《化学通报》网络版(Chemistry Online)2002年第8期论文摘要

[Ｗ 0 5 7]聚合物层状双氢氧化物纳米复合材料ＡｄｖａｎｃｅｉｎＳｔｕｄｉｅｓｏｆＰｏｌｙｍｅｒ ＬａｙｅｒｅｄＤｏｕｂｌｅＨｙｄｒｏｘｉｄｅＮａｎｏｃｏｍｐｏｓｉｔｅ杨亲正　张春光　孙德军 (山东大学胶体与界面化学教育部重点实验室　济南　 2 5 0 1 0 0 )介绍了聚合物层状双氢氧化物 (聚合物 ＬＤＨ)纳米复合材料的制备、结构、性能及应用前景。该体系是在无机物层叠片层的层间填充了聚合物客体而形成 ,由于在无机物叠层表面的化学组分与填充的聚合物基团存在着协调性 ,使聚合物 ＬＤＨ体系具有可剪裁性。聚合物 ＬＤＨ纳米复…     

放射标记法研究壳聚糖与牛血清白蛋白的自组装超薄膜

基片在两种带有相反电荷的聚电解质溶液中交替吸附 ,其表面形成致密有序的超薄膜的自组装 (ＥＳＡ ｅｌｅｃｔｒｏｓｔａｔｉｃｓｅｌｆ ａｓｓｅｍｂｌｙ)技术是由Ｄｅｃｈｅｒ及其合作者在 1 991年提出[1] ,由于简单易行 ,从一出现就受到了广大研究者的极大兴趣[2～ 4 ] .对生物材料来说 ,这无疑是一项非常重要且方便的表面改性手段 .因为生物材料在生物体内种植时 ,是否会被机体视为异物 ,关键在于机体与材料表面的相互作用 ,而与材料的本体性质基本无关[5] .因此利用这种技术 ,可对生物材料 ,特别是对那些生物相容性不好的材料表面进行…     

一种新型联萘基旋光共轭聚合物的圆二色谱和圆偏振荧光光谱

众所周知 ,聚合物的光电性质依赖于聚合物链的构象和 (或 )组成 ,通过在聚合物上引入手性单元 ,采用圆二色谱 ( CD)和圆偏振荧光光谱 ( CPL)等方法可表征聚合物结构 [1] .近年来 ,由于圆偏振光可用作光数据存储和液晶显示器背景光 [2 ] ,人们开始注重共轭聚合物圆偏振光材料的研究 .共轭聚合物的光致和电致圆偏振光的现象由一种带手性侧链的聚噻吩[3 ] 和一种带手性侧链的聚 (对苯撑乙烯 ) [4 ]产生 ,但它们的圆偏振荧光度 (用不对称因子 glum=2 ( IL-IR) / ( IL+IR)表示 ,IL 和 IR 分别指左圆偏振光强度和右圆偏振光强度 )相对较低 …     

A New Flavonol Glycoside from Anaphalis sinica Hance

ＩｎｔｒｏｄｕｃｔｉｏｎＳｅｖｅｒａｌｐｌａｎｔｓｏｆｇｅｎｕｓＡｎａｐｈａｌｉｓ(Ｃｏｍｐｏｓｉｔａｅ)ｈａｖｅｂｅｅｎｐｈｙｔｏｃｈｅｍｉｃａｌｌｙｓｔｕｄｉｅｄ ,ｆｒｏｍｗｈｉｃｈｆｌａｖａｎｏｉｄｓ[1,2 ] ,ｈｅｌｉｐｙｒｏｎｅ[3] ,ｃｈｌｏｒｏａｃｅｔｙｌｅｎｉｃｃｏｍｐｏｕｎｄｓｗｉｔｈａｄｉｈｙｄｒｏｐｙｒａｎｏｒｆｕｒａｎｒｉｎｇ[4] ａｎｄｐｈｔｈａｌｉｄｅｓｈａｖｅｂｅｅｎｒｅｐｏｒｔｅｄ[5 ] .Ａ .ｓｉｎｉｃａＨａｎｃｅ ,ｄｉｓｔｒｉｂｕｔｅｄｉｎＣｈｉｎａａｎｄａｌｓｏｆｏｕｎｄ…     

含手性末端基偶氮聚合物膜的全息光栅研究

偶氮苯侧链型高分子由于其含有偶氮苯基团 ,在光作用下会发生可逆的顺反异构过程 ,具有光致取向特性 ,在光学处理、衍射光学、投影显示、光开关等许多方面具有潜在的应用性[1] .近 1 0多年来国内外学者对此类化合物进行了广泛的研究 ,已有文献报道可利用Ａｒ+激光束在偶氮苯聚合物薄膜上直接“写入”表面凸起光栅 ,并且通过原子力显微镜观测到光栅起伏 .这种光栅很稳定 ,并可以利用光学方法“擦去” .偶氮苯聚合物上述独有的性质引起了许多学者的兴趣[2 ,3] .另一方面 ,由于旋光性聚合物在光学物理性质上的优势 ,我们已将手性基团引入偶氮苯…     

具有双光子吸收特性的咪唑类衍生物的合成及其光物理性能研究

分子在强激光作用下能同时吸收两个光子的现象称为双光子吸收(TPA),具有大的双光子吸收截面(σ2)的分子有多种用途,是目前光电子材料研究领域的热点之一.双光子吸收材料可应用于上转换激射[1]、光限幅[2]、光稳幅、三维光存储[3]、三维微加工[4,5]以及光动力疗法[6]等.但由于一般材料的双光子吸收截面很小,大大限制和束缚了双光子吸收材料的发展应用.     

简易荧光仪共振光散射光谱法测定蛋白质的研究

光散射是指一束光通过介质时 ,在入射光方向以外的各个方向观察到的一种光辐射现象。瑞利散射是散射光波长等于入射光波长 ,而且散射粒子又远小于入射光波长产生的弹性散射 ,其散射强度与波长四次方成反比[1 ] 。如果这种瑞利散射位于吸收带附近 ,则可引起散射强度的急剧增加 ,这种现象被称为共振瑞利散射 (ＲＲＳ) ,或称共振光散射 (ＲＬＳ) [2 ] 。 1 993年 ,Ｐａｓｔｅｒｎａｃｋ等首次用共振光散射技术研究了卟啉类化合物在核酸上的聚集 ,从而首次将该技术与化学过程联系起来。黄承志等利用卟啉在蛋白质或核酸上聚合组装时产生的增强的…     

《化学通报》网络版(Chemistry Online)2003年第2期论文摘要

[Ｗ 0 0 9]锂聚合物电解质的导电性能 ＡｄｖａｎｃｅｓｉｎＩｏｎｉｃＣｏｎｄｕｃｔｉｖｉｔｙｏｆＬｉｔｈｉｕｍＰｏｌｙｍｅｒＥｌｅｃｔｒｏｌｙｔｅｓ张虎成1,2 　轩小朋1,2 　王键吉1 　汪汉卿2 (1河南师范大学化学与环境科学学院　新乡　 4 5 3 0 0 2 ;2 中国科学院兰州化学物理研究所　兰州　 73 0 0 0 0 )综述了四种类型的锂聚合物电解质体系的特征及近年来的研究进展 ,着重阐明了聚合物的结构、离子传输机理和离子电导率之间的关系及影响聚合物电解质导电性能的因素。Ｅａｃｈｓｙｓｔｅｍｏｆａｌｌｆｏｕｒｓｙｓｔｅｍｓｆ…     

聚双(2-吡咯基乙氧基磷腈)的合成、氧化交联和导电性研究

有机 /无机杂化聚磷腈具有优良的加工性能和使用性能 ,可以在许多领域获得应用 [1] .具有光电活性的聚磷腈研究也引起了广泛的关注 [2～ 4 ] . Allcock等 [2 ] 合成了具有离子传导特性的聚磷腈 ,可应用于锂离子电池 .具有非线性光学特性的聚合物也有研究报道 [3 ] . L eung等 [4 ] 合成了具有电致发光基团的聚磷腈 ,部分聚合物具有蓝光发射的特征 .合成化学键合的聚 (N -烷基 )吡咯通用聚合物复合膜材料已经得到了重视[5,6] .本文合成了 2 -吡咯基乙醇 ,将其与反应性无机聚合物聚 (二氯 )磷腈进行高分子取代反应 ,合成了含吡咯侧基的聚磷…     

Preparation, characterization and gas-sensitive properties of nano-crystalline Cr_2O_3-Fe_2O_3 mixed oxides

Ｆｅｒｒｉｃｏｘｉｄｅ(αＦｅ2Ｏ3),ｃｈｒｏｍｉｃｏｘｉｄｅ(αＣｒ2Ｏ3)ａｎｄｔｈｅｉｒｍｉｘｅｄｃｏｍｐｏｕｎｄｓｈａｖｅｉｍｐｏｒｔａｎｔａｐｐｌｉｃａｔｉｏｎｉｎｍａｎｙｆｉｅｌｄｓ.Ｆｏｒｉｎｓｔａｎｃｅ,ｔｈｅｙｃａｎｂｅｕｓｅｄａｓｃａｔａｌｙｓｔｓｆｏｒｈｉｇｈｔｅｍｐｅｒａｔｕｒｅｗａｔｅｒｇａｓｓｈｉｆｔｒｅａｃｔｉｏｎ[1]ａｎｄｒｅｄｕｃｔｉｏｎｏｆＮＯｘｂｙＮＨ3[2],ａｓｒｅｆｒａｃｔｏｒｙｍａｔｅｒｉａｌｓ[3]ａｎｄｓｅｎｓｉｎｇｍａｔｅｒｉａｌｓ[4,5],ａｎｄｓｏｏｎ.Ｓｉｎｃ…     

表面起伏光栅形成速率的影响规律 Ⅰ.偶氮生色团种类和官能度的影响

设计并合成了含有不同生色团以及不同官能度的环氧树脂基偶氮高分子 ,系统研究了偶氮生色团的种类和官能度对光栅形成速率的影响规律 .实验结果表明 ,偶氮苯对位是羧基的聚合物的光栅形成速率明显快于偶氮苯对位是硝基的聚合物 ,光栅形成速率随偶氮生色团官能度的增加而加快 .这两类聚合物都可以形成规整的可擦式表面起伏光栅     

Synthesis and characterization of optically active polymers containing azo groups and (l)-α-amino acid moieties

The paper discusses the synthesis of new optically active azo diacids starting from two activated azo diesters (diethyl azodicarboxylate and ethyl phenylazocarboxylate) and various (l)-α-amino acids as: (l)-alanine, (l)-leucine, (l)-cysteic acid monohydrate and (l)-cystine. New chiral polymers derived from some of synthesized monomers were obtained under mild reaction conditions by unconventional polycondensation methods. The structure of synthesized compounds has been spectroscopically confirmed and the solubility, optical activity and thermal properties of the obtained materials are reported. To estimate the molecular weights of new polymers the ¹H-NMR and viscometric data were used and obtained values were compared with those of the polymers with alike chain structure synthesized by similar procedures.     

一种具有可逆光加工特性的偶氮聚电解质的合成与表征

合成一种具有可逆光加工特性的偶氮聚电解质(PAA-AZ),用核磁、热分析、紫外-可见光谱、接触角及GPC等手段对其进行了结构和性能表征.PAA-AZ的旋涂膜用线偏振Ar+激光照射一段时间,在原子力显微镜(AFM)下观测其表面,膜表面形成了规整有序纳米尺寸的三维表面图案表面起伏光栅(起伏深度为100nm).用氦氖激光检测了PAA-AZ旋涂膜一级衍射效率与光照时间的关系.     

重氮偶合反应合成超支化偶氮聚合物的光响应性能研究

利用重氮偶合反应和后重氮偶合反应制备了主链和端基含有不同假芪型偶氮苯生色团的超支化偶氮聚合物.利用氢核磁共振、紫外光谱、红外光谱等分析手段确定了合成聚合物的结构、玻璃化转变温度和光谱特性等.研究了聚合物光致二向色性的性能,此聚合物的取向有序度为0.063.用两束相干的P偏振Ar+激光对聚合物膜进行光加工,得到形状规则的正弦波形表面起伏光栅,末端偶氮苯基团的引入极大地增加了超支化偶氮聚合物的光响应速度.     

Synthesis and characterization of water-soluble PEGylated lignin-based polymers by macromolecular azo coupling reaction

Water-soluble PEGylated lignin polymers were efficiently synthesized by macromolecular azo coupling reaction between alkali lignin and PEG based macromolecular diazonium salts in alkaline water.     

Systematic Investigation of the Effect of Polymerization Routes on the Gas‐Sorption Properties of Nanoporous Azobenzene Polymers

Functional‐group‐oriented polymerization strategies have contributed significantly to the initial development of porous polymers and have led to the utilization of several well‐known organic transformations in the synthesis of these polymers. Because there are multiple polymerization routes that can be used to introduce the same chemical functionality, it is very important to demonstrate the effect of different polymerization routes on the gas‐sorption properties of these chemically similar polymers. Herein, we have studied the rich chemistry of azobenzenes and synthesized four chemically similar nanoporous azobenzene polymers (NABs) with surface areas of up to 1021 m² g^?1. The polymerization routes have a significant impact on the pore‐size distributions of the NABs, which directly affects the temperature dependence of the CO₂/N₂ selectivity. A pore‐width maximum of 6–8 Å, narrow pore‐size distribution, and small particle size (20–30 nm) were very critical for high CO₂/N₂ selectivity and N₂ phobicity, which is associated with azo linkages and realized at warm temperatures. Our findings collectively suggest that an investigation of different polymerization routes for the same chemical functionalization is critical to understand fully the combined effect of textural properties, local environment, and chemical functionalization on the gas‐sorption properties of nanoporous polymers.     

含三氰乙烯基强吸电子基团的环氧树脂基非线性光学聚合物的合成

非线性光学聚合物材料及其在聚合物电光调制器中的应用是目前国内外研究的前沿。环氧树脂类聚合物具有很好的成膜性及可化学交联性能,是一类非常好的非线性光学聚合物的基体材料。本论文从分子设计的角度出发,将含三氰乙烯基强吸电子取代基及噻吩芳杂环共轭结构非线性光学生色团成功引入环氧树脂类聚合物,并在生色团侧基上引入甲基取代基。结果表明,苯胺残基中侧位甲基取代基对于先驱聚合物的亲电取代反应程度及最后聚合物的紫外-可见光最大吸收波长均有一定的影响,对于没有侧甲基的BP-TA-TC和一个侧甲基取代基的BP-3-TA-TC其官能化度均可以达到80%以上,而对于含两个甲基取代的BP-3,5-TA-TC先驱聚合物其官能化度则相对较低(低于10%)。随着甲基取代数目的增多,最后非线性光学聚合物的最大吸收波长也有不同程度的蓝移。     

Epoxy-based azo polymers with high chromophore density: Synthesis,characterization and photoinduced birefringence

Three epoxy-based azo polymers(PEP-AZ-Cl,PEP-AZ-CN and PEP-AZ-NT) with high chromophore density were synthesized by using post-polymerization azo-coupling reactions between epoxy-based precursor polymer(PEP-AN) and diazonium salts of 4-chloroaniline,4-aminobenzonitrile and 4-nitroaniline,respectively.The structures and properties of the azo polymers were characterized by using ~1H-NMR,FT-IR,UV-Vis and thermal analyses.The photoinduced birefringence of the azo polymers was studied by irradiating spin-coated films of the polymers with laser beam at three different wavelengths(488,532,and 589 nm).The results indicate that the photoinduced birefringence of the azo polymers is related with the electron-withdrawing group on azo chromophores and the excitation wavelength.The excitation wavelength that can cause the efficient responses is determined by the absorption band positions of the azo chromophores,which are mainly affected by the electron-withdrawing group on the chromophores.Therefore,the azo polymers containing chromophores with different electron-withdrawing groups show different responsive behavior to the irradiation light at different wavelengths.When irradiated with 488 nm light,PEP-AZ-Cl shows the shortest time to reach the saturated birefringence but with the lowest saturation birefringence level compared with the other two azo polymers.When irradiated with 532 nm light,PEP-AZ-CN shows the shortest time to reach the saturated birefringence.When irradiated with 532 and 589 nm light,PEP-AZ-NT shows the highest saturation birefringence level.     

Reactive Polymeric Dyes as Textile Auxiliaries

Commercial and synthetic azobenzene derivatives were used for the synthesis of hydrophilic polymeric dyes. Two strategies based respectively on the polymerization of dye methacrylic derivatives with different monomers and on the functionalization of reactive polymers were investigated. Polymers containing rather small amounts of the selected dyes were generally obtained, very likely because of the electron withdrawing effect of azo chromophores. Almost quantitative conversions were recorded in the reaction of commercial dyes with maleic anhydride/methyl vinyl ether alternating copolymers. Some of the prepared polymeric dyes were preliminarily tested as textile finishing agents.     

SYNTHESIS AND CHARACTERIZATION OF COMB-LIKE POLYMERS BEARING HETEROCYCLIC AZO GROUP AND MESOGENIC GROUP

The synthesis and characterization of a series of novel comb-like polymethacrylates bearingheterocyclic azo group and mesogenic group are described. The thermal properties of the polymers such asthermal stability and phase transition behavior were investigated by thermogravimetric analysis, differentialthermal analysis and polarizing optical microscopy techniques. The experimental results show that all thesynthesized polymers do not exhibit liquid crystallinity except the homopolymer of the mesogenic monomerMAPB2 and the glass transition temperatures of the polymers increase with increasing content of azo moietyin polymers linearly.