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基于顺序狄尔斯-阿尔德点击反应和光聚合的淀粉-纤维素互穿网络水凝胶的制备与表征

Preparation and characterization of starch-cellulose interpenetrating network hydrogels based on sequential Diels-Alder click reaction and photopolymerization.

作者信息

Wei Hongliang, Li Songmao, Liu Zijun, Chen Hongli, Liu Yuhua, Li Weikun, Wang Gang

机构信息

School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou, PR China.

School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou, PR China.

出版信息

Int J Biol Macromol. 2022 Jan 1;194:962-973. doi: 10.1016/j.ijbiomac.2021.11.154. Epub 2021 Nov 27.

Abstract

Herein, starch-cellulose interpenetrating network (IPN) hydrogels were fabricated by sequential Diels-Alder click reaction and photopolymerization in water. Moreover, β-cyclodextrin, a commonly used host molecule in supramolecular chemistry, was also introduced to improve the performance of the IPN hydrogel. Firstly, the starch-based dienes were synthesized by modifying starch with N-maleoyl-β-alanine, and the cellulose-based dienophiles were obtained by the reaction of cellulose and furfurylamide succinate; Secondly, the as-synthesized starch-based dienes, cellulose-based dienophiles, polymerizable β-cyclodextrin, crosslinker, and acrylamide were dissolved in water and obtained a transparent solution. The solution was maintained in a water bath of 50 °C for 3 h, forming the first network via catalyst-free click Diels-Alder reaction, subsequently, the second network was formed by photopolymerization. Their preparation conditions were optimized via one-factor experiments and their properties and structures were characterized. Finally, 5- fluorouracil (5-Fu) was used as a model drug to study the sustained release behavior of the drug-loaded hydrogels. Release profile was found to fit in Ritger-Peppas kinetic model and polymer relaxation and drug diffusion made a valuable contribution to drug release. Taking into account the virtues of easily controllable photopolymerization and catalyst-free Diels-Alder reaction, the strategy described here has a potential application in the preparation of IPN hydrogels.

摘要

在此,通过在水中依次进行狄尔斯-阿尔德点击反应和光聚合反应制备了淀粉-纤维素互穿网络(IPN)水凝胶。此外,还引入了超分子化学中常用的主体分子β-环糊精来改善IPN水凝胶的性能。首先,用N-马来酰基-β-丙氨酸修饰淀粉合成淀粉基双烯体,通过纤维素与琥珀酸糠酰胺反应得到纤维素基亲双烯体;其次,将合成的淀粉基双烯体、纤维素基亲双烯体、可聚合β-环糊精、交联剂和丙烯酰胺溶解在水中,得到透明溶液。将该溶液在50℃水浴中保持3小时,通过无催化剂的狄尔斯-阿尔德点击反应形成第一个网络,随后通过光聚合形成第二个网络。通过单因素实验优化了它们的制备条件,并对其性能和结构进行了表征。最后,以5-氟尿嘧啶(5-Fu)为模型药物研究了载药水凝胶的缓释行为。发现释放曲线符合Ritger-Peppas动力学模型,聚合物松弛和药物扩散对药物释放有重要贡献。考虑到光聚合反应易于控制和狄尔斯-阿尔德反应无催化剂的优点,本文所述策略在IPN水凝胶的制备中具有潜在应用。

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