水溶性聚合物和两亲聚合物:9.新型丙烯酰胺基两亲单体及其两亲聚合物的单层膜研究

本文对新型两亲单体,2-丙烯酰胺基十六烷磺酸(AMC_(16)S),及其两亲聚合物PAMC_(16)S在空气-水界面上形成单层膜的特点进行了研究。AMC_(16)S可通过在亚相中添加Ca~(2+)或Cd~(2+)等多价阳离子在界面上原位生成不溶性磺酸盐的方法获得满意的成膜行为。PAMC_(16)S不溶于水,可直接成膜。发现,PAMC_(16)S的成膜行为与亚相的性质明显相关。纯水亚相下PAMC_(16)S的极限单体链节面积较大,如亚相含有Ca~(2+)或Cd~(2+),极限面积明显缩小,说明烷基碳氢链的排列趋向紧密。     

水溶性聚合物和两亲聚合物:14.丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物

水溶液中用硫酸亚铁-异丙苯过氧化氢氧化还原引发体系合成了丙烯酰胺(AM)/2-丙烯酰胺基十六烷磺酸铵(AMC_(16)SNH_4)无规共聚物。用元素分析、IR、~(13)C-NMR和~1H-NMR对其进行了表征。对水溶液性质的研究结果表明,与部分水解聚丙烯酰胺相比,这种新型共聚物有着优异的耐盐性、耐温性和贮存稳定性。     

两亲聚合物胶束自组装包药研究进展

两亲聚合物胶束具有突出的理化性能和独特功能,能够在溶液中自组形成具有核壳结构的聚合物胶束,同时实现药物的负载。自组装包药技术能够缓解我国药物辅料缺乏的现状,符合目前药物辅料发展的新趋势。通过自组装形成的聚合物胶束在药物控释、药物靶向载体、药物制剂开发、新型药物辅料等方面具有广阔的应用前景。本文综述了两亲聚合物胶束自组装包载药物的原理以及方法,重点介绍了三类两亲聚合物在自组装包药方面的最新研究成果和发展趋势。本文还对载药胶束在药物释放方面的应用进行了概述。     

水溶性聚合物和两亲聚合物23.两亲聚合物PAMC16S对螺(噁)嗪化学和物理行为的影响

研究了两亲聚合物聚 (2 -丙烯酰胺基十六烷磺酸 ) (PAMC16S)存在下 1 -乙基 -3 ,3 -二甲基螺 [吲哚啉 -萘并口恶嗪 ](SO -E)在水溶液中的增溶作用及PAMC16S对SO -E化学和光化学性质的影响。PAMC16S明显增加了SO -E在水相的溶解性 ,SO -E的最大增溶浓度随PAMC16S浓度增加呈线性增加规律。在PAMC16S存在下 ,新配制的SO -E溶液显示可逆的光致变色性 ,显色体呈红色 ,最大吸收峰位于 5 2 0nm ,在室温下的消色反应速度明显慢于无PAMC16S存在下的兰色显色体。SO -E/PAMC16S溶液是不稳定的 ,配制后较长时间即失去SO -E的正常光致变色性质。盐酸具有与PAMC16S相似的作用 ,SO -E/PAMC16S体系的不稳定性可用氨水中和的方法解决。1H -NMR结果表明SO -E在酸性介质中发生了不可逆的化学反应。     

水溶性聚合物和两亲聚合物 16.聚苯乙烯/聚丙烯酰胺嵌段聚合物的合成和表征

采用聚偶氮酯引发剂,合成了聚苯乙烯/聚丙烯酰胺嵌段聚合物(PSt/PAM)。考察了含偶氮基聚苯乙烯预聚物(pre-PSt)在1,4-二氧六环中引发AM的聚合反应行为,讨论了影响第二单体转化率和聚苯乙烯均聚物含量的因素。用元素分析、溶解性、红外光谱、DSC、TG和裂解色谱表征了PSt/PAM嵌段聚合物。     

水溶性聚合物和两亲聚合物18．2－丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异。由于手性碳原子的存在，与其相邻亚甲基的质子峰在~１ＨＮＭＲ谱上清楚地发生分裂。研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化学性质。发现聚合速度和所得聚合物分子量均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１／４时，观察不到胶束化现象。     

水溶性聚合物和两亲聚合物：23.两亲聚合物PAMC16S对螺恶嗪？…

研究了两亲聚合物聚（２－丙烯酰胺基十六烷磺酸）（ＰＡＭＣ１６Ｓ）存在下１－乙基－２,３－二甲基螺［吲哚啉－萘并恶嗪］（ＳＯ－Ｅ）在水溶液中的增溶作用及ＰＡＭＣ１６Ｓ对ＳＯ－Ｅ化学和光化学性质的影响。ＰＡＭＣ１６Ｓ明显增加了ＳＯ－Ｅ在水相的溶解性,ＳＯ－Ｅ的最大增溶浓度随ＰＡＭＣ１６Ｓ浓度增加呈线性增加规律。在ＰＡＭＣ１６Ｓ存在下,新配制的ＳＯ－Ｅ溶液显示可逆的光致变色性,显色体呈红色,最大吸收峰位     

Preparation and self-assembly of amphiphilic polymer with aggregation-induced emission characteristics

An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.     

水溶性聚合物和两亲聚合物18.2—丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异，由于手性碳原子的存在，与其相邻亚甲基的质子峰在ＨＮＭＲ谱上清楚地发生分裂，研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化化学性质，发现聚合速度和所得聚合物分子量均均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１     

Synthesis and Characterization of Small Band-gap Conjugated Polymers - Poly(pyrrolyl methines)

A kind of small band-gap conjugated polymers-poly (pyrrolyl methines) and their precursors-(poly pyrrolyl methanes) have been synthesized by a simple method and characterized by 1HNMR, FT-IR, TGA and UV-Vis. These polymers can be dissolved in high polar solvents such as DMSO, DMF or NMP. The results reveals that the band-gap of the synthesized conjugated polymers are in the range of 0.96～1.14 eV and they all belong to the small band-gap polymers. The conductivity of doped products with iodine is in the range of semiconductor.     

Novel fluorescent amphiphilic poly(allylamine) and their supramacromolecular self‐assemblies in aqueous media

Fluorescent amphiphilic polymers were produced by grafting different types and levels of hydrophobic pendant groups with intrinsic fluorescent properties (fluorenylmethoxy carbonyl (Fmoc), dimethylamino‐1‐naphthalenesulfonyl (Dansyl), and naphthalene (Naphth) to a water soluble homopolymer backbone, polyallylamine (PAA). Non‐fluorescent hydrophobic pendant group (cholesteryl moieties) were also grafted onto PAA. The polymers were characterized with elemental analysis, NMR and FTIR spectroscopy. All polymers formed self‐assemblies by probe sonication in water with sizes ranging from 120 to 199 nm and TEM images showed the presence of spherical particles. The critical aggregation concentration (CAC) varied from 0.093 to 1.5 mg ml^?1 depending on the type of hydrophobic pendant groups. The Cholesteryl and Dansyl polymers showed the presence of one CAC while the Fmoc and Naphth grafted polymers revealed the presence of two CACs. The first CAC observed was possibly due to intermolecular aggregation while the second CAC at the higher polymer concentration was the result of excimer formation revealed by their fluorescent spectra. We reasoned that Naphth and Fmoc aromatic pendant groups possess a flat stereochemistry, thus allowing π–π stacking at higher concentrations. The presence of the N‐dimethylamino group in the Dansyl moiety gives rise to a 3D structure, thus hindering any stacking. The understanding of the supramolecular assemblies formed by these fluorescent amphiphilic polymers will aid in the engineering of advanced materials with superior functionality for biomedical applications. Copyright © 2011 John Wiley & Sons, Ltd.     

A novel route to poly(2-hydroxyethyl methacrylate) and its amphiphilic block copolymers

The vinyl of the ester group of 2-vinyloxyethyl methacrylate was first selectively reacted with acetic acid to obtain 2-[1-(acetoxy)ethoxy]ethyl methacrylate ( 2 ). This protected monomer was subjected to anionic polymerization in tetrahydrofuran at −60°C in the presence of LiCl, using 1,1-diphenylhexyllithium as initiator. The molecular weight of the polymer could thus be controlled and a narrow molecular weight distribution obtained. The protecting group, 1-(acetoxy)ethyl, could be easily eliminated (by quenching the polymerization reaction with methanol and water) to generate poly(2-hydroxyethyl methacrylate) (poly(HEMA)). Block copolymers were also prepared by the sequential anionic polymerization of MMA and 2 or styrene and 2 . They possess narrow molecular weight distributions, and controlled molecular weights and compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1865–1872, 1998     

Synthesis of anionic amphiphilic carbosilane block copolymer: Poly(1,1‐diethylsilacyclobutane‐block‐methacrylic acid)

An amphiphilic block copolymer of silacyclobutane and methacrylic acid (MAA) was synthesized via a living anionic polymerization of 1,1‐diethylsilacylcobutane (EtSB). Sequential addition of 1,1‐diphenylethylene and t‐butyl methacrylate (tBMA) to living poly(EtSB) in the presence of lithium chloride gave poly(EtSB‐block‐tBMA) with narrow molecular weight distributions. The t‐butyl ester groups in the obtained polymer were readily hydrolyzed via heating in 1,4‐dioxane in the presence of concentrated aqueous hydrochloric acid. The block copolymer with a short MAA segment was soluble in chloroform and insoluble in methanol and basic water, whereas the block copolymer with a long MAA segment was soluble in methanol and basic water and insoluble in chloroform. The block polymer (EtSB/tBMA = 45/60) formed a monolayer film on the water surface; this was confirmed by surface pressure measurement. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 86–92, 2001     

Synthesis and emulsion copolymerization of amphiphilic poly(2-oxazoline) macromonomer possessing a vinyl ester group

The present article describes the synthesis and emulsion copolymerization of a block-type amphiphilic poly(2-oxazoline) macromonomer possessing a polymerizable vinyl ester group. The macromonomer was synthesized by one-pot two-stage block copolymerization of 2-oxazolines using vinyl iodoacetate as initiator. 2-Methyl- and 2-n-butyl-2-oxazolines were employed for the construction of hydrophilic and hydrophobic segments, respectively. The surface activities evaluated by the surface tension of the macromonomer in water were fairly good. Emulsion copolymerization of vinyl acetate with the macromonomer was carried out. The macromonomer acted as a polymeric surfactant, as well as a comonomer. The resulting copolymer latex particles were spherical and their diameter was in the sub-micron range. The effects of the composition of the macromonomer on the emulsion copolymerization and the resulting latex particles were examined. © 1993 John Wiley & Sons, Inc.