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1. 陕西科技大学 教育部轻化工助剂化学与技术重点实验室,西安,710021
2. 日本秋田县立大学系统科学技术学部,秋田,日本,015-0055
纸质出版日期:2015-5-20,
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覃家祥, 张敏, 李成涛, 苗妮娜, 张祎, 邱建辉. 结合分子模拟探讨PC脂肪酶催化PBS基共聚物降解的主链异构效应[J]. 高分子学报, 2015,(5):500-507.
Jia-xiang Qin, Min Zhang, Cheng-tao Li, Ni-na Miao, Yi Zhang, Jian-hui Qiu. Studies on the Effect of Isomerism in Main Chain on Enzymatic Degradation of PBS-based Copolymers with Combination of Molecular Modeling[J]. Acta Polymerica Sinica, 2015,(5):500-507.
覃家祥, 张敏, 李成涛, 苗妮娜, 张祎, 邱建辉. 结合分子模拟探讨PC脂肪酶催化PBS基共聚物降解的主链异构效应[J]. 高分子学报, 2015,(5):500-507. DOI: 10.11777/j.issn1000-3304.2015.14329.
Jia-xiang Qin, Min Zhang, Cheng-tao Li, Ni-na Miao, Yi Zhang, Jian-hui Qiu. Studies on the Effect of Isomerism in Main Chain on Enzymatic Degradation of PBS-based Copolymers with Combination of Molecular Modeling[J]. Acta Polymerica Sinica, 2015,(5):500-507. DOI: 10.11777/j.issn1000-3304.2015.14329.
采用固定化洋葱假单胞菌脂肪酶(Pseudomonas cepacia lipase
PC脂肪酶)为催化剂
在有机溶剂体系中研究了环己烷二甲醇和环己烷二甲酸对聚丁二酸丁二醇酯(PBS)的改性共聚物
即聚(丁二酸丁二醇-co-丁二酸环己烷二甲醇酯)(PBS-co-CHDMS)和聚(丁二酸丁二醇-co-环己烷二甲酸丁二醇酯) (PBS-co-BCHDA)的降解规律及其差异性.通过共聚物降解率随时间的变化、降解产物的MALDI-TOF-MS分析研究了共聚物降解规律
并以分子模拟分别研究了降解差异性和PC脂肪酶与底物的结合机制.研究结果表明
PC脂肪酶均可催化PBS基共聚物降解;在降解60 h后
相比较于PBS-co-BCHDA
PBS-co-CHDMS降解率均更大;其中PBS-co-10%CHDMS降解率最大
为85%.共聚物降解不仅生成了线型小分子
还产生了部分环状低聚物;此外
PBS-co-CHDMS降解产生的低聚物种类比PBS-co-BCHDA的要多.分子对接模拟结果表明
在氯仿中
PC脂肪酶与底物结合自由能的大小顺序为CMSCMBSCMBCABBSB
即含有丁二酸环己烷二甲醇酯(CHDMS)单元的底物与PC脂肪酶活性位点的对接更为稳定.
The enzymatic degradation of poly(butylene succinate-co-1
4-cyclohexane dimethanol succinate) (PBS-co-CHDMS)
poly(butylene succinate-co-butylene 1
4-cyclohexanedicarboxylic acid) (PBS-co-BCHDA) and poly(butylene succinate) (PBS) were performed with the aim to gain more underlying information about the degradation rules and differences in organic solvent.Among various hydrolytic enzymes the lipase from Pseudomonas cepacia (PC) was chosen for the studies.The rules of enzymatic degradation were investigated by molecular weight variation and MALDI-TOF-MS analysis of the degradation products.Additionally
mechanism of the combination between substrate and enzyme was studied with molecular docking.The results indicated that PBS-based copolymers showed an obvious degradation in chloroform.Compared to PBS-co-BCHDA
PBS-co-CHDMSs all showed a greater degradation rate after 60 h enzymatic degradation.Particularly maximum degradation was observed in PBS-co-10%CHDMS with a degradation ratio of ratio about 85%.The enzymatic degradation of PBS-based copolymers produced not only linear segments
but also cyclic oligomers.Furthermore
PBS-co-CHDMS produced more oligomers than PBS-co-BCHDA.According to the results of molecular docking
the free energy of binding between PC lipase and substrate in chloroform was in the order of CMSCMBSCMBCABBSB.That is
the docking of substrate containing 1
4-cyclohexane dimethanol succinate(CHDMS) in the active site of PC lipase was more stable than any other ones.
酶催化降解共聚物洋葱假单胞菌脂肪酶降解产物分子对接
Enzymatic degradationCopolyestersPseudomonas cepacia lipaseDegradation productsmolecular docking
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