Park H G, Chang H N, Dordick J S
Samsung Advanced Institute of Technology, Taejon, Korea.
Biotechnol Bioeng. 2001 Mar 5;72(5):541-7.
A chemoenzymatic approach was developed to prepare sucrose-containing aromatic polymers. The protease from Bacillus licheniformis catalyzed the transesterification of sucrose with a diester of terephthalic acid in pyridine to give the mono- and diester products. At 45 degrees C, >70% of sucrose was consumed after 1 day and sucrose diester began to form after 6 days when >95% of sucrose had been converted to sucrose monoester. The final yield of sucrose diester after 20 days was 13.8%. The sucrose monoester was identified as sucrose 1'-terephthalate and the diester products consisted of sucrose 6,1'-diterephthalate and sucrose 6',1'-diterephthalate in a ratio of 2:1. The sucrose diester products were polymerized with ethylene-glycol and ethylene-diamine to give poly(ethylene-terephthalate) and poly(ethylene-terephthalamide), with sucrose contained in the polymer backbone. The polycondensation reactions were carried out in dimethylsulfoxide (DMSO) at 70 degrees C using zinc acetate as a catalyst. The sucrose-containing polyester and polyamide were obtained at 65% yield for 24 h and at 73% yield for 12 h, respectively. End-group analysis of the polymers by (13)C-NMR or (1)H-NMR in DMSO provided a number average molecular weight of 3200 and 4300 Da, respectively. Structural analyses of the polymers were performed with (1)H-NMR, (13)C-NMR, and FTIR. On the basis of (13)C-NMR, acylation of the C1', C6, and C6' hydroxyls were maintained in the polymer backbones.
开发了一种化学酶法来制备含蔗糖的芳香族聚合物。地衣芽孢杆菌的蛋白酶催化蔗糖与对苯二甲酸二酯在吡啶中进行酯交换反应，生成单酯和二酯产物。在45℃下，1天后>70%的蔗糖被消耗，6天后蔗糖二酯开始形成，此时>95%的蔗糖已转化为蔗糖单酯。20天后蔗糖二酯的最终产率为13.8%。蔗糖单酯被鉴定为蔗糖1'-对苯二甲酸酯，二酯产物由蔗糖6,1'-二对苯二甲酸酯和蔗糖6',1'-二对苯二甲酸酯以2:1的比例组成。将蔗糖二酯产物与乙二醇和乙二胺聚合，得到聚合物主链中含有蔗糖的聚对苯二甲酸乙二酯和聚对苯二甲酰胺。缩聚反应在70℃的二甲基亚砜（DMSO）中使用醋酸锌作为催化剂进行。含蔗糖的聚酯和聚酰胺分别在24小时内以65%的产率和12小时内以73%的产率获得。在DMSO中通过(13)C-NMR或(1)H-NMR对聚合物进行端基分析，分别得到数均分子量为3200和4300 Da。用(1)H-NMR、(13)C-NMR和FTIR对聚合物进行结构分析。基于(13)C-NMR，聚合物主链中C1'、C6和C6'羟基的酰化得以保持。
