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Reaction of O with a diiron protein generates a mixed-valent Fe/Fe center and peroxide.

Proc. Natl. Acad. Sci. U.S.A.. 2019; 
BradleyJustin M,SvistunenkoDimitri A,PullinJacob,HillNatalie,StuartRhona K,PalenikBrian,WilsonMichael T,HemmingsAndrew M,MooreGeoffrey R,Le BrunNi
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摘要

The gene encoding the cyanobacterial ferritin Ftn is up-regulated in response to copper stress. Here, we show that, while Ftn does not interact directly with copper, it is highly unusual in several ways. First, its catalytic diiron ferroxidase center is unlike those of all other characterized prokaryotic ferritins and instead resembles an animal H-chain ferritin center. Second, as demonstrated by kinetic, spectroscopic, and high-resolution X-ray crystallographic data, reaction of O with the di-Fe center results in a direct, one-electron oxidation to a mixed-valent Fe/Fe form. Iron-O chemistry of this type is currently unknown among the growing family of proteins that bind a diiron site within ... More

关键词

diiron protein,electron transfer,ferritin,iron,tyrosyl rad