Dereli Busra, Baer Marcel D, Peters John W, Raugei Simone
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, United States.
J Phys Chem Lett. 2025 May 15;16(19):4602-4606. doi: 10.1021/acs.jpclett.5c00616. Epub 2025 May 1.
[4Fe-4S] clusters are ubiquitous in biology and are crucial to the more salient processes in energy metabolism, serving as intermediates in inter- and intramolecular electron transfer pathways. The [4Fe-4S] clusters are more prevalent, serving a variety of functions, and can remarkably adopt a surprising range of reduction potentials spanning more than 1 V. The characteristics of the environment, including charge, solvent access, and geometric distortion, finely modulate the reduction potential of iron/sulfur clusters. However, prior research has not yet systematically addressed cause and effect. In this work, we conducted a thorough theoretical assessment of how charge distribution and structural distortion contribute to the full range of reductions exhibited by biological [4Fe-4S] clusters. The work shows that the most significant contributions can be predicted for electrostatic interactions, which are directionally biased.
[4Fe-4S]簇在生物学中普遍存在，对能量代谢中更为显著的过程至关重要，充当分子间和分子内电子转移途径的中间体。[4Fe-4S]簇更为普遍，具有多种功能，并且能够显著呈现出超过1V的惊人还原电位范围。包括电荷、溶剂可及性和几何畸变在内的环境特征精细地调节铁硫簇的还原电位。然而，先前的研究尚未系统地探讨因果关系。在这项工作中，我们对电荷分布和结构畸变如何促成生物[4Fe-4S]簇所呈现的全部还原范围进行了全面的理论评估。这项工作表明，对于具有方向性偏差的静电相互作用，可以预测出其最显著的贡献。
