化. 相似文献
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用三烯烃三吡啶配体1,3,5三-((4-吡啶)-1,2-乙烯基)苯(tpeb)和M(NO_3)_2(M=Co,Ni,Zn,Cd)以及4种不同的有机羧酸(3,5-二溴苯甲酸(3,5-HDBB)、2,5-噻吩二羧酸(2,5-H_2TDC)、2,5-呋喃二羧酸(2,5-H_2FDC)、2,5-二溴对苯二甲酸(2,5-H_2DBTP))进行溶剂热反应,得到了[Zn(tpeb)(3,5-DBB)_2]_n(1)、[Co_2(tpeb)_2(2,5-TDC)_2]_n(2)、[Co_2(tpeb)_2(2,5-FDC)_2]_n(3)、[Co(tpeb)(2,5-DBTP)]_n(4)、[Ni(tpeb)(2,5-DBTP)]_n(5)、[Cd(tpeb)_(0.5)(2,5-DBTP)]_n(6)六个配位聚合物。对配合物1~6分别进行了单晶X射线衍射、粉末X射线衍射、红外、元素分析、热重、荧光等结构表征。配合物1~6结构独特且多样。配合物1是由[Zn(3,5-DBB)_2]单元通过配体tpeb桥联构筑的一维zigzag链状结构;配合物2和3是由一维梯状[Co(tpeb)]_n链分别与2种不同的五元杂环二取代羧酸桥联构筑而成的二维双层结构;配合物4和5均是由一维[M(2,5-DBTP)]_n(M=Co,Ni)链通过tpeb交叉连接而成的三维网络结构;配合物6则是由二维的[Cd(2,5-DBTP)]_n层状结构通过tpeb连接而成的三维互穿拓扑网络结构。配合物1~6的热稳定性较好,它们在固态时表现出不同的荧光性质。 相似文献
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《有机化学》2016,(8)
杯[4]-1,3-二氨基衍生物3分别与均苯四甲酸酐、1,4,5,8-萘四甲酸酐、3,4,9,10-苝四甲酸酐反应,以"2+2"的模式合成了三种大共轭芳香基桥联的双杯[4]芳烃4、5和6,产率为60%~70%.液液两相萃取实验表明化合物4~6对染料分子橙黄I(OI)和维多利亚蓝(VB)有较好萃取能力,化合物6对OI的萃取率达88.3%.紫外配合光谱、紫外滴定工作曲线和配合质谱均表明,主客体在DMSO溶液中形成1∶1的配合物,化合物6对OI的配合常数达2.80×105L·mol-1.化合物4~6的染料配合能力强弱次序为化合物4化合物5化合物6,这表明桥联芳香共轭基团在配合过程中有重要作用. 相似文献
7.
以N-(2-羧基苯)-N’-(氨乙基)草酰胺根阴离子(oxbe)为桥联配体, 端接二丙烯三胺(dpt), 合成了铜镍异双核配合物[Cu(oxbe) Ni(dpt)(H2O)]ClO4·0.5H2O. 通过元素分析和IR 光谱对配合物进行了表征, 利用X射线单晶衍射测定了其晶体结构. 该化合物分子间通过氢键相互作用, 形成双链状超分子结构. 5—300 K 变温磁化率研究结果表明, 化合物中双核体系 Cu(SCu=1/2)-Ni(SNi=1) 中心原子间通过草酰胺桥联发生较强的反铁磁相互作用(磁参数J=-62.3 cm-1, g=2.11). 相似文献
8.
选用2种具有较大共轭单元的配体1,4-二(2-(2-吡啶基)乙烯基)苯(2-bpeb)和1,2-二(4-吡啶基)乙烯(dpe),在溶剂热条件下与对苯二甲酸(H2PTA)和Co(NO3)2反应,制备了2种新型Co(Ⅱ)-MOFs。单晶结构显示:配合物1是由Co-2-bpeb链和Co-PTA链直接构筑成3D骨架,而配合物2则是由Co-PTA层通过dpe桥联形成3D骨架。因吡啶配体中存在较大的π共轭体系,所获得的2种配合物均具有较强的荧光性质。荧光传感实验表明,它们都可以作为荧光探针来检测Fe3+,并且具有良好的灵敏度和可回收性。 相似文献
9.
合成出化学式为 [(CuTPA) 3 ( μ3 CO3 ) ](ClO4) 4和 [(ZnTPA) 3 ( μ3 CO3 ) ](ClO4) 4(TPA为三 ( 2 甲基吡啶 )胺 )的配合物 .晶体结构分析表明 ,CO2 -3 作为三齿桥联配体分别把 3个Cu(TPA)单元和Zn(TPA)单元组装成一个新的三核Cu(Ⅱ )和三核Zn(Ⅱ )配合物 .CO2 -3 来自大气中的CO2 .Cu(Ⅱ )离子和Zn(Ⅱ )离子均为五配位三角双锥的配位构型 .变温磁化率测定表明 ,Cu(Ⅱ )离子之间存在着很弱的反铁磁相互作用 . 相似文献
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AiYouHAO JinShanWANG 《中国化学快报》2002,13(9):832-835
2-O-Acetonyl-β-cyclodextrin with a suitable average substitution degree of about 5.8, which could be used as a key intermediate for water soluble functional β-cyclodextrin derivatives, was prepared based on the proper oxidation of heptakis(6-O-dimethyl-tert-butylsilyl)-2-O-hydroxypropyl-β-cyclodextrin. 相似文献
12.
A novel β-cyclodextrin dimer bearing 2,9-diformyl-1,10-phenanthroline tether 4 has been synthesized and its inclusion complexation behavior with two triangular model substrates (RhB and BG) has been investigated through fluorescence and ultraviolet spectrometry.The result obtained indicated that novel bridged bis(β-cyclodextrin)s could significantly cnhance the original molccular binding ability of native β-cyclodextrin by cooperative binding of two hydrophobic cavities. 相似文献
13.
Xue Yan SHI Hong Chao GUO Zhen QIAO Shi Cong HOU Min WANG* Key Laboratory of Pesticide Chemistry Application Technology College of Applied Chemistry China Agricultural University Beijing 《中国化学快报》2002,(10)
For high bioactivity of chiral pesticides, more and more chiral isomers are prepared by enantiomer resolution or asymmetric synthesis, and the sales of chiral pesticides continuously increase in recent years1. 1S-Allethrone I and 1S-propargyllone II are indispensable intermediates for synthesizing 1S-bioallethrin and prallethrin respectively, which are representatives of chiral pesticides. Usually, 1S enantiomers of allethrone and propargyllone are more active than their 1R enantiomers wh… 相似文献
14.
8-氨基喹啉取代苯甲酰胺衍生物对汞离子和铜离子的识别 总被引:1,自引:0,他引:1
设计合成了可识别金属离子的荧光传感分子8-氨基喹啉取代苯甲酰胺衍生物,通过核磁共振谱和质谱表征其结构;利用其光谱性质研究了该系列物质对过渡金属离子Cu2+,Hg2+,Pb2+,Zn2+,Ni2+和Cd2+的识别性质,初步探讨了其识别机理。实验表明:在乙腈中,8-氨基喹啉苯甲酰胺的吸收光谱在509nm处对Cu2+有响应,溶液由无色变成红色;而其荧光光谱对Hg2+和Cu2+有良好的选择性,荧光增强倍率分别高达368和192,与金属离子形成结合比为1:1配合物。 相似文献
15.
Kai Jun LIAO Xiao Hua YAN Dong Yun ZHAO Xue Yi MA* Department of Chemistry National Laboratory of Applied Organic Chemistry Lanzhou University Lanzhou 《中国化学快报》2002,(3)
Lappaconitine (Figure 1) is a diterpenoid alkaloid, naturally occurring in roots and rhizomes of Aconitum and delphinium1. Lap reveals bradycardic and hypotensive activity2. But its application is restrained owing to its poor water solubility, toxicity and side effects on humans. In a number of pharmaceutical studies, b-CD has been reported to interact with many drug molecules to form inclusion complexes for improving the water solubility of drugs, and reducing their toxicity3. We have p… 相似文献
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Tsukube H Noda Y Kataoka Y Miyake H Shinoda S Kojima-Yuasa A Nishida Y Matsui-Yuasa I 《Dalton transactions (Cambridge, England : 2003)》2008,(30):4038-4043
A series of oligopyridine ligands were derived from amino acid amides in which amide oxygen and ternary nitrogen atoms were combined with pyridine moieties. 1H NMR and circular dichroism spectroscopic characterizations revealed that they formed stable Zn2+ complexes in neutral aqueous solutions and caused Zn2+ deficiency in the hepatic stellate cell systems. Since collagen synthesis was effectively promoted in the cells, the present oligopyridine derivatives worked as biocompatible ligands for Zn2+ complexation and cell activation. 相似文献
17.
Stereospecific and Stereoselective Rhodium(I)‐Catalyzed Intramolecular [2+2+2] Cycloaddition of Allene‐Ene‐Ynes: Construction of Bicyclo[4.1.0]heptenes
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Yuu Ohta Dr. Shigeo Yasuda Yuka Yokogawa Kei Kurokawa Prof. Dr. Chisato Mukai 《Angewandte Chemie (International ed. in English)》2015,54(4):1240-1244
Treatment of the allene‐ene‐yne substrates with [{RhCl(CO)2}2] effected the intramolecular [2+2+2]‐type ring‐closing reaction to produce various of tri‐ and tetracyclic derivatives containing a cyclopropane ring. The reaction is highly stereoselective as well as stereospecific with good to excellent yields. 相似文献
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Saudan C Balzani V Gorka M Lee SK Maestri M Vicinelli V Vögtle F 《Journal of the American Chemical Society》2003,125(15):4424-4425
We have investigated the formation of metal complexes between Zn2+ and two derivatives, 1 and 2, of the well-known 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand. Compound 1 is 1,4,8,11-tetrakis(naphthylmethyl) cyclam, and compound 2 is a dendrimer consisting of a cyclam core with appended 12 dimethoxybenzene and 16 naphthyl units. Compound 1 exhibits an emission band with a maximum around 480 nm, assigned to the formation of exciplexes between amine and excited naphthyl units. Dendrimer 2 exhibits three types of weak emission bands, assigned to naphthyl localized excited states (lambdamax = 337 nm), naphthyl excimers (lambdamax ca. 390 nm), and naphthyl-amine exciplexes (lambdamax = 480 nm). In CH3CN-CH2Cl2 1:1 v/v, titration of ligand 1 with Zn2+ causes the disappearance of the exciplex emission and the appearance of a strong naphthyl localized fluorescence; the titration plot is linear and reaches a plateau for a 1:1 stoichiometry, showing that a highly stable [Zn(1)]2+ complex is formed. In the case of 2, titration with Zn2+ causes the disappearance of the exciplex band, with a concomitant increase in the excimer and naphthyl localized emissions; the titration plot is again linear, but in this case it reaches a plateau for a 2:1 stoichiometric ratio, showing the unexpected formation of a [Zn(2)2]2+ complex. Such an unexpected stoichiometry for the complex of the dendritic ligand has been fully confirmed by 1H NMR titrations. The results obtained show that the dendrimer branches not only do not hinder, but in fact favor coordination of cyclam to Zn2+. 相似文献