N－甲基丙烯酰－N＇－嘧啶哌嗪与过硫酸钾引发体系引发的丙烯酰胺聚合

queous solution polymerization of acrylamide (AAm) was demonstrated by using initiation system consisting of N-methacryloyl-N '-pyrimidinopiperazine (MPMP ) and persulfate (KPS). The polymerization rate equation was obtained to beR_p = K_p[MPMP]^1/2 [KPS]^1/2 [AAm]^1.0The overall activation energy for the polymerization was calculated by Arrhenius quation to be Ea= 5.6 KJ/mol. The redox nature for the polymerization was clarified. A super high molecular weight up to 10⁷ of PAAm was obtained by using this initiation system. From the fluorescent analysis, it was confirmed that MPMP not only acted as a component of the redox system, but also entered into the acrylamide polymer chains.     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物的荧光光谱研究

我们曾报道过N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合、荧光性质及其单独或与过氧化物构成氧化还原体系以引发烯类单体聚合的研究。由于APP是分子中含有给电子生色基团和缺电子双键的丙烯酸类衍生物,其荧光表现有结构自猝灭现象并且聚合物的荧光也能被其它缺电子烯类单体如丙烯腈所淬灭。对于分子中含有多个氮原子的芳杂环叔胺丙烯酸类单体的研究,文献报道较少。本文合成了新的功能性单体N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP),并观察了单体及其聚合物溶液的荧光光谱。     

含生色基团烯类单体及其聚合物——N－丙烯酰基吩■嗪及其聚合物的合成和其荧光性质

含生色基团烯类单体及其聚合物——Ｎ－丙烯酰基吩嗪及其聚合物的合成和其荧光性质＊于淑艳姚光庆李福绵（北京大学化学系北京１００８７１）关键词Ｎ－丙烯酰基吩嗪,紫外－可见光谱,荧光光谱,“结构自猝灭”效应,Ｓｔｅｒｎ－Ｖｏｌｍｅｒ常数,荧光寿命我们曾报...     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

The photopolymerization of acrylonitrile (AN) sensitized by N-methacrylyl-N'-pyrimidi-nopiperazine (MPMP) and its polymer, P(MPMP) was studied kinetically. It was found that the photopolymerization rate of AN sensitized by monomeric MPMP is proportional to 0.35th power of MPMP concentration and 0.85th power of AN concentration, respectively. In the case sensitized by Polymeric MPMP, P(MPMP) is proportional to 0.30th power of P(MP-MP) concentration and 1.0 power of AN concentration, respectively. The overall activation energies for photopolymerization sensitized with MPMP and P(MPMP) were determined to be 4.71Kcal/mol and 4.58Kcal/mol,respectively.From the fluorescence analysis for P(AN) senstitized by either MPMP or P(MPMP),it was confirmed that MPMP and P(MPMP) not only sensitized the photopolymerization of AN but also entered into the P(AN) chains.     

聚N-甲基-N-(2-甲基丙烯酰氧乙基)-对-甲苯胺的荧光光谱及光诱导接枝丙烯腈共聚合

文献[1]报道N-甲基-N-(2-甲基丙烯酰氧乙基)苯胺(MEMA)单体,由于同一分子中含有缺电子碳碳双键和给电子发色基团(芳叔胺氮上孤对电子),因此当链节克分子浓度相等时,单体的荧光强度要比其均聚物的荧光强度低得多,归之为单体“结构自猝灭”所致。这是由于共存在单体分子中的吸电子双键基团和给电子的荧光基团在光照下于分子内或分子间产生激基复合物所致。这种现象称为“结构自猝灭现象”。聚合物无双键存在,因而其荧光强度比单体高得多。     

3-甲基丙烯酰胺基-9-乙基咔唑的合成、聚合及其光化学行为研究

含供电子芳杂环的丙烯酰类功能性单体的合成、聚合及光化学行为一直吸引着人们的兴趣 .原因之一是由于这类单体可用一般的自由基引发剂引发聚合 ,其聚合物表现出包括荧光及光引发行为的光化学性质甚被瞩目[1,2 ] .在以往的工作中发现 ,这类给电子性生色团的丙烯酰类单体在相同生色团浓度下的荧光强度明显低于其聚合物或饱和模型化合物 ,即表现出荧光结构自猝灭效应(ＳＳＱＥ) [3～ 5] .咔唑是一个强给电子性芳香杂环化合物 .虽然文献中已有关于含咔唑生色团的丙烯酰类单体报道 ,但很少涉及其荧光或光敏性质 .近来 ,我们合成了多个含有咔唑生…     

Photoinduced controlled/living free‐radical polymerization of 4‐methacryloyl‐1,2,2,6,6‐pentamethyl‐piperidenyl

The photoinduced solution polymerization of 4‐methacryloyl‐1,2,2,6,6‐pentamethyl‐piperidinyl (MPMP), used as a reactive hindered amine piperidinol derivative, was performed. The obtained MPMP homopolymer had a very narrow molecular weight distribution (1.06–1.39) according to gel permeation chromatography. The number‐average and weight‐average molecular weights increased linearly with the monomer conversion, this being characteristic of controlled/living free‐radical polymerizations. Electron spin resonance signals were detected in the MPMP homopolymer and in a polymer mixture solution, and they were assigned to nitroxide radicals, which were bound to the polymer chains and persisted at a level of 10^?9 mol/L during the polymerization. Instead of the addition of mediated nitroxide radicals such as 2,2,6,6‐tetramethyl‐piperidinyl‐1‐oxy (TEMPO), those radicals (>N? O ·) were formed in situ during the photopolymerization of MPMP, and so the reaction mechanism was understood as being similar to that of TEMPO‐mediated controlled/living free‐radical polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2659–2665, 2004     

Synthesis and Characterization of a Water‐Soluble Carboxylated Polyfluorene and Its Fluorescence Quenching by Cationic Quenchers and Proteins

We have developed a new intermediate monomer, 2,7‐[bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)‐9,9‐bis(3‐(tert‐butyl propanoate))]fluorene, that allows the easy synthesis of water‐soluble carboxylated polyfluorenes. As an example, poly[9,9′‐bis(3′′‐propanoate)fluoren‐2,7‐yl] sodium salt was synthesized by the Suzuki coupling reaction, and the properties of the polymer were studied in aqueous solutions of different pH. Fluorescence quenching of the polymer by different cationic quenchers (MV²⁺, MV⁴⁺, and NO₂MV²⁺; MV=methyl viologen) was studied, and the quenching constants were found to be dependent on the charge and electron affinity of the quencher molecule and the pH of the medium. The largest quenching constant was observed to be 1.39×10⁸ M ^?1 for NO₂MV²⁺ at pH 7. The change in polymer fluorescence upon interaction with different proteins was also studied. Strong fluorescence quenching of the polymer was observed in the presence of cytochrome c, whereas weak quenching was observed in the presence of myoglobin and bovine serum albumin. Lysozyme quenched the polymer emission at low protein concentrations, and the quenching became saturated at high protein concentrations. Under similar experimental conditions, the polymer showed improved quenching efficiencies toward cationic quenchers and a more selective response to proteins relative to other carboxylated conjugated polymers.     

硝基苯衍生物结构与其淬灭聚(2,5-二戊氧基对亚苯基亚乙炔基)荧光效率的关系

聚对亚苯基亚乙炔基(polyphenyleneethynylenes,PPEs)、聚噻吩(PTs)等作为具有共轭结构的电荷给体,在与含硝基、氰基等电荷受体发生电荷转移络合作用时,其荧光强度会随电荷受体结构的不同而产生不同程度的淬灭,而且响应灵敏度明显高于一般荧光小分子化合物[1~4].这是因为荧光小