Department of Chemistry, Duke University, Durham, North Carolina 27708, United States.
Department of Biochemistry, Duke University, Durham, North Carolina 27710, United States.
J Phys Chem B. 2024 Sep 19;128(37):8933-8945. doi: 10.1021/acs.jpcb.4c04637. Epub 2024 Sep 8.
Roller-coaster or undulating free energy landscapes, with alternating high and low potential cofactors, occur frequently in biological redox chains. Yet, there is little understanding of the possible advantages created by these landscapes. We examined the tetraheme subunit associated with reaction centers, comparing the dynamics of the native protein and of hypothetical (in silico) mutants. We computed the variation in the total number of electrons in wild type (WT) and mutant tetrahemes connected to an electron reservoir in the presence of a time-varying potential, as a model for a fluctuating redox environment. We found that roller-coaster free energy landscapes buffer the redox cofactor populations from these fluctuations. The WT roller-coaster landscape slows forward and backward electron transfer in the face of fluctuations, and may offer the advantage of sustaining the reduction of essential cofactors, such as the chlorophyll special pair in photosynthesis, even though an undulating landscape introduces thermodynamically uphill steps in multistep redox chains.
过山车或波浪形的自由能景观,具有交替的高和低势能辅助因子,在生物氧化还原链中经常出现。然而,对于这些景观可能带来的优势,人们知之甚少。我们研究了与反应中心相关的四血红素亚基,比较了天然蛋白和假设的(计算机模拟)突变体的动力学。我们计算了在时变势存在下,与电子储库相连的野生型(WT)和突变四血红素中总电子数的变化,作为波动氧化还原环境的模型。我们发现,过山车式的自由能景观缓冲了氧化还原辅助因子对这些波动的影响。WT 过山车式景观减缓了面对波动时的电子得失,并且可能具有维持重要辅助因子还原的优势,例如光合作用中的叶绿素特殊对,尽管在多步氧化还原链中,波浪形景观会引入热力学上坡步骤。
J Phys Chem B. 2024-9-19
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