环境中自由及结合态雌激素的酶降解转化研究进展  

A Review on Enzymatic Degradation and Transformation Mechanisms of Free and Conjugated Estrogens in the Environment

作　　者：余薇薇 杜邦昊 张敏讷 万巧玲 杨硕 赵晨菊 YU Wei-wei;DU Bang-hao;ZHANG Min-ne;WAN Qiao-ling;YANG Shuo;ZHAO Chen-ju(School of River and Ocean Engineering,Chongqing Jiaotong University,Key Laboratory of Hydraulic and Waterway Engineering of the Ministry of Education,Chongqing 400074;Chongqing Monitoring Station,Water Quality Monitoring Network of National Urban Water Supply,Chongqing 400060)

机构地区：[1]重庆交通大学河海学院水利水运工程教育部重点实验室,重庆400074 [2]国家城市供水水质监测网重庆监测站,重庆400060

出　　处：《生物技术通报》2019年第4期151-162,共12页Biotechnology Bulletin

基　　金：国家自然科学基金项目(51608079);国家内河航道整治工程技术研究中心开放基金项目(SLK2018A04);重庆交通大学河海学院研究生教育创新基金项目(YC2018002);重庆交通大学实验室开放基金项目(SYJ201608);重庆交通大学大学生创新创业训练计划项目(201810618052)

摘　　要：天然类固醇雌激素(SEs)可分为自由态(FEs)和结合态(CEs)两大类,环境中SEs的广泛存在对人类和动物的内分泌系统产生不同程度的干扰,危害生态系统的多样性及稳定性。目前,多种酶对环境中不同形态SEs的催化去除起到重要作用,总结了环境中氧化还原酶对FEs以及水解酶对CEs的去除作用,并阐述不同形态SEs的主要酶降解转化机理与路径。氧化还原酶催化FEs形成自由基,通过C-O-C、C-C共价键自耦合、相互耦合形成聚合产物,该过程易受到环境中有机质的影响;水解酶则通过解离硫酸盐或葡糖苷酸盐结合基团将CEs水解为相对应的FEs,硫酸盐结合态雌激素不易被解离,在环境中稳定性更强。讨论了酶在实际应用中存在的问题,对酶在污水及土壤环境中SEs的去除、酶的联用、固定化酶、酶工程等方面进行了展望,旨为环境中两种形态雌激素的酶降解转化研究提供理论借鉴。Natural steroid estrogens(SEs)can be classified into free(FEs)and conjugated(CEs)ones in the environment.These ubiquitous SEs in the environment have caused damages to the diversity and stability of ecosystem due to the recognized varied interfering effects on human and wildlife endocrine systems.At present,multiple enzymes play an important role in the catalytic removal of both FEs and CEs in the environment.This review summarizes the removal mechanisms of FEs and CEs by oxidoreductases and hydrolases,respectively,and elucidates the main proposed enzymatic degradation and transformation pathways of both FEs and CEs.Oxidoreductases catalyze FEs to generate radicals and subsequently form poly-products by covalent bond(C-O-C and C-C)self-and cross-coupling;meanwhile,the catalytic process is easily affected by organic compounds in the environment.As for CEs,these compounds can be deconjugated into their corresponding FEs by deconjugating sulfate or glucuronide groups via hydrolases;additionally,CSEs are recalcitrant to be deconjugated and more stable in the environment compared to CGEs.This review also discusses and highlights the further application of enzymes for removing SEs in wastewater and soil,combined use of enzymes,immobilization of enzymes,enzyme engineering,and so on,aiming at providing a theoretical reference for the degradation and transformation of FEs and CEs by enzymatic catalysis in the environment.

关 键 词：自由态雌激素 结合态雌激素 酶催化 耦合反应 解离 

分 类 号：X171.5[环境科学与工程—环境科学]