含萘酰亚胺生色团的单体及其均聚物荧光性能

以1,8-萘酰亚胺为原料,合成了两种含萘酰亚胺官能团的乙烯基单体（NAPa和NAPb）。通过核磁、元素分析、紫外吸收光谱等对化合物结构进行了表征。并以这两种化合物为单体,通过原子转移自由基聚合（ATRP）的方法合成了它们均聚物,用1H-NMR ,GPC等对均聚物的结构进行了表征。研究了单体及其聚合物在不同浓度、不同溶剂以及在聚合物薄膜中的激发和发射荧光光谱,考察了聚合物浓度、溶剂极性等对荧光的影响。结果表明,单体和均聚物都具有较强的绿色荧光, 均聚物的荧光量子效率(φPNAPa=0.34, φPNAPb=0.35)高于单体的荧光量子效率(φNAPa=0.25, φNAPb=0.27)。     

一种水溶性荧光示踪共聚物(AM-AMCO)的合成及性能研究

本文采用乳液聚合方法,以丙烯酰胺和7-烯丙基氧-4-甲基香豆素作为单体,过硫酸铵-亚硫酸氢钠为氧化还原引发剂,合成了一种水溶性荧光示踪二元聚合物。考察了温度、单体浓度、体系pH和引发剂浓度等条件对聚合物表观粘度的影响,确定了最佳合成条件,并对聚合物结构进行了红外表征。紫外、荧光及耐温抗盐性研究结果表明了该二元聚合物可作为潜在的油田示踪剂,并具有良好的耐温抗盐性能。     

可逆加成—断裂链转移自由基聚合在制备水溶性聚合物中的应用

水溶性聚合物在工业、农业、医药等领域都有着广泛用途,但随着近年对水溶性聚合物精细化的要求,寻找新的结构可控的聚合方法已成为迫切需求.由于可逆加成-断裂链转移(RAFT)自由基聚合具有适用单体范围广、反应条件温和、不受聚合方法的限制等优点,以及可控制聚合物的嵌段、接枝、梳型、星型、无规及梯度等结构,成为合成结构可控的水溶性聚合物的最有效手段之一.本文主要讨论了单体、引发剂、链转移剂、溶剂等组成对RAFT聚合反应的影响,并介绍了利用RAFT方法制备非离子、阴离子、阳离子及两性离子水溶性聚合物的实例.     

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…     

氨基氮杂环荧光分子改性苯乙烯马来酸酐共聚物的研究

荧光高分子材料 ,由于其独特光学性质 ,成为功能高分子研究热点[1～ 3 ] .一般而言 ,荧光聚合物的合成有两种方法 ,一是首先合成荧光单体 ,然后与其他适宜单体聚合 ,得到荧光聚合物 ,然而荧光单体结构复杂 ,提纯困难 ,难以获得高分子量、成膜性能好的聚合物[4] ;另一种方法是通过官能团的反应 ,用荧光物质对聚合物进行化学改性来制备[5,6] .苯乙烯 马来酸酐共聚物 (ＳＭＡ)是一类成本低廉 ,性能良好的商品化聚合物材料 ,主链中含有具有反应性能的酸酐基团 ,这就使通过化学改性制备荧光聚合物成为可能 .本文通过 2 氨基苯并咪唑 ( 1 ) ,4 …     

水溶性β-环糊精交联聚合物与分析试剂客体包结反应的研究

以环氧氯丙烷为交联剂, 合成了一种水溶性β-环糊精(β-CD)交联聚合物。与β-CD单体不同, 此种聚合物在与有机分子客体发生包结反应时, 聚合物中的β-CD单元具有协同作用。本文详细地研究了聚合物与一系列含有双客体的有机试剂的包结反应, 发现它在化合物的增溶以及分子吸收和荧光光谱的增强方面比β-CD单体具有更好的效果与功能。为超分子配合物在分析化学中的应用开拓了新的前景。     

水溶性含糖共轭聚合物的制备及应用

水溶性共轭聚合物具有优异的光学稳定性、高亮度、易于修饰和水溶性等特点,广泛应用于离子检测、蛋白检测和生物成像等领域。水溶性共轭聚合物主要通过在共轭聚合物的侧基或端基修饰水溶性的离子基团或水溶性聚合物实现其水溶性,水溶性共轭聚合物还可以通过引入功能性基团或聚合物使其具备不同的功能特性。糖化合物是天然存在的一类生物分子且大部分具有水溶性的特点,因此最近十几年来科研工作者将糖化合物引入共轭聚合物中以赋予共轭聚合物糖化合物的生物功能特性。本文总结了水溶性含糖共轭聚合物的制备方法、化学结构及其在凝集素、细菌检测和细胞荧光成像中的应用。最后总结了此类聚合物的特性、发展方向及目前所需解决的问题。     

原子转移自由基聚合(ATRP)在星形聚合物合成中的应用

综述了近10 年来采用原子转移自由基聚合(ATRP) 法合成星形聚合物的研究进展。从聚合单体、引发剂、聚合方法和反应条件以及聚合物性质等方面讨论了原子转移自由基聚合在星形聚合物合成中的应用,并根据聚合方法和引发剂对各种反应进行了分类。对原子转移自由基聚合技术在合成功能性复杂星形聚合物中的应用进行了展望。     

聚合物在荧光检测领域的应用

聚合物是由一种或几种重复单体以共价键连接形成的大分子化合物, 它不仅能够保持单体的性质, 而且由于聚合后单体间的协同作用, 使其表现出独特的性能. 聚合物作为基础材料在荧光检测领域得到广泛应用. 聚合物通过氢键作用、 亲疏水作用及范德华力等分子间相互作用, 实现了对特定目标物的选择性识别; 通过信号转换和放大功能, 可以将分子识别作用转化为荧光信号; 可以作为骨架连接多个识别单元, 通过多价结合作用等提高识别目标物的能力, 或连接不同的功能单元, 构建多功能的分子器件. 本文对聚合物在荧光检测领域的应用进行了概述.     

原子转移自由基聚合在制备水溶性聚合物中的应用

水溶性聚合物在工业、农业、医药等领域都有着广泛用途,但随着对水溶性聚合物精细化的要求,寻找新的结构可控的合成方法已成为迫切需求.而利用原子转移自由基聚合(ATRP)则可能得到分子量可控、分子量分布窄的水溶性聚合物.本文主要讨论了利用ATRP合成水溶性聚合物过程中单体、引发剂、催化剂、溶剂、反应温度和时间的影响,并结合聚丙烯酸类、聚丙烯酰胺类以及聚苯乙烯和聚丙烯酸酯的衍生物等具体实例加以了分析.     

共轭聚合物离子荧光化学传感器

荧光传感器能够将分子识别的信息转换成荧光信号,荧光法在灵敏度、选择性和实时原位检测等方面优势突出,最近已引起了人们很大的兴趣。本文主要介绍以共轭聚合物为基础的离子荧光化学传感器的近期研究进展,重点综述了共轭聚合物的荧光化学传感器在阳离子识别检测中的分子设计、合成、作用机理和应用,并展望了该领域的发展方向。     

Recent advances in synthetic methods and applications of photo-luminescent molecularly imprinted polymers

Molecularly imprinted polymers with photo-luminescent properties (PLMIPs) and PLMIPs-based hybrids have been widely studied in recent years because of their integrated merits from molecular imprinting technologies and PL properties. PLMIPs have superior capabilities for signal transducer and molecular recognition, exhibiting great potential as the constructing platforms for promising applications. During the past decade, numerous researches have mentioned PLMIPs. In terms of unique merits and important applications of PLMIPs, a timely, comprehensive and in-depth review on PLMIPs is significant and is still lacking currently. This review systematically summarizes recent advances of PLMIPs, focusing on different synthetic methods and applications. Based on different components and structures, PLMIPs include different categories. Synthetic methods majorly involve encapsulation polymerization of nanomaterials (fluorophores) into MIPs, copolymerization of fluorescent monomers, electro-polymerization, photo-polymerization, etc. Various engineering structures and luminescence properties of PLMIPs are highlighted Potential applications of PLMIPs mention significant research fields, including chemo/bio-detection, bio-imaging, functionalized separation materials, versatile sensing materials, optical devices, etc. We also discuss present status, probable challenges and future perspectives of PLMIPs. This review is desirable for scientists from broad research fields and can promote further development of MIPs-based functional materials, luminescent hybrid materials and other advanced optical materials.     

基于巯基点击反应与RAFT聚合的功能性聚合物合成

可逆加成-裂解链转移聚合(RAFT)由于单体适用面广、聚合条件温和、不受聚合方法的限制等特性, 已经成为活性合成聚合物的有效手段之一。点击化学(click chemistry)由于具有良好的选择性、模块性以及官能团耐受性等特点迅速成为许多研究领域,如药物、聚合物、功能材料等合成的有力工具,同时涌现出了多种基于巯基的点击反应。本文综述了近年来基于巯基的点击反应, 如巯基-烯、巯基-炔、巯基-异氰酸酯、巯基-环氧化物以及巯基-卤代烃等新型点击反应与RAFT聚合相结合在功能性聚合物的制备和修饰中的应用, 相信这两种手段的结合将在其中发挥积极的作用。     

表面引发聚合反应研究进展

表面引发聚合反应作为一种新的聚合反应可广泛应用于固体基底的表面修饰与改性。结合分子自组装技术,几乎各种类型的聚合反应都有可能在固体基底表面进行。本文对表面引发聚合反应的研究进展进行了综述,对反应类型、实验方法、研究动向以及在合成聚合物刷、形成图案化聚合物薄膜等方面的应用与发展前景作了介绍与讨论。     

My life with polymer science

This article describes the scientific investigations and accomplishments in the life of the author. After a dissertation on steroids, several years were spent on alkaloids and research on heterocyclic compounds. Much of the author's career was devoted to research on aldehyde polymerization, the discovery of the polymerization of higher aldehydes and their isotactic polymers, and haloaldehyde polymerization. The latter led to our work on the ceiling temperature of polymerization, on new polymerization techniques [involving the ceiling temperature and the concept of macromolecular asymmetry (polymer helicity)], and the genesis of chloral polymerization. Another important period was devoted to functional polymers, polymeric stabilizers, and polymeric drugs. Other research activities included studies of unusual polymers, head-to-head polymers, spacer groups in polymers, and oriental lacquers. Attention was also paid to the use of novel and unusual polymer intermediates, polymerization under extreme conditions and the preparation and behavior of uncommon polymer structures. Finally, it was recognized that macromolecules can be categorized with increasing frequency as polymers with broad and narrow molecular weight distributions and uniform polymers. The ultimate unity is isotopically pure uniform polymers, single macromolecular species. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 795–818, 2004     

“活性”/可控自由基聚合反应制备聚合物-蛋白质/多肽生物结合物

将蛋白质或多肽连接到高分子链上,能够改善蛋白质/多肽的稳定性、生物相溶性和溶解性而赋予其优异的应用性能,所得聚合物-蛋白质/多肽生物结合物已经被广泛应用于药物载体、生物材料、纳米材料等领域。本文介绍借助"活性"/可控自由基聚合反应制备新型功能高分子材料的原理与方法,以及其合成聚合物-蛋白质/多肽生物结合物的国内外研究进展。     

Controlled electropolymerization based on self-dimerizations of monomers

Electropolymerization is one of the most important methodologies to synthesize and develop conducting polymers. The complexity of the polymerization mechanism, ion doping processes and structural defects are considered to be symbiotic and unavoidable, making the stagnant state and huge band gap with advanced interdisciplinary research fields and important applications in the last three decades. Herein, we provide a point of view into controlled electropolymerization by regioselective activation reactions of monomers, where self-dimerizations instead of self-electropolymerizations were utilized. The resulting dimers play a role in the connections between functional building blocks to form functional polymers on demand. This account highlights the typical findings in controlled electropolymerizations as a forum for discussing new opportunities in exploiting novel designs and applications.     

Molecular-Integrated Phospholipid Polymer Nanoparticles with Highly Biofunctionality

Surface modifications of nanoparticles with phospholipid polymers composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), are summarized. The MPC can be available for various polymerization methods such as conventional radical polymerization and living radical polymerization, and easily copolymerized with other vinyl compounds. The MPC polymers have been widely used as biocompatible coating and stabilizer for nanoparticles even when they are under biological environment. Additionally, for immobilization of biomolecules, such as antibody and enzyme, the MPC polymers having active ester group are applicable. These MPC polymers coated on the nanoparticles immobilize protein under mild condition and the protein maintained bioactivity well. Moreover, introduction of functional inorganic nanocrystals inside of the nanoparticles is effective to obtain good imaging tool for specific cells. The potential of molecular integration on nanoparticles based on MPC polymer chemistry will be expanded nanobiosensing, nanoimaging and nanodiagnostic system.     

Vapor phase oxidative synthesis of conjugated polymers and applications

Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low‐cost electronic and optoelectronic devices, they are often difficult to process by wet‐chemical methods due to their very low to poor solubility in organic solvents. The use of vapor‐based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012