title: Activation of dioxygen by copper metalloproteins and insights from model complexes.
abstract: Nature uses dioxygen as a key oxidant in the transformation of biomolecules. Among the enzymes that are utilized for these reactions are copper-containing metalloenzymes, which are responsible for important biological functions such as the regulation of neurotransmitters, dioxygen transport, and cellular respiration. Enzymatic and model system studies work in tandem in order to gain an understanding of the fundamental reductive activation of dioxygen by copper complexes. This review covers the most recent advancements in the structures, spectroscopy, and reaction mechanisms for dioxygen-activating copper proteins and relevant synthetic models thereof. An emphasis has also been placed on cofactor biogenesis, a fundamentally important process whereby biomolecules are post-translationally modified by the pro-enzyme active site to generate cofactors which are essential for the catalytic enzymatic reaction. Significant questions remaining in copper-ion-mediated O2-activation in copper proteins are addressed.
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
authors.forename: David A
authors.initials: DA
authors.lastname: Quist
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
authors.forename: Daniel E
authors.initials: DE
authors.lastname: Diaz
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA.
authors.forename: Jeffrey J
authors.initials: JJ
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA. karlin@jhu.edu.
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D000818:Animals; D020134:Catalytic Domain; D003300:Copper / Q000378:metabolism*; D006801:Humans; D008667:Metalloproteins / Q000737:chemistry / Q000378:metabolism*; D010100:Oxygen / Q000378:metabolism*
chemical_list: D008667:Metalloproteins; D003300:Copper; D010100:Oxygen
keywords: Cofactor biogenesis; Copper; Copper enzymes; Dioxygen activation; Enzymatic mechanisms