Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides

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• 作者：Shabnam Hematian ; Isaac Garcia-Bosch ; Kenneth D. Karlin
• 刊名：Accounts of Chemical Research
• 出版年：2015
• 出版时间：August 18, 2015
• 年：2015
• 卷：48
• 期：8
• 页码：2462-2474
• 全文大小：880K
• ISSN：1520-4898

文摘

Our long-time niche in synthetic biological inorganic chemistry has been to design ligands and generate coordination complexes of copper or iron ions or both, those reacting with dioxygen (O₂) or nitrogen oxides (e.g., nitric oxide (NO_(g)) and nitrite (NO₂^{鈥?/sup>)) or both. As inspiration for this work, we turn to mitochondrial cytochrome c oxidase, which is responsible for dioxygen consumption and is also the predominant target for NO_(g) and nitrite within mitochondria. In this Account, we highlight recent advances in studying synthetic heme/Cu complexes in two respects. First, there is the design, synthesis, and characterization of new O₂ adducts whose further study will add insights into O₂ reductive cleavage chemistry. Second, we describe how related heme/Cu constructs reduce nitrite ion to NO_(g) or the reverse, oxidize NO_(g) to nitrite. The reactions of nitrogen oxides occur as part of CcO鈥檚 function, which is intimately tied to cellular O₂ balance.}