摘要/Abstract
环糊精是一类由吡喃葡萄糖单元构成的大环分子,能够通过包结作用与多种小分子、金属离子以及聚合物形成主-客体包结物,从而实现对客体分子理化性能的调控,被广泛用于制药、食品、化学、色谱、催化、生物技术、农业、化妆品、卫生、医学、纺织和环境等领域.然而,环糊精分子在众多应用领域不易操控,通过化学交联制备环糊精聚合物,形成以环糊精为主体的聚合物,则有望实现环糊精与交联基团的"集成"和"协同"作用,不但能有效解决环糊精分子的操控问题,而且能够赋予环糊精单分子所不具有的独特功能和理化性质,因此环糊精聚合物的设计合成及其应用吸引了广泛的研究兴趣.本综述介绍了环糊精聚合物领域的研究近况,对环糊精聚合物的种类按结构与性质进行了分类,系统介绍了各类环糊精聚合物的制备方法,重点介绍了近五年环糊精聚合物取得的新突破,并详细论述了各类环糊精聚合物在生物医药中的应用和其他领域的代表性应用,最后对环糊精聚合物作了简要总结和展望.
关键词: 环糊精, 聚合物, 化学交联, 药物载体, 超分子自组装
Cyclodextrins (CDs) are a family of macrocyclic oligosaccharides composed of α-1,4-linked D-glucopyranose units. The most commonly used CDs are α-, β-, and γ-CD, which consist of 6, 7, and 8 D-glucose units, respectively. They possess a relative hydrophobic inner cavity and a hydrophilic outer surface and can form inclusion complexes with various small molecules, metal ions and polymers, tailoring the physicochemical property of the guests, and thus have been widely used in the fields of pharmacy, food, chemistry, chromatography, catalysis, biotechnology, agriculture, cosmetics, hygiene, medicine, textiles and the environment, etc. However, it is difficult to manipulate the native CDs in some specific applications, they are crystallized solid and soluble in water but insoluble in most organic solvents. CD polymers (CDPs), such as crosslinked CDs or CD based hydrogels with various crosslinkers by chemical reactions, and CD based supramolecular polymers formed by physical interactions, can achieve the integration effect and synergy effect of CDs, crosslinkers and guest polymers, not only possessing the inclusion capacity of CDs, but also endowing CDs with other properties introduced by crosslinkers. The CDPs can be easily manipulated and they exhibit unique features that native CDs are lack of. Hence, the design, synthesis and applications of CDPs have attracted broad interests in recent years. This review focuses on the recent progress in CDPs, and different types of CDPs are identified and classified based on the structures and functions, namely CD based polyrotaxane, grafted CDs, crosslinked CDs and linear CDs, etc. Besides, the synthetic methodologies of CDPs are highlighted. Particular attention is paid to the breakthrough on the CDPs in the past five years, and their applications in biomedicine, such as drug delivery, gene delivery, target delivery, controlled release and cell imaging are discussed in detail. The typical applications in other fields such as absorption, environment remediation, thermal insulation, catalysis and slid-ring gels are also discussed in brief. Finally, the review provides brief summary and prospect of CDPs.
Key words: cyclodextrin, polymer, chemical crosslinking, drug carrier, supramolecular self-assembly
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