Distinguishing Protonation States of Histidine Ligands to the Oxidized Rieske Iron-Sulfur Cluster through N-15 Vibrational Frequency Shifts

作者：Jagger Benjamin R; Koval Ashlyn M; Wheeler Ralph A^*

来源：ChemPhysChem, 2016, 17(2): 216-220.

DOI：10.1002/cphc.201500838

• broken symmetry
• cytochromes
• density functional calculations
• electron transfer
• Rieske

The Rieske [2Fe-2S] cluster is a vital component of many oxidoreductases, including mitochondrial cytochromebc1; its chloroplast equivalent, cytochromeb6f; one class of dioxygenases; and arsenite oxidase. The Rieske cluster acts as an electron shuttle and its reduction is believed to couple with protonation of one of the clusters His ligands. In cytochromesbc1 and b6f, for example, the Rieske cluster acts as the first electron acceptor in a modified Q cycle. The protonation states of the clusters His ligands determine its ability to accept a proton and possibly an electron through a hydrogen bond to the electron carrier, ubiquinol. Experimental determination of the protonation states of a Rieske clusters two His ligands by NMR spectroscopy is difficult, due to the close proximity of the two paramagnetic iron atoms of the cluster. Therefore, this work reports density functional calculations and proposes that difference vibrational spectroscopy with N-15 isotopic substitution may be used to assign the protonation states of the His ligands of the oxidized Rieske [2Fe-2S] complex.

• 出版日期2016-1-18