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Well-Defined Selenium-Containing Aliphatic Polycarbonates via Lipase-Catalyzed Ring-Opening Polymerization of Selenic Macrocyclic Carbonate Monomer
ACS Macro Letters ( IF 5.8 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1021/acsmacrolett.8b00039
Chao Wei 1 , Yue Xu 1 , Bingkun Yan 1 , Jiaqian Hou 1 , Zhengzhen Du 1 , Meidong Lang 1
Affiliation  

The synthesis of well-defined, biodegradable selenium-containing polymers remains a formidable challenge in polymer chemistry. Herein, a selenic cyclic carbonate dimer monomer (MSe) was developed to generate well-defined, biodegradable aliphatic polycarbonates with selenide functionality on the backbone. The monomer was synthesized via the intermolecular cyclization of di(1-hydroxyethylene) selenide and diphenyl carbonate with lipase CA as catalysts in a mass of anhydrous toluene with very dilute monomer concentration. Then living ring-opening polymerization (ROP) was executed by solution method using the same lipase CA as catalysts. Similarly, the copolymerizations with commercial trimethylene carbonate (TMC) generated random copolymers demonstrated by 13C NMR, regulating the density of selenium functional groups. The resulting polymers exhibited a living polymerization characteristic, as evidenced by polymerization kinetics, predictable molecular weights, narrow molecular-weight distribution, and controlled copolymer compositions. Using hydrophilic macroinitiators (PEG), amphiphilic di/triblock copolymers could be obtained, suggesting their potential as controlled drug delivery system (DDS) and hydrogel scaffolds for tissue engineering.

中文翻译:

脂肪酶催化硒大环碳酸酯单体开环聚合制备明确的含硒脂肪族聚碳酸酯

定义明确的、可生物降解的含硒聚合物的合成仍然是聚合物化学中的一项艰巨挑战。在此,开发了一种含硒环状碳酸酯二聚体单体 (M Se ),以生成结构明确、可生物降解的脂肪族聚碳酸酯,该聚碳酸酯在主链上具有硒化官能团。该单体是通过二(1-羟基乙烯)硒化物和碳酸二苯酯在具有非常稀单体浓度的大量无水甲苯中以脂肪酶CA作为催化剂的分子间环化合成的。然后使用相同的脂肪酶CA作为催化剂,通过溶液法进行活性开环聚合(ROP)。类似地,与商业三亚甲基碳酸酯 (TMC) 的共聚产生了由13证明的无规共聚物C NMR,调节硒官能团的密度。所得聚合物表现出活性聚合特性,如聚合动力学、可预测的分子量、窄的分子量分布和受控的共聚物组成所证明的。使用亲水性大分子引发剂 (PEG),可以获得两亲性二/三嵌段共聚物,这表明它们具有作为受控药物递送系统 (DDS) 和用于组织工程的水凝胶支架的潜力。
更新日期:2018-02-22
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