Oxygen Binding, Activation, and Reduction to Water by Copper Proteins

Solomon, Edward I.; Chen, Peng; Metz, Markus; Lee, Sang‐Kyu; Palmer, Amy E.

doi:10.1002/1521-3773(20011217)40:24<4570::aid-anie4570>3.0.co;2-4

Cited by 806 publications

(622 citation statements)

References 79 publications

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“…The His456.458Lys mutant showed BO and ferroxidase activities, indicating that the electron from a substrate is finally transferred to dioxygen via type I Cu and the mutated trinuclear center (18)(19)(20)(21). However, the drastic decreases in the enzyme activities of His456.458Lys would have been brought about by the change in the redox potential of the type III Cu centers (the substitution of Lys for His would lower the redox potential of type III Cu, significantly suppressing the rate of intramolecular electron transfer) and/or by lowering of the affinity of the trinuclear center towards dioxygen (Table 2).…”

Section: His456458lys Mutant-mentioning

confidence: 99%

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Shimizu¹

2003

Journal of Biochemistry

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Type III Cu ligand, His456 and His458, of Myrothecium verrucaria (MT-1) bilirubin oxidases (BO) [EC 1.3.3.5] were doubly mutated as to Lys, Asp, and Val. In spite of perturbation of the type III Cu centers, these mutants were pale blue or colourless when isolated. However, they became intense blue on reaction with reducing agents such as dithionite, ascorbate, hexacyanoferrate(II), and octacyanotangstate(IV) under air, or with an oxidizing agent such as hexacyanoferrate(III), indicating that they are in mixed forms when expressed in Aspergillus oryzae. His456.458Lys and His456.458Asp mutated as to potential coordinating groups showed weak BO and ferroxidase activities, while His 456.458Val mutated as to non-coordinating groups showed no enzyme activity at all.

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Section: His456458lys Mutant-mentioning

confidence: 99%

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Shimizu¹

2003

Journal of Biochemistry

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“…[1][2][3][4][5][6][7][8] Tyrosinase 1,5,6,9 is one example of an enzyme whose active site incorporates a Cu 2 O 2 core, and substantial effort has also been devoted to the characterization of smaller inorganic models characterized by the same core. 2, [10][11][12][13][14][15][16][17][18] There are several motifs for the binding of molecular O 2 to two supported copper(I) atoms ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

et al. 2006

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The relative energetics of µ-η 1 :η 1 (trans end-on) and µ-η 2 :η 2 (side-on) peroxo isomers of Cu 2 O 2 fragments supported by 0, 2, 4, and 6 ammonia ligands have been computed with various density functional, coupledcluster, and multiconfigurational protocols. There is substantial disagreement between the different levels for most cases, although completely renormalized coupled-cluster methods appear to offer the most reliable predictions. The significant biradical character of the end-on peroxo isomer proves problematic for the density functionals, while the demands on active space size and the need to account for interactions between different states in second-order perturbation theory prove challenging for the multireference treatments. In the latter case, it proved impossible to achieve any convincing convergence.

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“…1 Nature exe--cutes this kinetically demanding multi--proton, multi--electron interconversion with remarkable selectivity and efficiency. Oxygen evolution is carried out at the Mn 4 Ca co--factor of the oxygen evolving complex of photosystem II 2 whereas oxygen reduction is carried out at the heme/Cu ac--tive site of cytochrome C oxidase 3 and Cu 3 cluster active sites of multicopper oxidases. 4 While these catalysts operate effi--ciently and selectively under benign conditions of neutral pH and ambient temperature and pressure, precious and base metal containing heterogeneous catalysts typically require highly alkaline or acidic electrolytes (Figure 1).…”

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confidence: 99%

Heazlewoodite, Ni₃S₂: A Potent Catalyst for Oxygen Reduction to Water under Benign Conditions

et al. 2015

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ABSTRACT:Electrodeposited thin films and nanoparticles of Ni 3 S 2 are highly active, poison and corrosion resistant catalysts for oxygen reduction to water at neutral pH. In pH 7 phosphate buffer, Ni 3 S 2 displays catalytic onset at 0.8 V vs the reversible hydrogen electrode, a Tafel slope of 109 mV/decade, and high Faradaic efficiency for four--electron reduction of O 2 to water. Under these conditions, the activity and stability of Ni 3 S 2 exceeds that of polycrystalline platinum and manganese, nickel, and cobalt oxides illustrating the catalytic potential of pairing labile first row transition metal active sites with a more covalent sulfide host lattice.The interconversion of water and O 2 is an essential chemistry underlying a future renewable energy economy. 1 Nature exe--cutes this kinetically demanding multi--proton, multi--electron interconversion with remarkable selectivity and efficiency. Oxygen evolution is carried out at the Mn 4 Ca co--factor of the oxygen evolving complex of photosystem II 2 whereas oxygen reduction is carried out at the heme/Cu ac--tive site of cytochrome C oxidase 3 and Cu 3 cluster active sites of multicopper oxidases. 4 While these catalysts operate effi--ciently and selectively under benign conditions of neutral pH and ambient temperature and pressure, precious and base metal containing heterogeneous catalysts typically require highly alkaline or acidic electrolytes ( Figure 1).The paucity of heterogeneous electrocatalysts capable of efficient oxygen reduction at neutral pH 5 arises from two seemingly divergent kinetic/materials requirements: 1) the catalyst must remain active in the presence of buffering elec--trolytes that are required to maintain neutral pH stability and deliver protons to drive the proton--coupled electron transfer (PCET) activation of O 2 6 and 2) the catalyst must resist protolytic corrosion under reducing conditions. Pre--cious metal catalysts such as Pt and Au meet the latter re--quirement but also strongly adsorb buffering electrolyte ions such as phosphate, degrading their catalytic efficiency. 7 In contrast, low valent mid to late first row transition metal ions are substitutionally labile, 8 allowing them to meet the first requirement, but this very property makes their corre--sponding oxides unstable with respect to corrosion in all but highly alkaline environments. 9Unlike metal oxides, bonding in transition metal sulfides is more covalent, inhibiting their corrosion under similar con--ditions. 10 Thus, we envisioned that both of the above re--quirements could be met if a labile first row transition metal active site ion can be exposed at the surface of a sulfide host lattice. Here, we illustrate the effectiveness of this design strategy by uncovering a novel earth abundant catalyst for oxygen reduction at neutral pH, the heazlewoodite phase of nickel sulfide, Ni 3 S 2 . Under phosphate buffered neutral pH conditions, Ni 3 S 2 outperforms state of the art ORR catalysts including MnO x and platinum owing to its unique combina--tion of labile ...

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Oxygen Binding, Activation, and Reduction to Water by Copper Proteins

Cited by 806 publications

References 79 publications

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

Heazlewoodite, Ni₃S₂: A Potent Catalyst for Oxygen Reduction to Water under Benign Conditions

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Oxygen Binding, Activation, and Reduction to Water by Copper Proteins

Cited by 806 publications

References 79 publications

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Type III Cu Mutants of Myrothecium verrucaria Bilirubin Oxidase

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu2O2 Models

Heazlewoodite, Ni3S2: A Potent Catalyst for Oxygen Reduction to Water under Benign Conditions

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Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

Heazlewoodite, Ni₃S₂: A Potent Catalyst for Oxygen Reduction to Water under Benign Conditions