重氮树脂—聚磷酸复合物

带有相反电荷 (通常在侧链 )的聚电解质 ,通过静电相互作用形成的复合物 ,称聚电解质复合物 (ＰＥＣ) .ＰＥＣ已有很多研究[1～ 3] ,也有一些应用的报道[4,5] .重氮树脂 (ＤＲ) ,一种由二苯胺 4 重氮盐与多聚甲醛在浓硫酸中缩合得到的缩聚物[6] ,因侧链带重氮基 ,所以是正离子聚电解质 .它能与各种负离子聚电解质生成感光性的ＰＥＣ ,并可用作光成像体系的感光剂[7,8] .ＤＲ与聚磷酸 (ＰＰＡ)生成重氮基为正离子 ,磷酸基为负离子的复合物 ,这种复合物文献上未有过报道 .本文初步研究了这种复合物的制备与性质 .1　重氮树脂 聚磷酸复合物 (…     

含[BMIM]Cl-ZnCl2和非质子溶剂的凝胶聚合物电解质的合成

以烯类单体MA、MMA、HEMA为基质,通过原位聚合,合成了同时含离子液体[BMIM]Cl-ZnCl2和非质子溶剂的一系列新型凝胶聚合物电解质,用FTIR、AC、TG等方法对其结构和性能进行了表征。研究表明,聚合物电解质具有复合物结构;[BMIM]Cl-ZnCl2和非质子溶剂PC﹑DMC的加入使聚合物电解质的室温离子电导率大大增加,达2.83×10⁻³ S/cm,且与温度的关系符合VTF方程;聚合物电解质的热分解温度大于275 ℃,显示出良好的热稳定性。     

丁苯胶乳的合成研究

以丁二烯和苯乙烯为单体、十二烷基硫醇为乳化剂,通过一步法合成了大粒径丁苯胶乳（SBR）.结果表明：乳化剂浓度、电解质浓度、固含量及单体加入方式是控制丁苯胶乳粒径大小的关键因素.通过适时补加乳化剂,选取适宜的电解质浓度、固含量及采用种子半连续加料方式有利于控制SBR粒径大小及分布.     

AM/DMC/C11AM疏水缔合聚两性电解质的合成、表征与溶液性质

通过Ritter反应合成弱阴离子型疏水单体丙烯酰胺基十一烷基酸(C11AM). 以丙烯酰胺(AM)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)和丙烯酰胺基十一烷基酸(C11AM)为原料, 在水介质中合成新型疏水缔合聚两性电解质AM/DMC/C11AM. 利用1H NMR确证了疏水单体和共聚产物的分子结构. 流变性和芘荧光探针的研究结果表明, AM/DMC/C11AM系列疏水缔合聚两性电解质由于兼具疏水缔合性质和反聚电解质效应, 使其具有较好的耐盐性能.     

强聚电解质对离子型芘衍生物探针的键合

由于芘单线态寿命长 ,单体态发射光谱精细结构对微环境极性敏感 ,在特定的环境下能形成激基缔合物 ,而且可作为非辐射能量转移过程的受体 ,因而被广泛应用于水溶性聚合物的研究 [1～ 3] .芘微溶于水 ,可以作为自由“探针”加入体系探测环境极性的变化与疏水微区的形成 .而离子型的芘衍生物由于良好的水溶性 ,可以同相反电荷的聚电解质发生静电键合 ,最近已经被用来研究聚电解质多层膜的结构 [4 ] .但是芘的离子衍生物同聚电解质键合的规律还不是十分清楚 ,例如聚电解质的电荷密度和化学结构对键合的影响 ,尤其是键合的化学计量关系 ,这对芘…     

电聚合导电聚吡咯的合成研究

用电化学法将吡咯单体聚合在电极上，于不同支持电解质的水溶液中得到聚吡啶薄膜。研究了电解质浓度、电解质阴离子种类及聚合时间对聚吡咯薄膜导电性能的影响。     

基于聚乙二醇接枝丙烯酸树酯光固化电解质的制备及性能研究

聚氧化乙烯(PEO)(聚乙二醇(PEG))和丙烯酸树脂在聚合物基电解质中具有很好的应用,本文通过紫外光引发单/双官能度的聚乙二醇接枝丙烯酸树脂单体聚合构建了离子电导率高、易于封装,可避免电解质泄漏的准固态聚合物电解质.通过调控聚乙二醇二甲基丙烯酸酯(PEGDA)和甲氧基聚乙二醇单甲基丙烯酸酯(PEGMA)2种单体的比例以及锂盐溶液的含量,成功制备出具有高离电导率的准固态聚合物电解质.采用傅里叶变换红外光谱仪(FTIR),电化学工作站对PEGMA/PEGDA基聚合物电解质进行表征,研究各组分比例对电解质的电化学性能影响.当PEGMA/PEGDA单体比例为75/25,锂盐溶液的占比为75%时,形成的薄膜状态电解质表现出1.96×10^?3 S·cm^?1的高离子电导率,较原始配比提高了14倍.将制备的电解质应用于电致变色器件,在580个变色循环后,器件依然可以实现稳定快速的颜色切换,2种颜色变换时间均在3 s以内,本文中研究的聚醚接枝丙烯酸树酯基电解质材料在电致变色器件中有较好的应用前景.     

基于聚乙二醇接枝丙烯酸树酯光固化电解质的制备及性能研究

聚氧化乙烯(PEO)(聚乙二醇(PEG))和丙烯酸树脂在聚合物基电解质中具有很好的应用,本文通过紫外光引发单/双官能度的聚乙二醇接枝丙烯酸树脂单体聚合构建了离子电导率高、易于封装,可避免电解质泄漏的准固态聚合物电解质.通过调控聚乙二醇二甲基丙烯酸酯(PEGDA)和甲氧基聚乙二醇单甲基丙烯酸酯(PEGMA) 2种单体的比例以及锂盐溶液的含量,成功制备出具有高离电导率的准固态聚合物电解质.采用傅里叶变换红外光谱仪(FTIR),电化学工作站对PEGMA/PEGDA基聚合物电解质进行表征,研究各组分比例对电解质的电化学性能影响.当PEGMA/PEGDA单体比例为75/25,锂盐溶液的占比为75%时,形成的薄膜状态电解质表现出1.96×10~(-3)S·cm~(-1)的高离子电导率,较原始配比提高了14倍.将制备的电解质应用于电致变色器件,在580个变色循环后,器件依然可以实现稳定快速的颜色切换,2种颜色变换时间均在3 s以内,本文中研究的聚醚接枝丙烯酸树酯基电解质材料在电致变色器件中有较好的应用前景.     

聚(二甲基丙烯酸多缩乙二醇酯—甲基丙烯酸锂)固体电解质研究

本文以聚乙二醇(PEG)为原料,在pEG端基引入双键,合成了PEG大分子单体。研究了PEG大分子单体—甲基丙烯酸锂(MALi)共聚及成膜反应,制备了单离子导电的共聚物薄膜,测定了其电性能,室温最高电导率可达10~(-6)Sem~(-1)以上,100℃时可达10~(-4)Scm~(-1),而且电导率—时间稳定性好。在力学性能方面,既柔韧且具有一定的强度,是作为固体电池电解质材料的理想材料。本文还研究了影响共聚物成膜性和电性能的因素,同时,采用DSC,X-射线衍射、IR等现代分析技术对聚合物主体材料及共聚物的结构和形态进行了研究。     

聚丙烯酸增稠剂的反相乳液聚合及其增稠性能

采用具有增稠和抗电解质作用的丙烯酸聚氧乙烯酯活性单体和具有聚合稳定作用的高分子表面活性剂,通过反相乳液聚合法合成了涂料印花用丙烯酸系增稠剂.研究了活性单体、交联剂、反应时间等因素对产物性能的影响.得出活性单体用量占共聚单体摩尔数的0.5%,交联剂占共聚单体质量的0.3%,反应时间为1.5h时,增稠剂的综合效果最好.     

Evaluation of 99mTc-HIDA complex as a cholescintigraphic agent (author's transl)

In the reaction labeling N-(2,6-dimethylphenylcarbamoylmethyl) iminodiacetic acid (HIDA) with 99mTc, several complexes with different chemical characteristics were observed to occur with slight changes in the labeling conditions. Among these complexes, a complex detected in the bile of rats was limited to one complex, named as complex II. The preparation method of 99mTc-HIDA complex II and the exchange reaction between this complex and penicillamine indicate that 99mTc is coordinated with HIDA as low-hydrolyzed 99mTc in this complex. This complex is excreted rapidly through the bile and within 1 hr, about 65% of the total activity injected is recovered from bile in rats. The organ distribution of this complex was studied in mice by radioassay and in rabbits by scintillation camera and, in both cases, the radioactivity was accumulated in the gallbladder. These results suggest that the 99mTc chemical state, low-hydrolyzed state, relates to the bile excretion behavior of this complex, a potentially useful cholescintigraphic agent.     

Synthesis,characterization, crystal structure,and biological activity of the copper complex

This work reports the synthesis and biological activity of the copper complex with 2–thenoyltrif-luoroacetone (HTTA). The complex was characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The crystal structure was determined by single-crystal X-ray diffraction. The complex exists as a parallelogram with four coordination sites occupied by the carbonyl oxygen atoms from HTTA. The antibacterial activity test shows that the complex exhibits better antibacterial ability against Escherichia coli and Staphylociccus aureus (MIC were about 180, 150 μg/ml, respectively) and can be considered as broad-spectral antimicrobial. The antitumor activity of the copper(II) complex is tested by methyl thiazolyl tetrazolium assays against human Leukemia cells K562. The copper(II) complex exhibits potent antitumor effects against K562 cell lines. The IC₅₀ value of the complex is about 0.01 μg/ml. The research shows that the complex can inhibit K562 tumor cell growth and generation and induce apoptosis. The inhibition ratio is accele by increasing the dosage and has a significant positive correlation with medication dosage.     

A study of host-guest complexation between amodiaquine and native cyclodextrin. Characterization in solid state and its in-vitro anticancer activity

Amodiaquine (AQ) has been used widely as an antimalarial drug. Amodiaquine is a mannich base 4-amino quinolone with a mode of action similar to that of chloroquine. The inclusion complex of AQ with β-Cyclodextrin (β-CD) in solution phase is studied from the ground and excited state with UV-Visible and fluorescence spectroscopy, respectively. A binding constant and stoichiometric ratio between AQ and β-CD are calculated by BH equation. The solid complexes are prepared by physical method (PM), kneading method (KM) and co-precipitation method (CP). The solid complex is characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and powder X-ray diffraction. The CP method gives the solid product with a better yield than that of physical mixture and KM products. The orientation and structure of the complex are proposed based on the analysis of Patch-Dock server. The anticancer activity also performed for pure AQ and their complex with β-CD. It is clearly shown that an improvement of anticancer activity of AQ while forming complex with β-CD. The solid inclusion complex behaves as the better anticancer ability than AQ alone.     

Anion directed synthesis of paddlane and trisilver tweezer complexes based upon silver coordination chemistry

Addition of AgBF4 or Ag(O3SCF3) to the tripodal ligand, Me3tacnRh(CCPh)3, yields a paddlane complex as well as a novel trinuclear silver "tweezer" complex based upon silver acetylene coordination chemistry. The paddlane is composed of two Me3tacnRh(CCPh)3 moieties held together by silver acetylene interactions. The tweezer complex is composed of one tripodal moiety with three silver atoms coordinated to each acetylene-Rh-acetylene face. The tweezer complex is stabilized by additional interactions, including a triflate anion which serves to cap the complex.     

Chelate resin-iron(II) complex: Adsorption and desorption of nitrogen monoxide at the dry state

A chelate resin-immobilized iron(II) complex was prepared from iron(II) and poly(styrenecodivinylbenzene) which is functionalized by iminodiacetic acid group. It is activated by drying after having been washed with methanol. The resin complex can rapidly adsorb nitrogen monoxide, and the nitrogen monoxide adsorbed on the complex can be released by the treatment with heat. The adsorption of nitrogen monoxide proceeds through the 1:1 complex formation of the NO molecule with the iron(II) atom, and its complex formation constant was calculated as 8330 atm^?1 at room temperature from Langmuir plots. This value does not depend on the solvents used for washing. The activation of the resin complex by the treatment of washing with methanol is derived by increasing the amount of effective iron(II) ions due to the increase in the surface area. Moreover, this resin complex was revealed to have high complex formation constant with NO and high durability to dioxygen compared with an aqueous solution of ethylenediaminetetraacetato–iron(II) complex, which is the corresponding monomeric absorbent commonly used for nitrogen monoxide.     

Calculations on the octupolar molecules with enhanced two-photon absorption cross sections based on the Zn (II) and Cu (I) as centers

The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials.     

Influence of carboxamido nitrogen donors on the redox potential of copper(III) complexes

The synthesis of a new copper(III) complex with aliphatic carboxamido-N and thiolato-S donors is reported. This complex was thoroughly characterized by ¹H NMR, UV–Vis spectroscopy, and cyclic voltammetry, as well as by single crystal X-ray crystallography. The copper(III) state in this complex is more stabilized than in the parent compound with aromatic carboxamido nitrogen donors.     

水溶性茂钛配合物的表征及其在芳香酸茂钛衍生物合成中的应用

二氯二茂钛与5－磺基水杨酸形成了较为稳定的水溶性配合物。由等摩尔系列 法确定了其组成为1:1,通过对含5－磺基水杨酸二茂钛配离子的不溶性配合物1的 结构分析表明,其中的羧基以双齿形式与钛配位,形成了四元环状结构。首次利用 该水溶性配合物在水相和两体系中得到了八种新的二茂钛芳香酸衍生物,为配合物 2 ～ 9。运用元素分析、IR及~1H NMR对它们的组成和结构进行了表征,结果表明 ,这八种配合物中羧基均以单齿形式与钛配位,且不含5－磺基水杨酸配体。     

Synthesis, structural characterization and catalytic activity of a multifunctional enzyme mimetic oxoperoxovanadium(V) complex

The synthesis and structural characterization of a novel oxoperoxovanadium(V) complex [VO(O(2))(PAH)(phen)] containing the ligands 2-phenylacetohydroxamic acid (PAHH) and 1,10-phenanthroline (phen) has been accomplished. The oxoperoxovanadium(V) complex was found to mimic both vanadate-dependent haloperoxidase (VHPO) activity as well as nuclease activity through effective interaction with DNA. The complex is the first example of a structurally characterized stable oxoperoxovanadium(V) complex with a coordinated bi-dentate hydroximate moiety (-CONHO(-)) from 2-phenylacetohydroximate (PAH). The oxoperoxovanadium(V) complex has been used as catalyst for the peroxidative bromination reaction of some unsaturated alcohols (e.g. 4-pentene-1-ol, 1-octene-3-ol and 9-decene-1-ol) in the presence of H(2)O(2) and KBr. The catalytic products have been characterized by GC-MS analysis and spectrophotometric methods. The DNA binding of this complex has been established with CT DNA whereas the DNA cleavage was demonstrated with plasmid DNA. The interactions of the complex with DNA have been monitored by electronic absorption and fluorescence emission spectroscopy. Viscometric measurements suggest that the compound is a DNA intercalator. The nuclease activity of this complex was confirmed by gel electrophoresis studies.     

Preparation of Tc-HA complex by displacement of thiourea from the hexakis(thiourea-S)technetium(III) complex

The complexation of technetium with humic acid is usually done by a reduction of pertechnetate by Sn²⁺ ions. A Tc-HA complex can be scavenged in a Sn-HA complex, if tin is present as reductant. The main aim of the study was a preparation of the Tc-HA complex without impurities of Sn ions or other metal reductant, which was performed by a ligand exchange with hexakis(thiourea-S)technetium(III) under nitrogen atmosphere at pH 5.5. The [Tc(tu)₆]³⁺ complex was prepared from TcO₄ ^- in acidic solution with thiourea as a reductant. Presence of the Tc-HA complex and other technetium species was determined by gel chromatography, paper chromatography and dialysis. Yield of Tc-HA complex was about 80% and reaction mixture contains about 20% of technetium dioxide, which is a side product of ligand-exchange.