Tuning catalytic bias of hydrogen gas producing hydrogenases,Journal of the American Chemical Society

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Tuning catalytic bias of hydrogen gas producing hydrogenases
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-12-09 , DOI: 10.1021/jacs.9b08756
Jacob H Artz _{1,

2} , Oleg A Zadvornyy ₁ , David W Mulder ₂ , Stephen M Keable ₃ , Aina E Cohen ₄ , Michael W Ratzloff ₂ , S Garrett Williams ₅ , Bojana Ginovska ₆ , Neeraj Kumar ₆ , Jinhu Song ₄ , Scott E McPhillips ₄ , Catherine M Davidson ₄ , Artem Y Lyubimov ₄ , Natasha Pence ₁ , Gerrit J Schut ₇ , Anne K Jones ₅ , S Michael Soltis ₄ , Michael W W Adams ₇ , Simone Raugei _{1,

6} , Paul W King ₂ , John W Peters _{1,

3,

6}

Affiliation

Hydrogenases display a wide range of catalytic rates and biases in reversible hydrogen gas oxidation catalysis. The interac-tions of the iron-sulfur containing catalytic site with the local protein environment are thought to contribute to differences in catalytic reactivity, but this has not been demonstrated. The microbe Clostridium pasteurianum produces three [FeFe]-hydrogenases that differ in "catalytic bias" by exerting a disproportionate rate acceleration in one direction or the other that spans a remarkable six orders of magnitude. The combination of high-resolution structural work, biochemical analyses, and computational modeling indicate that protein secondary interactions directly influence the relative stabiliza-tion/destabilization of different oxidation states of the active site metal cluster. This selective stabilization or destabilization of oxidation states can preferentially promote hydrogen oxidation or proton reduction and represents a simple yet elegant model by which a protein catalytic site can confer catalytic bias.

中文翻译：

调整产生氢气的氢化酶的催化偏差

氢化酶在可逆氢气氧化催化中表现出广泛的催化速率和偏差。含铁硫催化位点与局部蛋白质环境的相互作用被认为导致催化反应性的差异，但这尚未得到证实。巴氏梭菌微生物产生三种“催化偏差”不同的 [FeFe]-氢化酶，通过在一个方向或另一个方向施加不成比例的速率加速度，跨越六个数量级。高分辨率结构工作、生化分析和计算模型的结合表明，蛋白质次级相互作用直接影响活性位点金属簇不同氧化态的相对稳定/不稳定。这种氧化态的选择性稳定或不稳定可以优先促进氢氧化或质子还原，并且代表了一个简单而优雅的模型，通过该模型蛋白质催化位点可以赋予催化偏向。

更新日期：2019-12-09

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