Is Mo involved in hydride binding by the four-electron reduced (E4) intermediate of the nitrogenase MoFe protein?

Journal of the American Chemical Society
Dmitriy LukoyanovBrian M Hoffman

Abstract

We here report the first direct evidence addressing the possible involvement of Mo in substrate interactions during catalytic turnover. When the alpha-70(Ile) MoFe protein is freeze-trapped during H(+) reduction under Ar, the majority of the resting state EPR signal from the molybdenum-iron cofactor (FeMo-co) disappears and is replaced by the S = 1/2 signal of an intermediate that has been shown to be the E(4) MoFe state, which is activated for N(2) binding and reduction through the accumulation of 4 electrons/protons by FeMo-co. ENDOR studies of E(4) showed that it contains two hydrides bound to FeMo-co. We calculate that Mo involvement in hydride binding would require a vector-coupling coefficient for Mo of |K(Mo)| approximately > 0.2 and determine K(Mo) for the E(4) intermediate state through 35 GHz ENDOR measurements of a (95)Mo enriched MoFe protein, further comparing the results with those for the E(0) resting state. The experiments show that Mo of the resting-state FeMo-co is perturbed by the alpha-70(Ile) substitution and that the isotropic (95)Mo hyperfine coupling in E(4) is a(iso) approximately 4 MHz, less than that for the resting state. The decrease in a(iso) for (95)Mo of E(4) from the already small value in the r...Continue Reading

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Citations

Jan 8, 2013·Accounts of Chemical Research·Brian M HoffmanLance C Seefeldt
Jul 25, 2012·Journal of the American Chemical Society·R Adam KinneyBrian M Hoffman
Mar 31, 2012·Proceedings of the National Academy of Sciences of the United States of America·Dmitriy LukoyanovBrian M Hoffman
Nov 15, 2012·Proceedings of the National Academy of Sciences of the United States of America·Zhi-Yong YangLance C Seefeldt
Sep 26, 2013·Proceedings of the National Academy of Sciences of the United States of America·Zhi-Yong YangLance C Seefeldt
Jan 21, 2016·Journal of the American Chemical Society·Dmitriy LukoyanovBrian M Hoffman
Aug 14, 2015·Journal of the American Chemical Society·Yousoon LeeLeslie J Murray
May 14, 2016·Journal of the American Chemical Society·Ilija Čorić, Patrick L Holland
Sep 4, 2014·Journal of the American Chemical Society·Jonathan RittleJonas C Peters
Dec 22, 2017·Journal of Computational Chemistry·Per E M Siegbahn
Oct 26, 2018·Proceedings of the National Academy of Sciences of the United States of America·Simone RaugeiBrian M Hoffman
Jan 18, 2019·Physical Chemistry Chemical Physics : PCCP·Lili Cao, Ulf Ryde
Mar 1, 2012·Angewandte Chemie·Karen P ChiangPatrick L Holland
Jul 28, 2015·Zeitschrift für anorganische und allgemeine Chemie·Ragnar BjornssonSerena DeBeer
Mar 25, 2020·Chemical Science·Albert Th ThorhallssonRagnar Bjornsson
Nov 20, 2016·Angewandte Chemie·Yasuhiro OhkiHisao Nishiyama
Jan 12, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Sergey Zlatogorsky, Michael J Ingleson
Jan 1, 2021·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Casey Van StappenSerena DeBeer
Mar 5, 2020·Chemical Reviews·Andrew J JasniewskiYilin Hu
Mar 17, 2020·Chemical Reviews·Lance C SeefeldtBrian M Hoffman
Apr 3, 2020·Chemical Reviews·Casey Van StappenSerena DeBeer
May 22, 2021·The Journal of Physical Chemistry. a·Carlos Martín-Fernández, Jeremy N Harvey
Jun 15, 2021·Chemical Science·Zhi-Yong YangLance C Seefeldt
Jan 29, 2014·Chemical Reviews·Brian M HoffmanLance C Seefeldt
Apr 15, 2020·Journal of the American Chemical Society·Charles H Arnett, Theodor Agapie
Oct 26, 2012·The Journal of Physical Chemistry. a·Rubik AsatryanEli Ruckenstein
Aug 31, 2017·Journal of the American Chemical Society·Nimesh KhadkaLance C Seefeldt
Jul 10, 2013·Journal of the American Chemical Society·Feng NiCharles E McKenna
Feb 1, 2020·Journal of Chemical Theory and Computation·Lili Cao, Ulf Ryde

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