NRVS Studies of the Peroxide Shunt Intermediate in a Rieske Dioxygenase and Its Relation to the Native Fe O Reaction.
The Rieske dioxygenases are a major subclass of mononuclear nonheme iron enzymes that play an important role in bioremediation. Recently, a high-spin Fe-(hydro)-peroxy intermediate (BZDOp) has been trapped in the peroxide shunt reaction of benzoate 1,2-dioxygenase. Defining the structure of this int...
| Publicado en: | Journal of the American Chemical Society Vol. 140; no. 16; pp. 5544 - 5560 |
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| Autores principales: | , , , , , , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
4/25/2018
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=129345644&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 129345644 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 4/25/2018 vid: 140 iid: 16 pid: 997 pub: American Chemical Society artinfo: ui: 129345644 10.1021/jacs.8b01822 ppf: 5544 ppct: 16 formats: tig: atl: NRVS Studies of the Peroxide Shunt Intermediate in a Rieske Dioxygenase and Its Relation to the Native Fe O Reaction. aug: au: Sutherlin, Kyle D. Rivard, Brent S. Böttger, Lars H. Liu, Lei V. Rogers, Melanie S. Srnec, Martin Kiyoung Park Yoshitaka Yoda Shinji Kitao Yasuhiro Kobayashi Makina Saito Makoto Seto Hu, Michael Jiyong Zhao Lipscomb, John D. Solomon, Edward I. affil: Department of Chemistry, Stanford University, Stanford, California 94305, United States Department of Biochemistry, Molecular Biology, & Biophysics, University of Minnesota, Minneapolis, Minnesota 55455, United States J. Heyrovský Institute of Physical Chemistry, The Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Prague 8, Czech Republic Department of Chemistry, KAIST, Daejeon 34141, Republic of Korea Japan Synchrotron Radiation Research Institute, Hyogo 679-5198, Japan Research Reactor Institute, Kyoto University, Osaka 590-0494, Japan Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States su: Peroxides Dioxygenases Bioremediation Hydroperoxy radicals Benzoates Iron Density functional theory sug: subj: Peroxides Dioxygenases Bioremediation Hydroperoxy radicals Benzoates Iron Density functional theory ab: The Rieske dioxygenases are a major subclass of mononuclear nonheme iron enzymes that play an important role in bioremediation. Recently, a high-spin Fe-(hydro)-peroxy intermediate (BZDOp) has been trapped in the peroxide shunt reaction of benzoate 1,2-dioxygenase. Defining the structure of this intermediate is essential to understanding the reactivity of these enzymes. Nuclear resonance vibrational spectroscopy (NRVS) is a recently developed synchrotron technique that is ideal for obtaining vibrational, and thus structural, information on Fe sites, as it gives complete information on all vibrational normal modes containing Fe displacement. In this study, we present NRVS data on BZDOp and assign its structure using these data coupled to experimentally calibrated density functional theory calculations. From this NRVS structure, we define the mechanism for the peroxide shunt reaction. The relevance of the peroxide shunt to the native Fe/O reaction is evaluated. For the native Fe/O reaction, an Fe-superoxo intermediate is found to react directly with substrate. This process, while uphill thermodynamically, is found to be driven by the highly favorable thermodynamics of proton-coupled electron transfer with an electron provided by the Rieske [2Fe-2S] center at a later step in the reaction. These results offer important insight into the relative reactivities of Fe-superoxo and Fe-hydroperoxo species in nonheme Fe biochemistry. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2018 holdings: @attributes: islocal: N |
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