Template—free electrosynthesis of aligned poly（p—phenylene） microtubules

Poly （p-phenylene)(PPP) microtubules with diameters of 0.2-0.8μm and lengths of -10μm have been synthesized by direct oxidation of benzene in the mixed electrolyte of boron trifluoride diethyl etherate(BFEE)and trifluoroacetic acid(TFA)(BFEE:TFA=2:1,by volume),containing a certain amount dodecylbenzene-sul-fonate(SDBS)as surfactant.The microtubules were grown vertically on the working electrode surface.The tubular morphology has been confirmed by scanning and transmission electron microscopies and the chain structure of the skin of the tubules has been characterized by Raman spectros-copy.The electrode property,monomer/surfactant molar ration and the value of applied potentical have strong effects on the morphology of the microtubules.     

Study on the behaviors of poly（p-phenylene benzobisoxazole） in coagulation

Poly（p-phenylene benzobisoxazole）（PBO） is a candidate of high performance materials for many applications. PBO materials＇ properties are considered to be closely related to their fabrication process, especially coagulation. In this paper, the coagulation effect on the chemical and microstructure of PBO was investigated with the help of a PBO model compound, 2, 2＇-（ 1,4-phenylene） bis （5-amino-6-benzoxazolole）. During coagulation, the hetero-cyclic ring of the PBO structure was experienced cleavage and even being broken down completely under some extreme conditions. Wide-angle X-ray diffraction （WAXD） analysis showed that different coagulants could cause the microstructure difference in PBO materials. In a slow coagulation process, PBO molecular chains aligned more orderly in the side-by-side direction （200）.     

Probing the microenvironment of an oligo-（p-phenylene vinylene） derivative encapsulated in polymer-impregnated sol-gel silica matrix

Polymer-impregnated silica sol-gel composite materials are hosts for organics in advanced optics application. An oligo-phenylene vinylene derivative 4,4‘-(1,4-phenylene dithenylene)-bis-(N-methyl pyridinium iodide) (OPVD) was introduced to poly(hydroxyethyl methacrylate) (PHEMA)-impregnated silica composite film by the sol-gel process. By comparing the X-ray diffraction, UV-visible spectra, steady-state and time-resolved fluorescence spectra of OPVD in three solid matrices (PHEMA/silica composite film, pure PHEMA film, and pure silica film), the similar results of PHEMA/silica composite film and pure PHEMA film demonstrate that the OPVD is primarily surrounded by a PHEMA-like environment in the composite matrix. The model of such structure is presented, which is useful for further understanding and optimizing of properties of doped sol-gel materials.     

荧光猝灭法研究5-甲基-2-苯基-4-（苯氨基-苯亚甲基）吡唑-3（2H）-酮与牛血清白蛋白的相互作用

应用荧光猝灭法研究了5-甲基-2-苯基-4-（苯氨基-苯亚甲基）吡唑-3（2H）-酮（P）与牛血清白蛋白间的结合作用.确定了P对牛血清白蛋白的荧光猝灭过程的猝灭机理,测定了不同温度下该结合反应的结合常数,结合位点数及热力学参数.     

HPLC法测定2-对氯苯基-4-苯基-1,5-苯并硫氮杂（艹卓）-α-(丁二酰亚胺基)-β-内酰胺

建立了测定2对氯苯基-4-苯基-1,5-苯并硫氮杂 -α-(丁二酰亚胺基)-β-内酰胺的高效液相色谱(HPLC)分析法.结果表明该法重现性好,灵敏度高,快速,准确,平均回收率为96.9%～103%.     

HPLC法测定2—对氯苯基—4—苯基—1，5—苯并硫氮杂Zhuo—α—（丁二酰亚胺基）—β—内酰胺

建立了测定2－对氯苯基－4－苯基－1，5－苯并硫氮杂Zhuo－α-（丁二酰亚胺基）－β－内酰胺的高效液相色谱（HPLC）分析法。结果表明该法重现性好，灵敏度高，快速，准确，平均回收率为96.95-103%。     

一种聚对亚苯基亚乙烯基类交替型发光共聚物的合成与性能

采用Wittig反应合成了一种分子主链由烷氧基取代的1,4二苯乙烯基苯(聚对亚苯基亚乙烯基(PPV)的三个单元的齐聚物)与柔性隔离链段五缩六乙二醇组成的交替型蓝绿色发光共聚物(DMDSB-SEO)。相对于苯环的2,5-位上没有甲氧基的聚合物DSB-SEO来说,DMDSB-SEO结构中甲氧基的引入,显著提高了聚合物的光量子效率,调整了其电子结构和光物理性能,同时大大改善了聚合物的溶解性和成膜加工性。该聚合物可溶于氯仿、四氢呋喃等有机溶剂,具有优良的溶解性和成膜加工性能。文中应用原子力显微镜(AFM)和相差显微镜等手段,研究了聚合物的相态结构以及聚合物对锂盐的溶解能力,并对此类材料的合理结构设计进行了讨论。     

聚2,3,5,6-四甲氧基对苯乙炔的合成新方法

报道了以1，2，4，5—四甲氧基苯和1，2—二溴乙烷为单体，经过A1C13催化的烷基化聚合反应和四氯苯醌脱氢反应，合成聚2，3，5，6—四甲氧基对苯乙炔(PTMPV)的方法；考察了催化剂用量、烷基化反应时间、溶剂等因素对聚2，3，5，6—四甲氧基对苯乙烯(PTMPE)收率及分子量的影响。实验研究结果表明四氯苯醌脱氢反应是PTMPE脱氢合成PTMPV的适宜方法。采用IR和^1H—NMR等分析方法对PTMPV的结构进行了表征，结果表明PTMPV具有链状π—共轭结构特征。     

含四官能团单元的超支化聚苯撑乙烯的合成、表征及光物理性质

通过Gilch反应合成了结构新颖、含四官能团单元的超支化PPV聚合物P1～P3.聚合物的结构得到1H NMR和元素分析结果的确证.通过热重分析(TGA)得知,该类非结晶相的聚合物热分解温度较高,分别为371.7、386.6和391.8℃.所合成的聚合物固态时的紫外吸收及荧光发射相对于液态的紫外吸收及荧光发射,波长有明显的红移现象,并且该聚合物具有宽吸收、窄发射的特征,在电玫发光器件和聚合物太阳能电池器件中将有潜在的应用前景.     

新型荧光超支化聚苯醚的合成与性能研究

以9-蒽甲醇为改性单体,通过与末端为酚羟基的超支化聚苯醚发生Mitsunobu反应,制得了末端含蒽生色团的新型荧光超支化聚合物。热重分析（TGA）表明该聚合物具有良好的热稳定性,氮气和氧气环境下5%的热失重温度均约为257℃。在DMF溶液中,该聚合物的吸收光谱和发射光谱均表现出蒽单元的光谱特性,其最大吸收和发射波长分别为389nm和443nm。研究还发现,所得荧光超支化聚苯醚在激发－发射过程中发生了分子内能量迁移或转移,表现出了典型的主客体发射体系的特性。该聚合物薄膜的最大吸收和发射波长分别是393nm和450nm。     

各种烷氧基取代聚对苯乙炔的合成和表征

利用脱氯化氢的方法合成了聚(2-甲氧基-5-己氧基)对苯乙炔(PMOHOPV)、聚(2-甲氧基-5-辛氧基)对苯乙炔(PMOCOPV)、聚(2,5-二丁氧基)对苯乙炔(PDBOPV)、聚(2,5-二己氧基)对苯乙炔(PDHOPV)、聚(2,5-二辛氧基)对苯乙炔(PDCOPV)等5种聚合物发光材料.通过核磁和红外表征了它们的结构.通过热失重曲线考察了它们的热稳定性.并从温度、催化剂、反应时间、烷氧基取代等方面考察了对聚合物溶解性、分子量、发光性能等的影响.发现可以通过催化剂的用量来改变聚合物分子量,聚合物的分子量与聚合物的溶解性成正比.     

1,4—双氯甲基—2—甲氧基—5—烷氧基苯的合成

以对甲氧基苯酚为起始原料,以甲醛,多聚甲醛和浓盐酸为双氯甲基化试剂,合成了一系列的１,４－双氯甲基－２－甲氧基－５－烷氧基苯,产率较高,产品的结构由ＩＲ和＾１ＨＮＭＲ得到确认。     

N,N-二异丙基-3-(2-甲氧基-5-甲基苯基)-苯丙酰胺的还原

采用具有强活性的复合还原剂实现了叔酰胺的还原。讨论了不同的络合试剂，还原试剂，络合时间和反应温度对叔酰胺还原的影响，确定了三氯氧磷/锌粉还原法及还原N，N-异丙基-3-（2-四氧基-5-甲基苯基）-苯丙酰胺（1）的工艺路线，得到新药托特罗定的重要中间体N，N-二异丙基-3-（2-甲氧基-5-甲基苯基）-苯丙胺（2），收率为86%。     

A novel water-soluble anionic conjugated copolymer containing poly（p-phenylene vinylene） segments： Copolymer synthesis and multilayer construction by assembling poly（diallyl dimethyl ammonium chloride）

This paper reports the synthesis of a water soluble conjugated polymer poly（p-phenylene vinyleneco-sodium methacrylate） （ws-P（PV-co-SMA）） and the multilayer of the derived copolymer assembling poly（diallyl dimethyl ammanium chloride） （PDDA）. The self-assembling process of the multilayer was monitored by UV-vis absorption spectroscopy, and the data indicated a linear increase in film thickness with a number of ws-P（PV-co-SMA）/PDDA bilayers. The alternative deposition of ws-P （PV-co-SMA） and PDDA allowed the insertion of a non-conjugated layer between the conjugated layers, thus the migration of the photogenerated polarons was effectively confined in the isolated ws-P （PV-co-SMA） chains. Consequently, the photoluminescence quantum yield reached 0.68, 30 times higher than that of pure poly（p-phenylen vinylene）. The distinct electronic interactions between conjugated segments were confirmed by comparative analyses of the excitation spectra and time-resolved photoluminescence spectra of ws-P（PV-co-SMA） solid film and the assembled multilayers. The confinement effect of the PDDA layer on the photogenerated carriers was verified by the surface photovoltage spectroscopic measurement on both ws-P（PV-co-SMA） solid film and self-assembled multilayers.     

新法合成1,1-二氯-2-甲氧基-2-(5-羧甲氧呋喃-2)乙烯

提出了一种有效的、新的合成1.1-二氯-2-甲氧基-2-(5-羧甲氧呋喃-2)乙烯的方法.     

紫外光辐照对聚苯硫醚/纳米氧化钛复合材料的影响

采用FTIR、DSC、DMA对不同紫外光辐照时间的聚苯硫醚/纳米氧化钛复合材料的性能进行研究。随着纳米氧化钛含量的增加,材料的结晶度和贮能模量增加。纳米氧化钛的加入抑制了因紫外光引发造成的聚苯硫醚分子链的降解。紫外光辐照后,聚苯硫醚/6%纳米氧化钛复合材料的结晶度明显降低。