Theory Demonstrated a “Coupled” Mechanism for O2 Activation and Substrate Hydroxylation by Binuclear Copper Monooxygenases

2019 ◽  
Vol 141 (50) ◽  
pp. 19776-19789 ◽  
Author(s):  
Peng Wu ◽  
Fangfang Fan ◽  
Jinshuai Song ◽  
Wei Peng ◽  
Jia Liu ◽  
...  
Keyword(s):  
Binuclear Copper ◽  
O2 Activation ◽  
Substrate Hydroxylation

scholarly journals Mechanism of O2 activation and substrate hydroxylation in noncoupled binuclear copper monooxygenases

2016 ◽  
Vol 113 (43) ◽  
pp. 12035-12040 ◽  
Author(s):  
Ryan E. Cowley ◽  
Li Tian ◽  
Edward I. Solomon
Keyword(s):  
Long Range ◽  
Density Functional ◽  
Control Mechanism ◽  
Reorganization Energy ◽  
Hydrogen Atom Abstraction ◽  
Binuclear Copper ◽  
Fenton Chemistry ◽  
Late Step ◽  
Hormone Biosynthesis ◽  
Substrate Hydroxylation

Peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM) are copper-dependent enzymes that are vital for neurotransmitter regulation and hormone biosynthesis. These enzymes feature a unique active site consisting of two spatially separated (by 11 Å in PHM) and magnetically noncoupled copper centers that enables 1e– activation of O2 for hydrogen atom abstraction (HAA) of substrate C–H bonds and subsequent hydroxylation. Although the structures of the resting enzymes are known, details of the hydroxylation mechanism and timing of long-range electron transfer (ET) are not clear. This study presents density-functional calculations of the full reaction coordinate, which demonstrate: (i) the importance of the end-on coordination of superoxide to Cu for HAA along the triplet spin surface; (ii) substrate radical rebound to a CuII hydroperoxide favors the proximal, nonprotonated oxygen; and (iii) long-range ET can only occur at a late step with a large driving force, which serves to inhibit deleterious Fenton chemistry. The large inner-sphere reorganization energy at the ET site is used as a control mechanism to arrest premature ET and dictate the correct timing of ET.

Features of Formation of Mononuclear and Binuclear Copper(II) Complexes with 2,2'-Bipyridyl and closo-Decaborate Anion

2020 ◽  
Vol 65 (9) ◽  
pp. 1343-1350
Author(s):  
E. A. Malinina ◽  
V. V. Avdeeva ◽  
S. E. Korolenko ◽  
S. E. Nefedov ◽  
L. V. Goeva ◽  
...  
Keyword(s):  
Binuclear Copper ◽  
Closo Decaborate Anion

Molecular structures and magnetic properties of .mu.-phenolato binuclear copper(II) complexes incorporating chloro, hydroxo, and azido exogenous bridging ligands

1988 ◽  
Vol 27 (21) ◽  
pp. 3710-3716 ◽  
Author(s):  
Azdine Benzekri ◽  
Patrick Dubourdeaux ◽  
Jean Marc Latour ◽  
Jean Laugier ◽  
Paul Rey
Keyword(s):  
Magnetic Properties ◽  
Molecular Structures ◽  
Binuclear Copper ◽  
Bridging Ligands

Chemical and Spectroscopic Studies of the Binuclear Copper Active Site

1982 ◽  
pp. 263-290
Author(s):  
Richard S. Himmelwright ◽  
Nancy C. Eickman ◽  
Aloysius F. Hepp ◽  
Edward I. Solomon
Keyword(s):  
Active Site ◽  
Spectroscopic Studies ◽  
Binuclear Copper

scholarly journals Direct measurement of enthalpy and entropy changes in NH3 promoted O2 activation over Cu‐CHA at low temperature

ChemCatChem ◽  
2021 ◽  
Author(s):  
Xueting Wang ◽  
Lin Chen ◽  
Peter N. R. Vennestrøm ◽  
Ton V. W. Janssens ◽  
Jonas Jansson ◽  
...  
Keyword(s):  
Low Temperature ◽  
Direct Measurement ◽  
O2 Activation ◽  
Entropy Changes ◽  
Enthalpy And Entropy Changes ◽  
Enthalpy And Entropy
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