Y463M BthA 活性位点处稳定的亚铁卟啉。
A Stable Ferryl Porphyrin at the Active Site of Y463M BthA.
机构信息
Boston University, Department of Chemistry, Boston, Massachusetts 02215, United States.
Carnegie Mellon University, Department of Chemistry, Pittsburgh, Pennsylvania 15213, United States.
出版信息
J Am Chem Soc. 2020 Jul 15;142(28):11978-11982. doi: 10.1021/jacs.0c04023. Epub 2020 Jul 1.
Abstract
BthA is a diheme enzyme that is a member of the bacterial cytochrome c peroxidase superfamily, capable of generating a highly unusual Fe(IV)Fe(IV)═O oxidation state, known to be responsible for long-range oxidative chemistry in the enzyme MauG. Here, we show that installing a canonical Met ligand in lieu of the Tyr found at the heme of MauG associated with electron transfer, results in a construct that yields an unusually stable Fe(IV)═O porphyrin at the peroxidatic heme. This state is spontaneously formed at ambient conditions using either molecular O or HO. The resulting data illustrate how a ferryl iron, with unforeseen stability, may be achieved in biology.
摘要
BthA 是一种二血红素酶，属于细菌细胞色素 c 过氧化物酶超家族，能够产生一种非常不寻常的 Fe(IV)Fe(IV)═O 氧化态，已知该氧化态负责酶 MauG 中的长程氧化化学。在这里，我们表明，在 MauG 相关电子转移的血红素处用典型的 Met 配体取代 Tyr，会导致在过氧化物酶血红素处生成一种异常稳定的 Fe(IV)═O 卟啉。该状态在环境条件下使用分子 O 或 HO 可自发形成。所得数据说明了在生物学中如何实现一种具有意外稳定性的铁氧还蛋白。
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