| http://purl.uniprot.org/citations/16401082 | http://www.w3.org/1999/02/22-rdf-syntax-ns#type | http://purl.uniprot.org/core/Journal_Citation |
| http://purl.uniprot.org/citations/16401082 | http://www.w3.org/2000/01/rdf-schema#comment | "Cytochromes P450cam and P450BM3 oxidize alpha- and beta-thujone into multiple products, including 7-hydroxy-alpha-(or beta-)thujone, 7,8-dehydro-alpha-(or beta-)thujone, 4-hydroxy-alpha-(or beta-)thujone, 2-hydroxy-alpha-(or beta-)thujone, 5-hydroxy-5-isopropyl-2-methyl-2-cyclohexen-1-one, 4,10-dehydrothujone, and carvacrol. Quantitative analysis of the 4-hydroxylated isomers and the ring-opened product indicates that the hydroxylation proceeds via a radical mechanism with a radical recombination rate ranging from 0.7 +/- 0.3 x 10(10) s(-1) to 12.5 +/-3 x 10(10) s(-1) for the trapping of the carbon radical by the iron-bound hydroxyl radical equivalent. 7-[2H]-alpha-Thujone has been synthesized and used to amplify C-4 hydroxylation in situations where uninformative C-7 hydroxylation is the dominant reaction. The involvement of a carbon radical intermediate is confirmed by the observation of inversion of stereochemistry of the methyl-substituted C-4 carbon during the hydroxylation. With an L244A mutation that slightly increases the P450(cam) active-site volume, this inversion is observed in up to 40% of the C-4 hydroxylated products. The oxidation of alpha-thujone by human CYP1A2, CYP2C9, CYP2C19, CYP2D6, CYP2E1, and CYP3A4 occurs with up to 80% C-4 methyl inversion, in agreement with a dominant radical hydroxylation mechanism. Three minor desaturation products are produced, with at least one of them via a cationic pathway. The cation involved is proposed to form by electron abstraction from a radical intermediate. The absence of a solvent deuterium isotope effect on product distribution in the P450cam reaction precludes a significant role for the P450 ferric hydroperoxide intermediate in substrate hydroxylation. The results indicate that carbon hydroxylation is catalyzed exclusively by a P450 ferryl species via radical intermediates whose detailed properties are substrate- and enzyme-dependent."xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.org/dc/terms/identifier | "doi:10.1021/bi051840z"xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/author | "Jiang Y."xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/author | "He X."xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/author | "Ortiz de Montellano P.R."xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/date | "2006"xsd:gYear |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/name | "Biochemistry"xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/pages | "533-542"xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/title | "Radical intermediates in the catalytic oxidation of hydrocarbons by bacterial and human cytochrome P450 enzymes."xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://purl.uniprot.org/core/volume | "45"xsd:string |
| http://purl.uniprot.org/citations/16401082 | http://www.w3.org/2004/02/skos/core#exactMatch | http://purl.uniprot.org/pubmed/16401082 |
| http://purl.uniprot.org/citations/16401082 | http://xmlns.com/foaf/0.1/primaryTopicOf | https://pubmed.ncbi.nlm.nih.gov/16401082 |
| http://purl.uniprot.org/uniprot/P08684#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |
| http://purl.uniprot.org/uniprot/P05181#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |
| http://purl.uniprot.org/uniprot/P33261#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |
| http://purl.uniprot.org/uniprot/P11712#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |
| http://purl.uniprot.org/uniprot/P10635#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |
| http://purl.uniprot.org/uniprot/P05177#attribution-62766D287EEF7625772760E6174C1054 | http://purl.uniprot.org/core/source | http://purl.uniprot.org/citations/16401082 |