Flavodiiron nitric oxide reductases: Recent developments in the mechanistic study and model chemistry for the catalytic reduction of NO

Khatua, Suman; Majumdar, Amit

doi:10.1016/j.jinorgbio.2014.09.018

Cited by 45 publications

(86 citation statements)

References 83 publications

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“…[4] As for O 2 activation/reduction,NOreduction can also be promoted in nature by diiron enzymes.F lavo-diiron NO reductases (FNORs), which belong to the widespread family of flavo-diiron proteins (FDPs), are found in all three life domains of bacteria, archaea, and protozoan pathogens,a re such non-heme diiron enzymes. [5][6][7] Further to the O 2 reductase activity of FDPs,F NORs exhibit NO reductase (NOR) activity by converting NO to N 2 Othat can directly modulate ab road range of ligand-gated ion channels in our body. Utilizing FNORs,p athogenic bacteria can detoxify NO, preventing it from reaching toxic levels,t hereby gaining resistance to the central immune agent NO in humans.…”

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confidence: 99%

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

Lai

et al. 2019

Angew Chem Int Ed

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The second coordination sphere constitutes adistinguishing factor in the active site to modulate enzymatic reactivity.T ou nravel the origin of NO-to-N 2 Or eduction activity of non-heme diiron enzymes,herein we report astrong second-coordination-sphere interaction between ac onserved Tyr 197 and the key iron-nitrosyl intermediate of Tm FDP (flavo-diiron protein), which leads to decreased reaction barriers towards N-N formation and N-O cleavage in NO reduction. This finding supports the direct coupling of diiron dinitrosyl as the N-N formation mode in our QM/MM modeling,a nd reconciles the mechanistic controversy of external reduction between FDPs and synthetic biomimetics of the iron-nitrosyls.T his work highlights the application of QM/MM 57 Fe Mçssbauer modeling in elucidating the structural features of not only first, but also second coordination spheres of the key transient species involved in NO/O 2 activation by non-heme diiron enzymes.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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confidence: 99%

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

Lai

et al. 2019

Angew Chem Int Ed

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“…[2] More recently, the one-electronreduced form of NO, nitroxyl (NO  /HNO), has been shown to mediate a wide range of biological responses. [3] For example, both ferric and ferrous hemes are capable of binding HNO to form {FeNO} 7 and {Fe(H)NO} 8 complexes, respectively. [4] Such {Fe(H)NO} 8 type species have also been proposed as key intermediates in the catalytic cycles of fungal NO reductase (Cyt.…”

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The Fe₂(NO)₂ Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry

et al. 2019

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“…Binuclear iron sites are employed by enzymes for varied biological processes that entail dioxygen activation (hemerythrin, MMO, RNRs), NO reduction (FNORs), and H 2 chemistry, and feature in the active sites of hydrolases (PAPs, GliJ) . The combination of two redox‐active iron centers in close proximity confers advantages for catalysis, including cooperative binding and activation of substrates, and the use of both metal ions for multi‐electron processes.…”

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Structural Differences and Redox Properties of Unsymmetric Diiron PDIxCy Complexes

2020

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We present two bimetallic iron complexes, [Fe 2 (PDIeCy)(OTf ) 4 ] (1) and [Fe 2 (PDIpCy)(THF)(OTf ) 4 ] (2) coordinated by an unsymmetric ligand. The new ligand, PDIeCy (PDI = pyridyldiimine; e = ethyl; Cy = cyclam), is a variant of the previously reported PDIpCy (p = propyl) ligand, featuring a shorter linker between the two metal coordination sites. The structural and electronic properties of 1 and 2, both in the solid and solution state, were analyzed by means of X-ray crystallography, and spectroscopic methods, including 19 F-NMR. The two ligand platforms yield markedly different diiron structures: the PDIeCy ligand permits formation of a bridged, μ-OTf complex, while the [a] 499 two iron centers of the PDIpCy-based 2 remain unconnected, directly, under all conditions examined. Both compounds contain electronically non-coupled high-spin (S = 2) ferrous centers, as established by Mössbauer spectroscopy and magnetic susceptibility studies. Cyclic voltammetry demonstrates the rich redox chemistry of the compounds, involving both ligand and metal-centered redox processes. Moreover, we synthesized the two-electron reduced [Fe 2 (PDIeCy)] 2+ form of 1, which contains the dianionic PDI 2ligand, and represents a two-electron charge localized complex.group, to support dinuclear complexes thereof (Scheme 1). [29] We reported the synthesis of non-coupled homo-and heterobimetallic Ni-and Zn-containing PDIpCy complexes. We now have focused our attention on diiron compounds. Iron offers Scheme 1. Synthesis of 1 and 2.

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Flavodiiron nitric oxide reductases: Recent developments in the mechanistic study and model chemistry for the catalytic reduction of NO

Cited by 45 publications

References 83 publications

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

The Fe₂(NO)₂ Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry

Structural Differences and Redox Properties of Unsymmetric Diiron PDIxCy Complexes

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Flavodiiron nitric oxide reductases: Recent developments in the mechanistic study and model chemistry for the catalytic reduction of NO

Cited by 45 publications

References 83 publications

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

Origin of Nitric Oxide Reduction Activity in Flavo–Diiron NO Reductase: Key Roles of the Second Coordination Sphere

The Fe2(NO)2 Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry

Structural Differences and Redox Properties of Unsymmetric Diiron PDIxCy Complexes

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The Fe₂(NO)₂ Diamond Core: A Unique Structural Motif In Non‐Heme Iron–NO Chemistry