Resonant Inelastic X-ray Scattering on Ferrous and Ferric bis-imidazole Porphyrin and Cytochrome c: Nature and Role of the Axial Methionine-Fe Bond

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Kroll, ThomasStanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Linac Coherent Light Source, Menlo Pk, CA 94025 USA (author)

Resonant Inelastic X-ray Scattering on Ferrous and Ferric bis-imidazole Porphyrin and Cytochrome c : Nature and Role of the Axial Methionine-Fe Bond

Article/chapterEnglish2014

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2014-12-18
American Chemical Society (ACS),2014
electronicrdacarrier

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LIBRIS-ID:oai:DiVA.org:uu-239173
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-239173URI
https://doi.org/10.1021/ja5100367DOI

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Language:English
Summary in:English

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Subject category:art swepub-publicationtype

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Axial Cu–S(Met) bonds in electron transfer (ET) active sites are generally found to lower their reduction potentials. An axial S(Met) bond is also present in cytochrome c (cyt c) and is generally thought to increase the reduction potential. The highly covalent nature of the porphyrin environment in heme proteins precludes using many spectroscopic approaches to directly study the Fe site to experimentally quantify this bond. Alternatively, L-edge X-ray absorption spectroscopy (XAS) enables one to directly focus on the 3d-orbitals in a highly covalent environment and has previously been successfully applied to porphyrin model complexes. However, this technique cannot be extended to metalloproteins in solution. Here, we use metal K-edge XAS to obtain L-edge like data through 1s2p resonance inelastic X-ray scattering (RIXS). It has been applied here to a bis-imidazole porphyrin model complex and cyt c. The RIXS data on the model complex are directly correlated to L-edge XAS data to develop the complementary nature of these two spectroscopic methods. Comparison between the bis-imidazole model complex and cyt c in ferrous and ferric oxidation states show quantitative differences that reflect differences in axial ligand covalency. The data reveal an increased covalency for the S(Met) relative to N(His) axial ligand and a higher degree of covalency for the ferric states relative to the ferrous states. These results are reproduced by DFT calculations, which are used to evaluate the thermodynamics of the Fe–S(Met) bond and its dependence on redox state. These results provide insight into a number of previous chemical and physical results on cyt c.

Subject headings and genre

NATURVETENSKAP Kemi Fysikalisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Physical Chemistry hsv//eng

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Hadt, Ryan GStanford Univ, Dept Chem, Stanford, CA 94305 USA (author)
Wilson, Samuel AStanford Univ, Dept Chem, Stanford, CA 94305 USA (author)
Lundberg, MarcusUppsala universitet,Teoretisk kemi,Stanford Univ, Dept Chem, Stanford, CA 94305 USA(Swepub:uu)marlu250 (author)
Yan, James J.Stanford Univ, Dept Chem, Stanford, CA 94305 USA (author)
Weng, Tsu-ChienStanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA (author)
Sokaras, DimosthenisStanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA (author)
Alonso-Mori, RobertoStanford Univ, SLAC Natl Accelerator Lab, Linac Coherent Light Source, Menlo Pk, CA 94025 USA (author)
Casa, DiegoArgonne Natl Lab, Adv Photon Source, Argonne, IL 60439 USA (author)
Upton, Mary H.Argonne Natl Lab, Adv Photon Source, Argonne, IL 60439 USA (author)
Hedman, BrittStanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA (author)
Hodgson, Keith O.Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA (author)
Solomon, Edward I.Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA (author)
Stanford Univ, Dept Chem, Stanford, CA 94305 USA; Stanford Univ, SLAC Natl Accelerator Lab, Linac Coherent Light Source, Menlo Pk, CA 94025 USAStanford Univ, Dept Chem, Stanford, CA 94305 USA (creator_code:org_t)

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In:Journal of the American Chemical Society: American Chemical Society (ACS)136:52, s. 18087-180990002-78631520-5126

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By the author/editor: Kroll, Thomas; Hadt, Ryan G; Wilson, Samuel A; Lundberg, Marcus; Yan, James J.; Weng, Tsu-Chien; show more...; Sokaras, Dimosth ...; Alonso-Mori, Rob ...; Casa, Diego; Upton, Mary H.; Hedman, Britt; Hodgson, Keith O ...; Solomon, Edward ...; show less...

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