Rationally tuning the reduction potential of a single cupredoxin beyond the natural range.
Rationally tuning the reduction potential of a single cupredoxin beyond the natural range.
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氧化还原过程是化学和生物学中许多功能的核心，从光合作用和呼吸作用中的远程电子转移（ET）到工业和燃料电池研究中的催化作用。大自然通过仅使用有限数量的氧化还原活性剂来实现这些功能。在这些领域中的一个长期存在的问题是如何在氧化还原活性位点或ET性质几乎没有变化的情况下在宽范围内微调氧化还原电位。解决这个问题不仅将推进我们对氧化还原过程中长程非共价相互作用作用的基本理解，而且还允许设计具有定制氧化还原电位的氧化还原活性蛋白质，用于诸如人工光合中心或用于能量转换的燃料电池催化剂的应用。我们在这里已经证明，两个重要的二级配位圈相互作用（疏水性和氢键）能够将铜氧还蛋白天青（Az）的还原电位调节到700 mV范围以上，超过任何单核铜氧还蛋白报道的最高和最低还原电位，而不会干扰金属结合位点超出铜氧还蛋白家族的典型结合位点。我们还表明，个人的结构特征的影响是加性的，氧化还原电位调整的AZ现在是可预测的整个范围内的铜氧还蛋白电位。
Redox processes are at the heart of numerous functions in chemistry and biology, from long-range electron transfer (ET) in photosynthesis and respiration to catalysis in industrial and fuel cell research. Nature accomplishes these functions by employing only a limited number of redox-active agents. A long-standing issue in these fields is how redox potentials are fine-tuned over a broad range with little change to the redox-active site or ET properties. Resolving this issue will not only advance our fundamental understanding of the roles of long-range, non-covalent interactions in redox processes, but also allow for design of redox-active proteins having tailor-made redox potentials for applications such as artificial photosynthetic centers or fuel cell catalysts for energy conversion. We have shown here that two important secondary coordination sphere interactions, hydrophobicity and hydrogen-bonding, are capable of tuning the reduction potential of the cupredoxin azurin (Az) over a 700 mV range, surpassing the highest and lowest reduction potentials reported for any mononuclear cupredoxin, without perturbing the metal binding site beyond what is typical for the cupredoxin family of proteins. We also demonstrate that the effects of individual structural features are additive and that redox potential tuning of Az is now predictable across the full range of cupredoxin potentials.
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