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http://purl.uniprot.org/citations/27936663http://www.w3.org/1999/02/22-rdf-syntax-ns#typehttp://purl.uniprot.org/core/Journal_Citation
http://purl.uniprot.org/citations/27936663http://www.w3.org/1999/02/22-rdf-syntax-ns#typehttp://purl.uniprot.org/core/Journal_Citation
http://purl.uniprot.org/citations/27936663http://www.w3.org/1999/02/22-rdf-syntax-ns#typehttp://purl.uniprot.org/core/Citation
http://purl.uniprot.org/citations/27936663http://www.w3.org/2000/01/rdf-schema#comment"Coproheme decarboxylase catalyzes two sequential oxidative decarboxylations with H2O2 as the oxidant, coproheme III as substrate and cofactor, and heme b as the product. Each reaction breaks a C-C bond and results in net loss of hydride, via steps that are not clear. Solution and solid-state structural characterization of the protein in complex with a substrate analog revealed a highly unconventional H2O2-activating distal environment with the reactive propionic acids (2 and 4) on the opposite side of the porphyrin plane. This suggested that, in contrast to direct C-H bond cleavage catalyzed by a high-valent iron intermediate, the coproheme oxidations must occur through mediating amino acid residues. A tyrosine that hydrogen bonds to propionate 2 in a position analogous to the substrate in ascorbate peroxidase is essential for both decarboxylations, while a lysine that salt bridges to propionate 4 is required solely for the second. A mechanism is proposed in which propionate 2 relays an oxidizing equivalent from a coproheme compound I intermediate to the reactive deprotonated tyrosine, forming Tyr. This residue then abstracts a net hydrogen atom (H) from propionate 2, followed by migration of the unpaired propionyl electron to the coproheme iron to yield the ferric harderoheme and CO2 products. A similar pathway is proposed for decarboxylation of propionate 4, but with a lysine residue as an essential proton shuttle. The proposed reaction suggests an extended relay of heme-mediated e-/H+ transfers and a novel route for the conversion of carboxylic acids to alkenes."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.org/dc/terms/identifier"doi:10.1021/jacs.6b11324"xsd:string
http://purl.uniprot.org/citations/27936663http://purl.org/dc/terms/identifier"doi:10.1021/jacs.6b11324"xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Gauss G.H."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Gauss G.H."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"DuBois J.L."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"DuBois J.L."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Lukat-Rodgers G.S."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Lukat-Rodgers G.S."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Rodgers K.R."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Rodgers K.R."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Streit B.R."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Streit B.R."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Peters J.W."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Peters J.W."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Celis A.I."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Celis A.I."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Moraski G.C."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Moraski G.C."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Shisler K."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/author"Shisler K."xsd:string
http://purl.uniprot.org/citations/27936663http://purl.uniprot.org/core/date"2017"xsd:gYear