Search Results - "HOFFMAN, Brian M."
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Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage
Published in Chemical reviews (23-04-2014)“…The vital role that nitrogenase plays in sustaining life is examined from a biomolecular perspective. Nitrogen fixation is shown to occur in lightning and the…”
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Particulate methane monooxygenase contains only mononuclear copper centers
Published in Science (American Association for the Advancement of Science) (10-05-2019)“…Bacteria that oxidize methane to methanol are central to mitigating emissions of methane, a potent greenhouse gas. The nature of the copper active site in the…”
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Mechanism of Mo-dependent nitrogenase
Published in Annual review of biochemistry (01-01-2009)“…Nitrogen-fixing bacteria catalyze the reduction of dinitrogen (N(2)) to two ammonia molecules (NH(3)), the major contribution of fixed nitrogen to the…”
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Reductive Elimination of H2 Activates Nitrogenase to Reduce the NN Triple Bond: Characterization of the E4(4H) Janus Intermediate in Wild-Type Enzyme
Published in Journal of the American Chemical Society (24-08-2016)“…We proposed a reductive elimination/oxidative addition (re/oa) mechanism for reduction of N2 to 2NH3 by nitrogenase, based on identification of a…”
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The Elusive 5′-Deoxyadenosyl Radical: Captured and Characterized by Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Spectroscopies
Published in Journal of the American Chemical Society (31-07-2019)“…The 5′-deoxyadenosyl radical (5′-dAdo·) abstracts a substrate H atom as the first step in radical-based transformations catalyzed by…”
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Structural and spectroscopic characterization of an Fe(VI) bis(imido) complex
Published in Science (American Association for the Advancement of Science) (16-10-2020)“…Nitrogen lifts iron to hexavalence The myriad ways that iron can interact with oxygen have been amply studied in biochemical and geochemical contexts. More…”
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Internal dynamics of a supramolecular nanofibre
Published in Nature materials (01-08-2014)“…Variations in the internal conformational dynamics of supramolecular nanostructures may be important for their function, yet such dynamics have been difficult…”
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Mechanism of Nitrogenase H2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects
Published in Journal of the American Chemical Society (27-09-2017)“…Nitrogenase catalyzes the reduction of dinitrogen (N2) to two ammonia (NH3) at its active site FeMo-cofactor through a mechanism involving reductive…”
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Kinetic Understanding of N2 Reduction versus H2 Evolution at the E4(4H) Janus State in the Three Nitrogenases
Published in Biochemistry (Easton) (02-10-2018)“…The enzyme nitrogenase catalyzes the reduction of N2 to ammonia but also that of protons to H2. These reactions compete at the mechanistically central ‘Janus’…”
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From micelles to bicelles: Effect of the membrane on particulate methane monooxygenase activity
Published in The Journal of biological chemistry (06-07-2018)“…Particulate methane monooxygenase (pMMO) is a copper-dependent integral membrane metalloenzyme that converts methane to methanol in methanotrophic bacteria…”
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Electron Transfer within Nitrogenase: Evidence for a Deficit-Spending Mechanism
Published in Biochemistry (Easton) (01-11-2011)“…The reduction of substrates catalyzed by nitrogenase utilizes an electron transfer (ET) chain comprised of three metalloclusters distributed between the two…”
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Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X‑ray Absorption Spectroscopy
Published in Journal of the American Chemical Society (20-07-2016)“…Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an…”
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On reversible H₂ loss upon N₂ binding to FeMo-cofactor of nitrogenase
Published in Proceedings of the National Academy of Sciences - PNAS (08-10-2013)“…Nitrogenase is activated for N ₂ reduction by the accumulation of four electrons/protons on its active site FeMo-cofactor, yielding a state, designated as E ₄,…”
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Electron transfer precedes ATP hydrolysis during nitrogenase catalysis
Published in Proceedings of the National Academy of Sciences - PNAS (08-10-2013)“…The biological reduction of N ₂ to NH ₃ catalyzed by Mo-dependent nitrogenase requires at least eight rounds of a complex cycle of events associated with…”
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A mixed-valent Fe(II)Fe(III) species converts cysteine to an oxazolone/thioamide pair in methanobactin biosynthesis
Published in Proceedings of the National Academy of Sciences - PNAS (29-03-2022)“…SignificanceMethanobactins (Mbns), copper-binding peptidic compounds produced by some bacteria, are candidate therapeutics for human diseases of copper…”
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Characterization of a long overlooked copper protein from methane- and ammonia-oxidizing bacteria
Published in Nature communications (15-10-2018)“…Methane-oxidizing microbes catalyze the oxidation of the greenhouse gas methane using the copper-dependent enzyme particulate methane monooxygenase (pMMO)…”
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Crystal Structure and Characterization of Particulate Methane Monooxygenase from Methylocystis species Strain M
Published in Biochemistry (Easton) (29-11-2011)“…Particulate methane monooxygenase (pMMO) is an integral membrane metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria. Previous…”
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Organometallic and radical intermediates reveal mechanism of diphthamide biosynthesis
Published in Science (American Association for the Advancement of Science) (16-03-2018)“…Diphthamide biosynthesis involves a carbon-carbon bond-forming reaction catalyzed by a radical S-adenosylmethionine (SAM) enzyme that cleaves a carbon-sulfur…”
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Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5′-dAdo• “Free Radical” Is Never Free
Published in Journal of the American Chemical Society (10-06-2015)“…Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-l-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating…”
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Identification of the Valence and Coordination Environment of the Particulate Methane Monooxygenase Copper Centers by Advanced EPR Characterization
Published in Journal of the American Chemical Society (20-08-2014)“…Particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol in methanotrophic bacteria. As a copper-containing enzyme, pMMO has…”
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