“活性”/可控自由基聚合制备两性离子聚合物及其应用

两性离子聚合物是在高分子链段上包含丰富等量阴离子基团与阳离子基团的聚合物,因具备优异的亲水性、生物相容性等独特的性质,近年来在抗污染、生物医药等领域展示了极广阔的应用前景。按照其结构特征,可以大体被分为混合电荷型与甜菜碱型两性离子聚合物。目前两性离子聚合物的制备方法多种多样,从实际应用的角度出发,使用"活性"/可控自由基聚合制备两性离子聚合物具有独特的优势,如分子量可控、易于制备复杂结构聚合物等,这些特性拓宽了两性离子聚合物的应用领域。本文沿"单体直接聚合"和"聚合物后修饰"两条路径,介绍了使用"活性"/可控自由基聚合制备两性离子聚合物的优势及进展,同时从抗污染材料、生物医药材料、物质检测与分离等方面概述了两性离子聚合物的主要应用,并对其未来发展作出展望。     

两性离子聚合物的生物应用

两性离子聚合物具有亲水的阴、阳离子基团,能够高度水化从而具有独特的抗生物污染性能,即能够阻抗非特异性蛋白质的吸附、细菌黏附和生物膜的形成,这种特性使得此类材料在生物医学等相关领域得到越来越多的应用。本文概略介绍了现有两性离子聚合物的抗生物污染机理——空间排斥效应和水化理论。基于抗生物污染性质,两性离子聚合物可用于防污涂层、抗菌涂层、抗凝血材料、生物医学诊断、药物传输、基因传递载体、分离膜以及船体涂料中。本文综述了两性离子聚合物的应用进展,分析了当前研究中需要解决的问题以及发展趋势,并展望了其应用前景。     

两性离子基团改性分离膜的抗污染机理及研究进展

抗污染机理的研究对设计和合成抗污染膜材料具有指导意义。两性离子聚合物作为一种新型的抗污染膜材料逐渐受到人们的关注。本文从研究膜污染的成因及其影响因素出发,阐述了分离膜的抗污染机理及两性离子基团改性分离膜的抗污染特点,同时根据两性离子基团改性分离膜方式的不同,系统总结了近年来此类分离膜的研究进展,并对分离膜抗污染机理的研究和两性离子改性高分子分离膜未来的发展趋势作出展望。     

两性离子聚合物的合成及应用

两性离子聚合物因独特的链结构,使其具有卓越的化学性能、良好的热稳定性与水化性能,尤其是具有"反聚电解质效应溶液行为"这一特点,近年来引起了广泛关注。因大多数两性离子聚合物链内引入了—OH,—COOH,—SO3H等亲水基团,使其具有抗蛋白质污染、抗细菌黏附及抗凝血等性能。迄今为止,人们已合成了很多新型的、功能化的两性离子聚合物并将其应用于石油工业、生物医用材料、药物合成和污水处理等各个领域。本文主要对两性离子聚合物的结构、性质、合成方法、应用、最新研究成果及发展前景等作了简单的概述和分析,并对它的合成方法和应用作了主要介绍,以期对两性离子聚合物的研究和发展有所借鉴。     

甲基丙烯酰乙基磺基甜菜碱类聚合物的生物应用

两性离子聚合物具有阴阳离子基团,能够高度水化,具有优异的生物相容性。甲基丙烯酰乙基磺基甜菜碱(SBMA)聚合物因其独特的两性离子链结构,具有抗蛋白质污染、抗细菌黏附及抗凝血等抗生物污染性能,这种特性使其在生物医学等相关领域得到越来越多的应用。本文介绍了其抗生物污染的水化理论,对甲基丙烯酰乙基磺基甜菜碱类聚合物的结构、性质、合成方法及表面构建方法等作了概述和分析,对其在人造器官材料、组织工程、生物分离、生物监测、温度敏感材料等方面的应用作了重点介绍,并分析了目前应用存在的问题和潜在的应用前景。     

两性离子聚合物的研究进展

两性离子聚合物是一类整体呈电中性,在同一单体侧链上同时含有阴、阳离子基团的高分子材料。因其水化能力强、生物相容性好等特点,在生物医药等领域得到了广泛研究和应用。本综述首先对两性离子聚合物的性质、分类、合成等方面进行了简单的概述;然后针对两性离子聚合物在防污涂层、蛋白质改性、药物递送、膜分离材料等4个方面的应用介绍其研究进展;最后对两性离子聚合物未来的发展进行了简单的评述和展望。     

羧基甜菜碱型两性离子聚氨酯水凝胶的制备及水下抗原油黏附性能

通过4-溴丁酸乙酯和N-甲基二乙醇胺之间的亲核取代反应制备得到季铵离子型二元醇. 以季铵离子型二元醇与六亚甲基二异氰酸酯(HDI)三聚体为基本原料, 通过聚加成反应制备得到聚氨酯预聚体. 进一步经碱性水解等过程后制备得到不同水解时间的羧基甜菜碱型两性离子聚氨酯水凝胶(CBPU). 结果表明, 水解 60 min后的羧基甜菜碱型两性离子聚氨酯水凝胶不仅具有较好的机械性能, 而且对十六烷、 煤油、 石油醚、 异辛烷甚至原油的水下油接触角(UOCA)均达160°以上, 水下油黏附力均为0. 该羧基甜菜碱型两性离子聚氨酯水凝胶在防油涂层、 油水分离膜以及防污减阻等方面均具有重大的应用前景.     

两性离子聚合物涂层的研究与应用进展

两性离子聚合物是一类整体呈电中性,在同一单体侧链上同时含有阴、阳离子基团的高分子材料,因其独特的分子结构和理化性质引起了人们广泛的关注。两性离子聚合物具有极强的水化能力,通过结合水分子可以在材料表面形成一层致密的水化层,使其成为涂层材料功能化的良好选择,在诸多领域具有潜在的应用价值。从介绍两性离子聚合物的分类及聚合物涂层的制备方法入手,进一步对两性离子聚合物在海洋防污、生物医学和膜分离技术中的应用研究进展进行论述,最后对两性离子聚合物及涂层的发展进行总结和展望。     

可生物降解抗污材料

研究和开发抗生物污染材料,降低蛋白质的非特异性吸附和微生物的附着生长,不仅可以大大提高仪器的灵敏度,降低植入材料在愈合过程中的副作用,如炎症和血栓等,还可以节省很多航海时所需的能源和动力。目前抗污染材料多为亲水性的聚乙烯醇、聚(N-乙烯基吡咯烷酮)、聚(2-口恶唑啉)、聚乙二醇和两性离子聚合物。虽然这些材料抗污染能力强,但是分子链大多为聚丙烯酸酯或聚丙烯酰胺,不具有可生物降解性。可生物降解抗污材料可通过将抗污功能分子引入到可生物降解的基质分子(如脂肪族聚酯、聚碳酸酯、聚多肽和多糖等)中得到。本文综述了可生物降解抗污材料的研究进展,首先介绍了生物污染的危害,抗生物污染材料的分类、特征和存在的问题。重点综述了可生物降解抗污材料的研究现状,从亲水性聚合物(如聚乙二醇、两性离子聚合物)和抗污剂具体阐述了可降解抗污材料的抗污机理、合成、结构和性能,并对可生物降解抗污材料的未来发展进行了展望。     

甜菜碱型两性离子聚合物P(AM-DMAPAAS)的盐溶液性质

将丙烯酰胺丙基二甲基胺（DMAPAA）和1,3-丙基磺内酯,在55 ℃下反应20 h,合成了3-（丙烯酰胺丙基二甲胺基）丙磺酸盐（DMAPAAS）,将其在盐溶液中与丙烯酰胺（AM）单体进行自由基共聚合反应,获得净电荷为零的磺基甜菜碱型两性离子共聚物P(AM-DMAPAAS);对该两性离子共聚物进行了表征和溶解性评价。 研究结果表明,共聚物在NaCl溶液中的粘度比在纯水中的大,在Mg2+和Ca2+盐溶液中的粘度更大,且随着溶液浓度的增大而增大,表现出明显的反聚电解质溶液性质。 升高相同温度,两性离子共聚物的粘度保留率是普通聚丙烯酰胺的1.4倍。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.