A Bi-enzymatic Convergent Cascade for ε-Caprolactone Synthesis Employing 1,6-Hexanediol as a "Double-Smart Cosubstrate'
A Bi-enzymatic Convergent Cascade for ε-Caprolactone Synthesis Employing 1,6-Hexanediol as a "Double-Smart Cosubstrate'
复制标题
DOI：
10.1002/cctc.201500511
复制
发表时间：
2015-08-01
期刊：
影响因子：
4.5
通讯作者：
Kara, Selin
中科院分区：
文献类型：
--
作者：
Bornadel, Amin;Hatti-Kaul, Rajni;Kara, Selin
以会聚方式设计了由Baeyer-Villiger单加氧酶和醇脱氢酶（ADH）组成的双酶级联，以利用2摩尔当量的环己酮（CHO）和1当量的1，6-己二醇作为“双智能共底物”来生产ε-己内酯（ECL），水作为唯一副产物。本文报道的会聚酶级联反应在环境条件下在水中进行，对于辅因子是自给自足的，并且将所有起始材料并入所需产物ECL中。在所研究的不同酶中，来自不动杆菌NCIMB 9871的环己酮单加氧酶与来自乙醇嗜热厌氧杆菌的ADH偶联催化的反应显示出最好的结果，24小时后CHO的转化率达到91%，产物滴度为2gL（-1）。偶联系统的放大（50 mL）比小规模反应表现得更好，并且在18 h内实现了>99%的CHO转化率和20 mM的ECL浓度。
A bi-enzymatic cascade consisting of a Baeyer-Villiger monooxygenase and an alcohol dehydrogenase (ADH) was designed in a convergent fashion to utilise two molar equivalents of cyclohexanone (CHO) and one equivalent of 1,6-hexanediol as a 'double-smart cosubstrate' to produce epsilon-caprolactone (ECL) with water as sole by-product. The convergent enzymatic cascade reaction reported herein, is performed at ambient conditions in water, is self-sufficient with respect to cofactor, and incorporates all starting materials into the desired product, ECL. Among different enzymes explored, the reaction catalysed by cyclohexanone monooxygenase from Acinetobacter sp. NCIMB 9871 coupled with ADH from Thermoanaerobacter ethanolicus showed the best results, reaching 91% conversion of CHO after 24h with a product titre of 2gL(-1). Scale-up of the coupled system (50mL) performed better than the small-scale reactions and >99% conversion of CHO and ECL concentration of 20mM were achieved within 18h.