期刊文献+
共找到2篇文章
< 1 >
每页显示 20 50 100
精准调控Baeyer-Villiger单加氧酶的底物选择性以避免拉唑亚砜的过氧化
1
作者 吴殷琦 陈倩倩 +9 位作者 陈琦 耿强 张巧玉 郑宇璁 赵晨 张龑 周佳海 王斌举 许建和 郁惠蕾 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第8期157-167,共11页
氧化酶催化的分子功能化是非常具有吸引力的研究领域之一,其中,高度选择性氧化反应对手性分子的构建至关重要.大量研究集中在对氧化酶立体选择性和区域选择性的分子改造上,而由于底物选择性差引起的过度氧化问题长期被忽视.Baeyer-Villi... 氧化酶催化的分子功能化是非常具有吸引力的研究领域之一,其中,高度选择性氧化反应对手性分子的构建至关重要.大量研究集中在对氧化酶立体选择性和区域选择性的分子改造上,而由于底物选择性差引起的过度氧化问题长期被忽视.Baeyer-Villiger单加氧酶(BVMOs)是一类多功能的生物催化剂,可以在脂肪族或环状酮底物的羰基附近插入一个氧原子,具有较高的区域选择性.BVMOs还可以催化包括硫、氮和磷在内的杂原子的不对称氧化.由于其温和的反应条件和较好的对映选择性,BVMOs催化硫醚不对称氧化生成手性亚砜被认为是一种极具吸引力且绿色清洁的合成方法.BVMOs可以催化硫醚不对称氧化生成有价值的手性亚砜,但亚砜过氧化生成无用的副产物砜限制了其进一步应用.这种过度氧化的本质原因是BVMOs对底物选择性不足,导致目标产物亚砜被进一步氧化.本文建立了一个数学模型,将酶对硫醚和亚砜两种相似底物之间的特异性常数之比(kcat/Km)定义为酶对底物选择性.随后使用蛋白结构引导的底物通道工程方法精准调控了拉唑硫醚单加氧酶AcPSMO的底物选择性,成功地将亚砜的过氧化降至最低.酶促氧化奥美拉唑硫醚24h后,突变体F277L生成的副产物砜含量低于1%(mol/mol),而野生型的砜含量为65%.分子动力学模拟和量子力学/分子力学研究结果表明,黄素氢过氧化物(FADH-OOH)周围改变的氢键网络可以调节亚砜氧化的机制和活性.此外,重新设计的AcPSMO突变体也成功地应用于其它手性拉唑亚砜的可控合成.综上,本文开发的精确控制氧化酶底物选择性的方法对于提高其它杂原子生物氧化反应的底物特异性具有借鉴意义. 展开更多
关键词 Baeyer-Villiger单加氧酶 手性亚砜 过度氧化 底物选择性 蛋白质工程 分子动力学模拟 量子力学/分子力学研究
下载PDF
Mirror,mirror on the wall,which is the greenest of them all?A critical comparison of chemo-and biocatalytic oxyfunctionalisation reactions
2
作者 yinqi wu Caroline E.Paul Frank Hollmann 《Green Carbon》 2023年第2期227-241,共15页
This review article critically compares two widely used types of catalysis,chemo-and biocatalysis,and provides insights on their greenness according to specified parameters.A comparative analysis of the environmental ... This review article critically compares two widely used types of catalysis,chemo-and biocatalysis,and provides insights on their greenness according to specified parameters.A comparative analysis of the environmental impact of chemo-and biocatalytic oxyfunctionalisation reactions based on published experimental data reveals that both methods produce comparable amounts of waste,with the majority stemming from the solvent used.However,it is emphasised that the synthesis of the catalysts themselves,including biocatalysts,should also be considered when assessing their environmental impact.The review underscores the complexity of assessing the environmental impact of catalytic oxyfunctionalisation reactions.The article also discusses the relationship between solvent properties and the energy demands for chemical transformations and downstream processing,underlining that the choice of solvent can significantly influence the environmental impact of a catalytic process.Additionally,the review highlights the importance of considering the recyclability of reagents and the secondary CO_(2)emissions caused by the energy requirements of the reaction when evaluating the environmental impact of a catalytic process.Each chemo-and biocatalysis produce a certain environmental impact,the greenness of either method is dependent on several factors,including the type of waste generated,the recyclability of reagents,and secondary CO_(2)emissions.This review therefore recommends using consistent metrics and a comprehensive life cycle assessment approach to evaluate this environmental impact,and highlights the importance of considering the synthesis of the catalysts themselves. 展开更多
关键词 Green chemistry Catalysis BIOCATALYSIS Chemocatalysis Environmental impact Oxidative reactions
原文传递
上一页 1 下一页 到第
使用帮助 返回顶部