Polymeric Catalysts

The present-day position in the field of polymeric catalysts is outlined. The following selected groups of polymeric catalysts are discussed: synthetic hydrolases, immobilized enzymes, phase-transfer catalysts, nucleophilically active bases, polymers with conjugated π-systems, photosensitizers, polymers as carriers for catalytically active metals or ions, and immobilized homogeneous catalysts. Polymeric catalysts have the following valuable properties: insoluble polymeric catalysts are readily separable from reaction solutions and can often be re-used without loss of activity; a hydrophobic matrix protects the organometallic active center from deactivation by oxygen and water; by fixation of finely divided metals on an ion exchanger, multistage reactions may be effected successively in one reactor. Polymeric carriers may influence the catalytic properties; for example, in the case of immobilized enzymes on polyionic carriers the pH of the activity maximum may be shifted.     

Polymeric electrochromics

Conducting polymers are excellent candidates for applications in displays, mirrors, windows, light-emitting diodes, photovoltaics, near-infrared devices and electrochromic devices. From these potential applications, in this article, we will focus on the electrochromic polymers and devices. Although several objective studies have been conducted in the last decade, bringing to light many advantages over other types of electrochromics, polymeric electrochromics have not yet received the industrial attention that they deserve. One of the most important and dazzling advantages of polymers over the other types of electrochromics is the ease of modification of a polymer's backbone, that changes almost the entire properties of the material and switches many disadvantages into advantages. Our recent completion of the deficient third leg of additive primary colour space was a very good example of tailoring the polymer backbone. This discovery could be considered as one of the milestones of commercialization of polymeric electrochromics. In this article, we will also discuss the completion of the additive primary colours, red, green and blue (RGB), in polymeric electrochromics and their ways of commercialization.     

Polymeric Metallocarbenes

Three types of polymeric metallocarbenes were synthesized: heterocarbene, diarylcarbene, and alkylidene complexes. They were thermally more stable than their low molecular weight analogs. They exhibited ¹³C-NMR signals for the carbene carbons at very low magnetic field. They were characterized by typical metallocarbene reactions, such as nucleophilic substitution and oxidation, as well as cyclopropanation of unsaturated carboxylates. Thus, metallocarbenes, as an important category of organometallic compounds or intermediates, have gained entry to polymer chemistry.     

高分子固体电解质

本文叙述了高分子固体电解质的离子传导机理、特点及国内外近年来的研究进展和应用前景。     

高分子LB膜

概述了高分子Langmuir-Blogett膜,并依其成膜方式分别介绍了可聚合LB膜、聚合物的LB膜及其它几种LB膜。     

具有自修复能力的聚合物材料

各项性能已经达到工程材料指标要求的聚合物材料，在使用过程中不可避免地会产生裂纹，进而在使用过程中包藏着隐患，直至丧失使用价值。裂纹的早期修复，特别是自修复是一个现实而重要的问题。本文介绍了两类修复机制，即共价键与非共价键愈合，重点分析了近年来按共价键机理愈合、具有自修复能力的聚合物材料的研究成果、优缺点及发展前景。     

高分子效应

用许多杰出的实例,从高分子骨架的机械支架作用、邻基效应、协同效应、模板聚合等诸方面探论了高分子效应。     

Polymeric Electron Carriers

Polymers containing 1,4-dihydronicotinamide (P-NAH) alloxan (P-A), and viologen (P-V²⁺) moieties were synthesized and characterized. P-NAH reduced various organic substances such as lipoic acid, alloxan, and viologens and also immobilized quinone mediated by alloxan. P-A was reduced to the polymer-bearing alloxan radical and the dialuric acid structure without crosslinks by one- and two-electron reduction, respectively, and P-A also mediated the redox reaction occurring between aqueous and organic (water-immiscible) layers. P-V²⁺ was converted to the stable viologen radical reversibly by one-electron reduction. Electric potentials and currents on photo-reduction of P-V²⁺ and catalytic behavior of P-V²⁺ in the reduction of carbonyl compounds were examined.     

自修复高分子材料

高分子材料制造和使用过程中,经常由于内部的微裂纹和局部损伤,而导致性能下降,影响使用寿命。自修复高分子材料模仿生物体损伤愈合的原理,自行发现裂纹并通过一定机理自行愈合,是一种有着广泛应用需求的高分子智能材料,包括含修复剂型和不含修复剂型两类。它的特点在于自动化、精准化。本文旨在结合近年来最新的研究成果,介绍并归纳多种典型的自修复体系,总结各种优化手段,并针对已发展的自修复材料存在的局限性,对其研究前景进行合理的展望。     

Environment-Responsive Polymeric Hydrogels

Some polymers may respond by changing their physico-chemical perperties when the environmental conditions such as pH, temperature and ionic strength are varied. For example,thermosensentive polymers can exhibit a sharp change in solubility in a solvent such as water at a certain temperature known as the lower critical solution temperature (LCST). The responsiveness of the polymeric materials has important technological implications since they can be employed for various applications. The responsiveness of such polymers can be varied by means of copolymerization, chemical modification of the polymer, or the addition of reagents into the solutions. It is interesting and important to tune predictably the responsiveness of the polymers for the different applications. The sensitivity towards the external environment can be modulated by the relative hydrophilicity of the copolymers, hence the chemical structure and composition of the comonomers used.     

Polymeric membrane pervaporation

Pervaporation is an efficient membrane process for liquid separation. The past decades had witnessed substantial progress and exciting breakthroughs in both the fundamental and application aspect of pervaporation. This review provided an analytical overview on the potential of pervaporation for separating liquid mixtures in terms of the solubility parameter and the kinetic parameter of solvents. Focus of the review was given to the fundamental understanding of the membrane. Research progress, challenges and opportunities, and the prospect of pervaporation were also discussed. The thermodynamic approach of pervaporation, featuring emphasizing membrane/species interactions, though gained great successes in the past decades, is now facing its toughest challenge in the org–org separation. A kinetic era of pervaporation, featuring emphasizing diffusion selectivity, as well as the synergy between the selective diffusion and sorption, is in the making, and this approach will eventually find solutions to the challenging org–org separation.     

Thermoresponsive Polymeric Nanoemulsions

Summary: Solutions of poly(N‐isopropylacrylamide) (PNIPA) with added sodium dodecyl sulfate (SDS) were investigated by light scattering methods at temperatures of 15–40 °C. The formation of well‐defined nanoparticles of PNIPA was observed on heating at low SDS additions. The effects of PNIPA and SDS concentrations and the molecular weight of PNIPA on nanoparticle parameters were investigated. An interpretation based on stabilization of PNIPA nuclei by SDS was suggested.

The proposed mechanism of nanoparticle formation.     

聚合物发光材料

描述了聚合物的发光原理及发光器件构造,详细地介绍了聚合物发光二极管的发展历史及最新动态,着重于颜色的调谐、发光效率的提高等方面。     

Polymeric Janus Particles

Since de Gennes’ Nobel lecture in 1991, in which he coined the term “Janus grains”, research into asymmetric particles has boomed. Macroscopic, microscopic and nanoscopic particles have been prepared in which certain parts of their surface differ in chemical composition, polarity, color, or any other property. Spherical, cylindrical, disc‐like, snowman‐, hamburger‐, and raspberry‐like structures have been synthesized from organic or inorganic materials or even as hybrids of both. Synthetic strategies towards such particles vary greatly from simple polymer mixtures to the bulk self‐assembly of sophisticated terpolymers to immobilization methods of symmetric particles. Polymeric Janus particles are particularly promising, as they can often be prepared cheaply and sometimes even on larger scales.     

Polymeric Materials 2000

Russian Journal of Applied Chemistry -     

Polymeric coumarin derivatives

Summary Copolymers of vinylpyrrolidone with coumarin, umbelliferone, esculetin, osthole, ostholic acid, meranzin hydrate, isoimperatorin, oxypeucedanin hydrate, isooxypeucedanin, gosferol, pranchimgin, and marmesin have been synthesized and their structures have been studied.On the basis of a study of UV, IR, and NMR spectra, and also of chemical properties, it has been established that copolymerization takes place at the 3,4 double bond of the lactone ring and side chains do not participate in polymerization.In a pharmacological study of monomeric coumarins and their copolymers it was found that they all possess well-defined spasmolytic and hypotensive properties.Leningrad Sanitary-Hygienic Medical Institute. Institute of Macromolecular Compounds, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 714–720, November–December, 1974.     

刺激响应降解型聚合物水凝胶

作为一类重要的高分子材料,聚合物水凝胶由于其优良的理化性能和生物学特性而被广泛应用于生物医药领域,降解特性是其作为生物医用材料的重要性能指标。刺激响应降解型水凝胶是指在环境因素刺激下凝胶网络发生响应性断裂,进而产生凝胶-溶胶或溶胀-降解转变的一类智能高分子材料。这一响应降解特性可通过将环境敏感性断裂基团引入到聚合物凝胶网络中来实现。与水凝胶常规的水解、酶解相比,刺激响应降解因具有空间或时间上的可控特性而引起人们的广泛关注。本文重点介绍了pH响应、光响应以及氧化还原响应降解型聚合物水凝胶的设计方法、降解机理及其最新研究进展,并对刺激响应降解型水凝胶未来的研究方向进行了展望。     

温度响应性单分子聚合物胶束

单分子聚合物胶束和传统的胶束一样具有核-壳结构,因其结构固定并具有良好的热力学稳定性而越来越受到研究者的关注。当这类胶束的核层或者壳层含有温敏性高分子的时候就可以形成具有温度响应性的单分子聚合物胶束。近年来,人们在温敏性的单分子聚合物胶束的合成与性能研究方面做了大量的工作。本文概述了具有温度响应行为的单分子聚合物胶束的类型、制备方法以及应用等方面取得的新进展,同时结合本实验室的工作,总结了基于超支化大分子的温敏性单分子聚合物胶束的相转变行为研究,并对这类胶束体系的发展进行了展望。