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葡萄糖酸内酯羟基选择性重排反应引发脂肪族聚酯研究

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刘程琳,宋汪泽,郑玉斌.葡萄糖酸内酯羟基选择性重排反应引发脂肪族聚酯研究[J].,2020,60(5):456-464
葡萄糖酸内酯羟基选择性重排反应引发脂肪族聚酯研究
Study of aliphatic polyesters initiated by selective rearrangement of hydroxyl groups in glucosactone
DOI:10.7511/dllgxb202005002
中文关键词:葡萄糖酸内酯生物质开环聚合两亲性聚合物药物包载
英文关键词:glucosactonebiomassring open polymerizationamphiphilic polymerdrug encapsulation
基金项目:国家自然科学基金资助项目(2170202521978039);中央高校基本科研业务费专项资金资助项目(DUT20YG120).
作者单位
刘程琳,宋汪泽,郑玉斌
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中文摘要:
通过对葡萄糖酸内酯进行伯羟基保护以及分子内开环重排,合成了一种基于糖类结构的五元环状三羟基引发剂.该引发剂具有3个仲羟基结构,在有机碱1,5,7 三氮杂二环[4.4.0]癸 5 烯(TBD)的催化下,控制内酯单体如丙交酯、己内酯与羟基的投料比,采用控制聚合法获得一系列具有不同相对分子质量的三臂聚乳酸以及三臂聚己内酯,通过聚合后脱保护及偶联聚乙二醇的策略制备了一系列两亲性三臂聚酯并用于药物载体的研究.利用核磁、质谱、傅里叶红外变换等对生物质引发剂进行了结构表征,利用凝胶色谱、核磁等对三臂聚酯进行了结构表征,通过纳米粒度仪对其自组装后胶束的性质进行了探究.结果表明,该生物基三臂引发剂为稳定的五元环结构,并成功制备了相对分子质量可控且分布较窄的三臂两亲性聚酯,该聚合物可以自组装成粒径为100~200 nm的胶束,并实现疏水药物的包载.
英文摘要:
Five member ring, three hydroxyl group initiators were successfully synthesized via the intramolecular ring open rearrangement of the primary hydroxyl group protected glucosactone. Such initiator is a kind of carbohydrate based compound originated from the glucose with three secondary hydroxyl groups. Three arm polylactic acid (PLA) and polycaprolactone(PCL) with various relative molecular mass were prepared with organic alkali 1, 5, 7 triazabicyclo[4.4.0] dec 5 ene (TBD) as the catalyst via the controlled polymerization method by varying the feeding ratios of the monomers as lactide and caprolactone to the hydroxyl group. A series of amphiphilic three arm polyester were prepared by the conjugation of polyethylene glycol (PEG) at the end of the chain, then post functionalization for the drug encapsulation study. NMR, MS, FT IR were used to fully characterize the structure of the bio based initiators. GPC and NMR were used to characterize the obtained three arm polyesters. Nano particle size meter was used to test the particle size of the self assembled micelles. Results indicate that the bio based three arm initiators are stable five member ring initiators. The relative molecular mass of the three arm amphiphilic polyester is controlled and narrow. The polymer can be self assembled to micelles with the particle size of 100 200 nm. Hydrophobic drug could be successfully encapsulated into the micelles formed by such amphiphilic polymers.
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