甲壳素/壳聚糖接枝共聚反应

综述了近年来甲壳素/壳聚糖接枝共聚的研究进展。以不同单体分类，分别综述了壳聚糖与小分子乙烯基单体、大分子聚乙二醇单体、聚乳酸单体、环糊精、树状大分子接枝的研究，并介绍了新的接枝技术——生物催化接枝共聚，以及接枝壳聚糖衍生物的应用。     

壳聚糖接枝共聚改性最新研究进展

壳聚糖是一种天然高分子,也是迄今为止唯一发现的阳离子碱性多糖。壳聚糖分子链中富含羟基和氨基等反应性官能团,具有生物相容性、生物可降解性、抗菌性、无细胞毒性等优良性能,在生化、医药、环保、农业等领域有广泛的应用前景。然而,由于其大分子具有较好的立构规整性和较强的氢键作用,除稀盐酸、稀醋酸外,壳聚糖不溶于水和其它有机溶剂,因而限制了它的应用范围。为了扩大其应用领域,常通过接枝共聚反应来改善壳聚糖的性能。本文介绍了壳聚糖接枝共聚改性的最新研究进展,包括自由基引发接枝法、偶联接枝法以及催化接枝法。     

甲壳素和壳聚糖在离子液体中的溶解、材料化以及衍生化

甲壳素和壳聚糖是可再生的大分子生物质资源.由于分子内和分子间的强烈氢键作用,甲壳素和壳聚糖不能溶解在水或常规有机溶剂中,这极大地限制了其在诸多领域中的应用.离子液体作为一种新型绿色溶剂,对甲壳素和壳聚糖具有优良的溶解作用.本文综述了离子液体对甲壳素和壳聚糖的溶解性能和溶解机理,概述了均相溶液体系中纤维、膜、凝胶等材料的制备以及酰化、接枝共聚、交联、降解、希夫碱化等多种衍生化反应,总结了离子液体在甲壳素和壳聚糖化学研究中面临的挑战并对其进行了展望.     

壳聚糖-丙烯酰胺接枝共聚及其絮凝性能

壳聚糖-丙烯酰胺接枝共聚及其絮凝性能;壳聚糖;丙烯酰胺;接枝共聚;絮凝     

阻聚剂在接枝共聚中抑制均聚的作用

高分子的接枝共聚是改变现有高分子材料性能和合成新型高分子材料,以获得人们预期的优良性能和特殊功能的重要方法之一。天然橡胶、合成高分子、天然纤维(纸、棉、羊毛等)、化学纤维皆可通过不同单体进行接枝共聚。但是接枝共聚的化学方法中存在最大的问题是伴随产生大量均聚物,这是反应中所不希望的。     

甲壳素和壳聚糖在伤口敷料中的应用

天然高分子甲壳素和壳聚糖以其良好的生物相容性、生物可降解性、无毒、止血、止痛、抗菌、促进伤口愈合并减少疤痕等优点,在伤口敷料方面的研究正在引起人们的重视。本文对甲壳素和壳聚糖适于作为伤口敷料的优异性能从机理上进行了讨论,并介绍了通过甲壳素、壳聚糖及其衍生物制备性能优异的伤口敷料的研究进展。     

米根霉细胞壁结构性多糖与丙烯酸接枝共聚反应研究

化学改性天然高分子絮凝剂是利用天然高分子物质进行化学改性而成的。与人工合成的有机高分子絮凝剂相比,它具有选择性大、无毒、价廉、易降解等优点,因此将会有广阔的应用前景,近几年,将乙烯基单体接枝到生物高分子上的工作引起了人们的兴趣,这种天然高分子与合成高分子的结合有可能得到理想的性能,获得新的材料：如生物降解塑料、絮凝剂、离子交换剂等,目前这方面的研究主要中在纤维素、淀粉和壳聚糖的接枝共聚上。     

甲壳素和壳聚糖在离子液体中的溶解与改性

甲壳素及壳聚糖作为生物大分子材料难溶于诸多溶剂,从而限制了其应用和修饰改性。因此,研究与开发良好的溶剂体系具有重要意义。本文首先对甲壳素及壳聚糖在各种离子液体中的溶解性能和溶解机理进行了详细综述,其次概述了甲壳素与壳聚糖在离子液体介质中进行修饰的化学反应研究(如:水解作用、酰基化反应和接枝共聚反应等),最后提出离子液体作为一类可回收循环使用的良好溶解介质将会对甲壳素及壳聚糖的实际应用和修饰改性提供更好的媒介,并拓宽甲壳素及壳聚糖的研究与应用领域。     

甲壳素基新材料研究进展

甲壳素/壳聚糖良好的生物相容性、生物可降解性及独特的生理活性使其成为非常有应用价值的天然高分子材料,当前已成为新材料领域的研究热点.甲壳素/壳聚糖具有良好的可加工性能,可固定贵金属、半导体纳米材料等活性催化物质,同时其本身也具有催化作用,是一类绿色环境友好的高分子催化材料.良好的生物相容性和生物可降解性使甲壳素/壳聚糖...     

利用高分子多基元协同效应增强脂质体稳定性的研究

通过合成接枝胆固醇的壳聚糖水溶性高分子，并利用所接枝胆固醇的插膜能力，诱导高分子贴附于脂质体表面，形成高分子-脂质体复合物.研究发现，壳聚糖水溶性高分子可以起到屏蔽膜表面电荷的作用，同时该体系利用高分子链上多位点修饰的疏水基团与磷脂分子之间的疏水作用和高分子多基元之间共价连接的协同效应，增强了脂质体的抗融合及抗表面活性剂能力.该复合策略制备过程简便快捷，在体外实验中已展现出良好的稳定性，在长循环药物递送方面具有潜在的应用.     

Studies on graft copolymerization onto cellulose derivatives. XXIX. Photo-induced graft copolymerization of methyl methacrylate onto chitin and oxychitin

Graft copolymerization of methyl methacrylate (MMA) onto chitin and oxidized chitin was carried out by a noncatalytic photo-induced and a photo-sensitized method. The isolation method of grafted chains without a decrease in their degree of polymerization (DP) by sulfuric acid hydrolysis and the effects of some factors on the conversion and the grafted chain length have been studied. In case of the photo-induced graft copolymerization, if a small amount of dimethylformaldehyde (DMF) is added in the polymerization system, the induction period is shortened and the degree of grafting and the apparent number of grafted chains increase. The degree of grafting and the apparent number of grafted chains of the oxidized chitin containing a small amount of C?O groups are greater than those of the untreated chitin, but a further increase in C?O groups decreases these values. In the presence of this two species of the chitin samples, the polymerization reaction was carried out as functions of monomer and chitin concentrations. From these results, the mechanisms of the photo-induced graft copolymerization were discussed. It is also clear that the conversion and the apparent number of grafted chains by the noncatalytic photo-induced method are generally larger than those by the photo-sensitized method, and the grafting activity with hydrogen peroxide (HPO) is higher than that with azobisisobutyronitrile (AIBN).     

壳多糖与丙烯酸丁酯的乳液接枝共聚研究

以十二烷基苯磺酸钠为乳化剂，过硫酸钾－亚硫酸氢钠为引发剂，研究了壳多糖与丙烯酸丁醋的乳液共聚合，结果表明当［Ｋ２Ｓ２Ｏ８］＝［ＮａＨＳＯ３］＝２．５７×１０－３ｍｏｌ·１－１，［ＢＡ］＝０．６８ｍｏｌ．１－１，［Ｃｈｉｔｏｓａｎ］＝１９．２ｇ·ｌ－１，在７０℃下反应５小时，共聚反应的接技率和接枝效率均较高．用红外光谱，差热分析，Ｘ射线衍射，扫描电镜对接技共聚物进行了表征，此外测试了共聚物胶乳成膜的机械性能，表明用丙烯酸丁酯对壳多糖进行接枝改性，可提高壳多糖的韧性，扩大其应用范围．     

水溶性甲壳素及其膜的制备与表征

通过对高脱乙酰度壳聚糖进行均相乙酰化反应，制得脱乙酰度为51．7％的水溶性甲壳素，产物有很好的水溶性．通过红外光谱、X-射线衍射、差热分析等测试表征了水溶性甲壳素结构．结果表明，水溶性甲壳素的结构发生了较大变化，结晶性显著下降是导致水溶性增加的主要原因．     

Preparation and Characterization of Chitosan Hydrochloride

Chitin 1 is a biodegradable and nontoxic polysaccharide widely spread among marine and terrestrial invertebrates and fungi. It is usually obtained from waste materials of the sea food-processing industry, mainly shells of crab, shrimp, prawn and krill. Native chitin occurs in such natural composite materials usually combined with inorganics, proteins, lipids and pigments. Its isolation calls for chemical treatments to eliminate these contaminants, some of which maybe coimmercially explored. By treating crude chitin with aqueous 40～50% sodium hydroxide at 110～115℃ chitosan is obtained. However, the fully deacetylated product is rarely obtained due to the risks of side reactions and chain deplolymerization. Chitosan and chitin are closely related since both are linear polysaccharides containing 2-acetamido-2-deoxy-D-glucopyranose and 2-amino-2-deoxy-D-glucopyranose units joined by β (1→4) glycosidic bonds. They can be distinguished by their contents of the above-mentioned units and by their solubilities in aqueous media. The acetylated units predominate in chitin while chitosan chains contain mostly deacetylated units. Chitin is soluble in a very limited number of solvents while chitosan is soluble in aqueous dilute solutions of a number of mineral and organic acids, being the most common ones, the hydrochloric and acetic acids. In aqueous dilute acid media chitosan forms salts, producing polyelectrolyte chains bearing positive charges on the nitrogen atoms of their amine groups. In fact the salt of chitosan may be formed in a separate step or as a consequence of the presence of acid in the water suspension of the neutralized form of chitosan.     

Preparation and release characteristics of cisplatin albumin microspheres containing chitin and treated with chitosan

Cisplatin (CDDP) containing albumin microspheres and microcapsules incorporating biodegradable macromolecules, chitin and chitosan, were prepared, and their CDDP content and releasing ability and susceptibility to various enzymes were examined. Chitin was incorporated during preparation of the microspheres, while chitosan was used to treat preformed microspheres. CDDP content was remarkably increased by chitin; when chitin was incorporated at a concentration of 1.5%, the CDDP content of the microspheres was found to be 16.2% (1.8 times that with no addition of chitin). CDDP release was suppressed by chitin and chitosan. The 50% CDDP release time was about 1.5 h when no chitin was added, but about 16 h was required when chitin was incorporated into the microspheres at a concentration of 1.5%. Chitin and chitosan suppressed the decomposition by protease. The microspheres treated with 70% deacetylated chitosan showed the greatest susceptibility to lysozyme. In conclusion, CDDP release can be controlled by the use of chitin or chitosan, and the microspheres should show no immunogenicity in vivo because of their susceptibility to lysozyme.     

INFLUENCE OF MOLECULAR WEIGHT OF CHITIN AND ITS THREE DERIVATIVES ON CRITICAL CONCENTRATION OF LYOTROPIC LIQUID CRYSTALLINE PHASE TRANSITION*

The critical concentration of lyotropic liquid crystalline phase transition for chitin derivatives was determinedusing a polarization microscope. The influence of molecular weight on critical concentration of liquid crystalline solution forchitin, chitosan, cyanoethyl chitosan and propionyl chitin successively increases as the chain rigidity decreases. Therefore itcan be used as an indicator of the chain rigidity.     

接枝壳聚糖在药学领域的应用

壳聚糖无毒、具有良好的生物相容性、可生物降解性、无免疫反应和无致癌性等优点,可安全可靠地用于药物中.可是壳聚糖仅溶解在少数稀酸中,从而限制了其广泛的应用.对壳聚糖进行接枝,可使其溶解性增加,或增加一些其它性能,扩大其应用范围.本文从接枝聚合方法和应用的角度,综述了近年来壳聚糖的接枝共聚产物在药学领域的研究进展,包括:聚丙烯酸类、丙烯酰胺类、乙烯基类、聚乙二醇类、聚丙交酯(聚乳酸)类、脂肪酸类、具特殊功能的分子和其它疏水性侧链等,并提出未来的发展方向.     

Functionalization of chitosan polymer and their applications

The deacetylated derivative of chitin i.e. chitosan is an advantageous and interesting bioactive polymer. Despite its biodegradability, it consists of many reactive primary and secondary hydroxyl (–OH) and amino (–NH₂) functional groups which allow the possibilities of chemical modifications. The several chemical modifications such as alkylation, acylation, quaternization, phthaloylation, sulfation, thiolation, carboxymethylation, graft copolymerization etc. carried out. The chemical modification results various types of derivatives with modified properties for specific applications in varied area mainly of pharmaceutical, biomedical, biotechnological, cosmetic, agricultural, food and non-food industries as well as in water treatment, paper, and textile industry. The ability of chitosan to undergo versatile modifications and applications presents a great opportunity to scientific community and to industry.     

微波辅助壳聚糖接枝聚乳酸共聚物的合成及表征

在微波辅助下,以辛酸亚锡为催化剂、壳聚糖(CS)为大分子引发剂引发消旋丙交酯（D,L-LA）本体开环聚合制备了壳聚糖接枝聚乳酸共聚物。通过正交实验研究了微波功率、催化剂用量、反应温度和反应时间对聚合反应的影响,确定了最佳合成条件。并通过红外光谱、元素分析、核磁共振氢谱、X-射线衍射和热分析对接枝共聚物的结构与性能进行了表征。结果表明,在微波条件下,能快速、有效地合成预定结构的壳聚糖接枝聚乳酸共聚物;聚乳酸支链的引入,有效削弱了壳聚糖分子间和分子内较强的氢键作用,与相应的壳聚糖比较,共聚物的结晶性能下降,热分解温度降低;原料配比对共聚物的结构与性能有显著影响,随nD,L-LA/nCS糖环数值增大,共聚物中平均乳酰单元数逐渐增大,共聚物的结晶性能、起始分解温度逐渐下降。