亚相酸度及金属离子对2-十六氨基甲酰基-8-羟基喹啉成膜性能的影响

合成了两亲配体2-十六氨基甲酰基-8-羟基喹啉(简称HHQ),研究了亚相酸度及金属离子对HHQ成膜性能的影响。金属离子的半径、电荷及核外价电子层结构不同是影响HHQLang-muir单分子层膜性能的本质原因。从含有Ni²⁺、Cu²⁺离子的亚相表面所制备的多层LB膜的吸收光谱中产生了一个新的吸收峰。     

含冠醚结构单元螺吡喃化合物的逆光致变色性质及其对碱金属离子的识别作用

吲跺啉螺吡喃是一类重要的有机光致变色化合物,当被紫外光和可见光照射时可逆地异构化．一系列的研究表明它在非银材料、非线性光学器件以及高分辨率的信息存贮和再现等诸方面的应用价值［１］．９０年代以来,Ｉｎｏｕｙｅ［２,３］,Ｋｉｍｕｒａ［４－６］和吴成泰等［７－９］曾将冠醚结构单元引入螺吡喃,研究了对碱金属离子的识别作用及其由此诱导含冠醚螺吡喃化合物的异构化现象．由于冠醚化合物对金属离子具有特定的络合作用,当在含冠醚螺吡喃化合物中加入某些金属离子时,能诱发螺吡喃结构的异构化,从而强烈地影响异构化平衡,…     

Synthesis and luminescence of polymeric metal complexes based on 1,10-phenanthroline and 8-hydroxyquinoline

A ligand containing different coordination groups, 5-([1,10]phenanthroline-[4,5-f]imidazo-2-yl)-8-hydroxyquinoline (PhenI8Q) has been synthesized and two corresponding polymeric metal complexes Cu(II) (1) and Zn(II) (2) were prepared by coordination polymerization of the ligand with copper(II) and zinc(II) halides, respectively. The ligand was characterized by ¹H-NMR, ¹³C-NMR, and Fourier transform-infrared (FT-IR) and its corresponding polymeric metal complexes 1 and 2 were characterized by FT-IR, UV-Vis, elemental analysis, thermal gravimetric analysis, and conductivity measurements. The absorption spectra and luminescence of the ligand, 1, and 2 were investigated by UV-Vis and fluorescence spectroscopy at room temperature. Compared with the ligand, the fluorescence spectra of the polymeric metal complexes exhibit blue shifts in dimethyl sulfoxide (DMSO) solution and bathochromic shifts in the solid state. Complexes 1 and 2 emit blue light with emission maximum (λ _{f max}) at 449 and 431 nm in DMSO solution and at 485 and 484 nm in the solid state, respectively.     

高分子化8-羟基喹啉锂的合成与静电自组装研究

设计合成了甲基丙烯酸二甲氨基乙酯(DM)含量为9.69%的丙烯酸甲酯共聚物(CPA),将制得的5-氯甲基-8-羟基喹啉(CHQ)挂接到CPA上,得到季铵型高分子化8-羟基喹啉(CPA-HQ)后,与金属离子Li+配位得到CPA-HQ-Li.化合物结构通过红外、紫外和荧光光谱等表征.多层超薄膜用CPA-HQ-Li和聚阴离子电解质(全氟磺酸)通过静电自组装制得.自组装膜的紫外和荧光相对于溶液(溶剂为四氢呋喃)发生了红移,膜的紫外吸收强度随组装膜层数增加线性增大,荧光强度随膜层数增加线性递减.高分子化8-羟基喹啉锂溶液和自组装膜的紫外和荧光光谱与文献报道一致.实验结果表明这种材料可用于有机电致发光器件(OLEDs)的制备.     

γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物的合成与表征

利用缺位填充法合成了12个γ-[SiW10O36]8-夹心型稀土元素单取代多酸化合物K13[Ln(SiW10O36)2]·nH2O(Ln=La3+,Ce3+,Pr3+,Nd3+,Sm3+,Eu3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Yb3+).通过元素分析确定其组成,由红外光谱、紫外-可见吸收光谱、循环伏安及室温磁化率测定结果确认稀土离子与γ-[SiW10O36]8-相配位;183WNMR及荧光光谱结果则表明,稀土离子处于2个γ-[SiW10O36]8-构成的八配位环境中,标题化合物具有夹心型D2d对称性结构.     

5,10,15,20-四(对氯苯基)卟啉羟基稀土配合物的光谱研究

研究了四(对氯苯基)卟啉及其羟基稀土配合物的紫外-可见光谱、红外光谱和拉曼光谱,对主要谱带进行了经验归属,讨论了中心离子对紫外光谱和共振拉曼光谱结构敏感带频率的影响.     

新型Salen型配合物的合成和表征及轴向配位热力学

采用金属模板法合成了四个新型Salen型单、双核金属配合物,并用元素分析、核磁共振(1HNMR)、电喷雾质谱(ESI-MS)、傅里叶变换红外光谱(FT-IR)等手段进行了表征.使用紫外-可见(UV-Vis)光谱滴定法和圆二色(CD)光谱研究了主体金属镍配合物与咪唑类含氮小分子的轴向配位反应热力学性质.结果表明:主体与咪唑(Im)和N-甲基咪唑(N-MeIm)的配位数是2,而与2-Et-4-MeIm和2-MeIm的配位数是1;轴配体系的热力学数据显示主体与咪唑类配体的平衡常数按K苓(Im)K苓(N-MeIm)K苓(2-Et-4-MeIm)K苓(2-MeIm)顺序依次减小;测得的△rHm苓和△rSm苓数据表明该轴向配位反应为放热、熵增加过程.     

Studies on DNA cleavage and antimicrobial screening of transition metal complexes of 4-aminoantipyrine derivatives of N2O2 type

A new series of transition metal complexes of Cu(II), Ni(II), Zn(II) and VO(IV), were synthesized from the Schiff base (L) derived from 4-aminoantipyrine, 3-hydroxy-4-nitrobenzaldehyde and acetylacetone. The structural features were arrived from their elemental analyses, magnetic susceptibility, molar conductance, Mass, IR, UV-Vis., ¹H NMR and ESR spectral studies. The data show that the complexes have composition of [ML]X type. The UV-Vis., magnetic susceptibility and ESR spectral data of the complexes suggest a square-planar geometry around the central metal ion except for VO(IV) complex which has square-pyramidal geometry. The redox behavior of copper and vanadyl complexes were studied by cyclic voltammetry. The antimicrobial screening tests were also recorded and gave good results in the presence of metal ion in the ligand system. The nuclease activity of the above metal complexes shows that the copper and nickel complexes cleave DNA through redox chemistry, whereas other complexes are not effective.     

基于罗丹明-B的双通道铜离子荧光探针及其活细胞的应用(英文)

本文介绍了一种紫外-可见和荧光双通道铜离子探针,该探针基于罗丹明-B,通过水合肼为桥梁来连接三苯胺,便利而廉价。其在水体系下对铜离子显示出了良好的选择性和极高的灵敏度(2.78×10-8mol·L-1)。并且,通过初步的活细胞测试,表明该铜离子探针有着良好的生物相容性和细胞穿透性,在生物、医药领域有着非常大的潜力。     

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

The ternary piroxicam (Pir; 4-hydroxy-2-methyl-N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA chelates were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.     

Synthesis and DNA binding studies of Ni(II), Co(II), Cu(II) and Zn(II) metal complexes of N1,N5-bis[pyridine-2-methylene]-thiocarbohydrazone Schiff-base ligand

The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl2(H2L)]·nH2O (MNi, Co, Cu and Zn) were synthesized by forming complexes of the N1,N5-bis[pyridine-2-methylene]-thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), 1H and 13C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (Kb) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions.     

具有π共轭骨架的Salen-卟啉型同、异双核配合物的合成及谱学性质

设计合成了两类具有π共轭骨架的Salen-卟啉型配体及金属配合物. 以Salen-卟啉半体及相应的醛为原料, 运用金属模板法合成了单核镍和双核镍Salen-卟啉型金属配合物. 在单核镍的基础上可得到异双核镍、锌Salen-卟啉型金属配合物. 通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱、电喷雾质谱(ESI-MS)和荧光光谱等多种谱学手段对其结构进行了表征. 研究表明, 单核镍及异双核镍、锌配合物中, 镍离子落入Salen 部分的配位空腔, 而锌离子则是与卟啉部分形成锌卟啉大环结构。由于卟啉环流效应及分子π共轭结构的影响, 导致配体上的氢原子的化学位移向高场或低场移动. 当金属离子与配体配位之后,卟啉部分的紫外-可见光谱的Soret带和Q带均发生显著变化, 而荧光则出现猝灭现象.     

铁邻菲咯啉、8-羟基喹啉配合物/Y型分子筛的制备、表征及催化苯酚羟化的研究

制备了铁邻菲咯啉、8-羟基喹啉配合物/Y型分子筛(简记为FePhen/Y,FeOx/Y)。用元素分析, TG-DTA, UV-Vis, IR, SEM, BET及XRD等方法确定了分子筛笼中金属配合物的生成及其晶体结构, 考察了实验参数对苯酚转化率及产物选择性的影响。     

5-氟尿嘧啶修饰卟啉的合成及抗肿瘤活性

合成了一种5-氟尿嘧啶修饰的自由卟啉(5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)卟啉)及其2种金属卟啉配合物:5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锰卟啉和5-[2-(5-氟尿嘧啶-3-基)乙氧基苯基]-10,15,20-三(4-甲氧基苯基)锌卟啉。 通过紫外可见光谱(UV-Vis)、红外光谱(IR)和核磁共振谱氢谱(¹H NMR)对目标化合物进行了结构表征。 用噻唑蓝法(MTT法)测定了自由卟啉、锰卟啉及锌卟啉分别对肺腺癌细胞株A549、肝癌细胞株Bel7402和人结肠癌细胞株HCT-8的抑制活性。 其中,锰卟啉对人结肠癌细胞株HCT-8的半抑制浓度为IC₅₀为17.8 mg/L,具有一定的细胞毒作用。     

Co(II) and Cu(II) complexes of 2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidine

The Co(II) and Cu(II) complexes of 2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidine (trimethoprim) were synthesized and characterized by elemental analysis, UV-Vis and IR spectroscopy, magnetic susceptibility measurements, EPR (Cu complexes) and single crystal X-ray studies. The molecular structures of the compounds consist of dimeric metal ions in distorted octahedral environments, bridged with four acetate ions and each metal ion coordinated to one trimethoprim through the pyrimidinyl nitrogen atom.     

新型富勒烯膦金属配合物的合成

用配体取代法合成了新型富勒烯膦金属配合物——C60.双(二苯基膦)戊烷合钯[C60Pd(dpppe),1],其结构经UV-Vis,IR,XPS及元素分析表征。在1的分子结构中,C60以σ-π配位方式与Pd配位,形成新型的η2-C60双齿膦金属配合物。     

Solution and solid-state interactions in a supramolecular ruthenium photosensitizer-polyoxometalate aggregate

The intermolecular interactions between a ruthenium-based photosensitizer ([Ru(tbbpy)(2)(biH(2))](2+)) and a molecular metal oxide ([β-Mo(8)O(26)](4-)) are investigated in solution and in the solid state. The supramolecular interactions were studied using (1)H-NMR, UV-Vis and emission spectroscopy, ESI mass spectrometry and single-crystal X-ray diffraction. The formation of supramolecular aggregates was observed both in the crystal lattice and in solution. In addition, it is shown that aggregation in solution can be controlled by the competitive formation of ion pairs.     

MeAPO-5分子筛的合成及其在肉桂醇选择氧化反应中的催化性能

采用水热法合成了一系列杂原子磷铝分子筛MeAPO-5(Me=Co,Fe,Cu,Zn,Mn),并利用X射线衍射(XRD),热重-差热分析(TG-DTA),电感耦合等离子体原子发射光谱(ICP-AES)和漫反射紫外-可见光谱(DRUV-Vis)等技术对分子筛的结构,化学组成以及金属离子的存在状态进行了表征.结果表明,合成的纯相MeAPO-5分子筛具有较高的结晶度,金属杂原子种类显著影响其在MeAPO-5分子筛中的存在状态,取代度及合成样品的结晶度.Co2+,Fe3+,Zn2+和Mn2+较易进入分子筛骨架,而Cu2+较难进入.通过考察MeAPO-5分子筛在肉桂醇氧化反应中的催化性能,发现CoAPO-5分子筛具有良好的选择氧化催化性能,1,4-二氧六环是较好的溶剂,调变反应温度可以有效调控产物的选择性.     

嫁接型席夫碱配合物的制备及其催化性能

应用超声波技术在温和条件下以氯丙基三甲氧基硅烷为偶联剂, 制得了嫁接过渡金属Zn, Cu, Fe和Co的N,N-双水杨醛缩二乙烯三胺席夫碱配合物[SiO₂-M(NNOO)], 并与传统加热搅拌法制得的样品的物性和催化性能做了比较. 应用IR和UV-Vis谱学技术对其进行了初步表征, 结果表明, 两种方法制得的嫁接型配合物的红外光谱均呈现出胺基和席夫碱相应基团的特征吸收, 配体和配合物红外和紫外光谱之间的差别表明配合物结构的存在. 将所制得的样品在苯乙烯选择氧化制苯甲醛反应中进行了催化性能的测试, 考察了反应时间和催化剂对苯乙烯转化率和选择性的影响, 结果表明苯乙烯转化率均在90%以上, 苯甲醛选择性最高可达93.5%, 产物选择性与反应时间和催化剂中过渡金属的类型均有关系.     

Synthesis, spectral characterization of Schiff base transition metal complexes: DNA cleavage and antimicrobial activity studies

A new series of transition metal complexes of Cu(II), Ni(II), Co(II), Mn(II), Zn(II), VO(IV), Hg(II) and Cd(II) have been synthesized from the Schiff base (L) derived from 4-aminoantipyrine, 3-hydroxy-4-nitrobenzaldehyde and o-phenylenediamine. Structural features were obtained from their elemental analyses, magnetic susceptibility, molar conductance, mass, IR, UV-Vis, ¹H NMR and ESR spectral studies. The data show that these complexes have composition of ML type. The UV-Vis, magnetic susceptibility and ESR spectral data of the complexes suggest a square-planar geometry around the central metal ion except VO(IV) complex which has square-pyramidal geometry. The redox behaviour of copper and vanadyl complexes was studied by cyclic voltammetry. Antimicrobial screening tests gave good results in the presence of metal ion in the ligand system. The nuclease activity of the above metal complexes shows that Cu, Ni and Co complexes cleave DNA through redox chemistry whereas other complexes are not effective.