Phonon-assisted electron-proton transfer in [FeFe] hydrogenases: Topological role of clusters
Phonon-assisted electron-proton transfer in [FeFe] hydrogenases: Topological role of clusters
复制标题
[FeFe]氢化酶中的声子辅助电子-质子转移：簇的拓扑作用
DOI：
10.1016/j.bpj.2023.03.027
复制
发表时间：
2023
影响因子：
3.4
通讯作者：
Arragain, Simon
中科院分区：
文献类型：
--
作者：
Chalopin, Yann;Cramer, Stephen P.;Arragain, Simon
[FeFe]氢酶是具有合成或消耗分子氢()的独特能力的酶。这一功能依赖于复杂的催化机制，包括活性中心和两个不同的电子和质子转移网络协同工作。通过基于[FeFe]氢酶结构的太赫兹振动的分析，我们能够预测和鉴定在催化位置存在速率促进振动以及与已报道的电子和质子转移网络中涉及的功能残基的耦合。我们的发现表明，团簇的位置受到支架对热涨落的响应的影响，这反过来又通过声子辅助机制驱动电子转移网络的形成。因此，我们解决了通过皮秒动力学将分子结构与催化功能联系起来的问题，同时使用折叠编码的局域振动的概念来提高辅因子或簇带来的功能增益。
[FeFe] hydrogenases are enzymes that have acquired a unique capacity to synthesize or consume molecular hydrogen (). This function relies on a complex catalytic mechanism involving the active site and two distinct electron and proton transfer networks working in concert. By an analysis based on terahertz vibrations of [FeFe] hydrogenase structure, we are able to predict and identify the existence of rate-promoting vibrations at the catalytic site and the coupling with functional residues involved in reported electron and proton transfer networks. Our findings suggest that the positioning of the cluster is influenced by the response of the scaffold to thermal fluctuations, which in turn drives the formation of networks for electron transfer through phonon-assisted mechanisms. Thus, we address the problem of linking the molecular structure to the catalytic function through picosecond dynamics, while raising the functional gain brought by the cofactors or clusters, using the concept of fold-encoded localized vibrations.