疏水环境对逆醛醇反应的影响：与计算设计酶的比较。
The effect of the hydrophobic environment on the retro-aldol reaction: comparison to a computationally-designed enzyme.
机构信息
College of Charleston, Department of Chemistry and Biochemistry, 66 George Street, Charleston, SC 29424, USA.
出版信息
Org Biomol Chem. 2013 Dec 28;11(48):8419-25. doi: 10.1039/c3ob41898g. Epub 2013 Nov 5.
Recent work on a computationally-designed retroaldolase RA-61 suggested that most of the rate-acceleration brought about by this enzyme was due to non-specific interactions with the aromatic substrate. To provide a benchmark for the role of non-specific interactions in this system, we measured the second-order rate constant for the amine-catalysed retro-aldol reaction of methodol in the presence of non-specific hydrophobic pockets such as micelles. We found that a simple micellar system, that consists of a positively-charged surfactant and a long-chain amine, can accelerate the retro-aldol reaction of methodol by 9500-fold. This effect rivals the 10(5)-fold rate acceleration of RA-61. Similar results were obtained with BSA used as the catalyst, implying that the retro-aldol reaction of methodol can be greatly accelerated by non-specific hydrophobic pockets that contain an amino group.
最近一项针对计算机设计的 retroaldolase RA-61 的研究表明，该酶带来的大部分速率加速是由于与芳香族底物的非特异性相互作用。为了为该系统中非特异性相互作用的作用提供基准，我们测量了在存在非特异性疏水口袋（如胶束）的情况下，methanolol 的胺催化 retro-aldol 反应的二级速率常数。我们发现，一个简单的胶束体系，由带正电荷的表面活性剂和长链胺组成，可以使 methanolol 的 retro-aldol 反应加速 9500 倍。这种效果可与 RA-61 的 10（5）倍速率加速相媲美。使用 BSA 作为催化剂时也得到了类似的结果，这意味着含有氨基的非特异性疏水口袋可以大大加速 methanolol 的 retro-aldol 反应。
Zotero 插件