Directed evolution of cytochrome c for carbon-silicon bond formation: Bringing silicon to life.
Directed evolution of cytochrome c for carbon-silicon bond formation: Bringing silicon to life.
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细胞色素 c 的定向进化促进碳-硅键形成：赋予硅生命。
DOI：
10.1126/science.aah6219
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发表时间：
2016-11-25
期刊：
影响因子：
--
通讯作者：
Arnold FH
中科院分区：
文献类型：
--
作者：
Kan SB;Lewis RD;Chen K;Arnold FH
催化碳-硅键形成的酶在自然界中是未知的，尽管这两种元素在自然界中丰富。这种酶将扩大生物学的催化能力，使生命系统能够进入以前只对合成化学开放的化学空间。我们已经发现血红素蛋白在生理条件下通过卡宾插入到硅-氢键中来催化有机硅化合物的形成。该反应在体外和体内进行，适应广泛的底物具有高化学和对映选择性。利用定向进化，我们增强了海洋红温菌细胞色素c的催化功能，实现了比最先进的合成催化剂高15倍以上的营业额。这种碳-硅键形成生物催化剂提供了一种环境友好且高效的制备对映体纯有机硅分子的途径。
Enzymes that catalyze carbon–silicon bond formation are unknown in nature, despite the natural abundance of both elements. Such enzymes would expand the catalytic repertoire of biology, enabling living systems to access chemical space previously only open to synthetic chemistry. We have discovered that heme proteins catalyze the formation of organosilicon compounds under physiological conditions via carbene insertion into silicon–hydrogen bonds. The reaction proceeds both in vitro and in vivo, accommodating a broad range of substrates with high chemo- and enantioselectivity. Using directed evolution, we enhanced the catalytic function of cytochrome c from Rhodothermus marinus to achieve more than 15-fold higher turnover than state-of-the-art synthetic catalysts. This carbon–silicon bond-forming biocatalyst offers an environmentally friendly and highly efficient route to producing enantiopure organosilicon molecules.