PMID- 19645472 OWN - NLM STAT- MEDLINE DCOM- 20091229 LR - 20131121 IS - 1520-5126 (Electronic) IS - 0002-7863 (Linking) VI - 131 IP - 33 DP - 2009 Aug 26 TI - Identification of a radical intermediate in the enzymatic reduction of oxygen by a small laccase. PG - 11680-2 LID - 10.1021/ja900751c [doi] AB - The enzyme mechanism of the Cu-containing small laccase (SLAC) from Streptomyces coelicolor has been investigated by optical and electron paramagnetic resonance spectroscopy. A new intermediate was identified after the reaction of molecular oxygen with the reduced trinuclear site of the type-1-depleted (T1D) form of the enzyme. It has the fingerprint of a biradical with a triplet ground state. One of the spins resides on a Cu in the trinuclear site, tentatively identified as the type-2 site, while the other spin derives from a protein-based radical. The latter is tentatively identified as a tyrosyl radical on the basis of the similarity of the optical characteristics with those observed for a Cu tyrosyl radical pair. The spin-spin distance was found to be 5.0 +/- 0.2 A. FAU - Tepper, Armand W J W AU - Tepper AW AD - Leiden Institute of Chemistry, Leiden University, Leiden, The Netherlands. FAU - Milikisyants, Sergey AU - Milikisyants S FAU - Sottini, Silvia AU - Sottini S FAU - Vijgenboom, Erik AU - Vijgenboom E FAU - Groenen, Edgar J J AU - Groenen EJ FAU - Canters, Gerard W AU - Canters GW LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't PL - United States TA - J Am Chem Soc JT - Journal of the American Chemical Society JID - 7503056 RN - 0 (Free Radicals) RN - EC 1.10.3.2 (Laccase) RN - S88TT14065 (Oxygen) SB - IM MH - Absorption MH - Catalytic Domain MH - Electron Spin Resonance Spectroscopy MH - Free Radicals/analysis/metabolism MH - Laccase/chemistry/*metabolism MH - Models, Molecular MH - Oxidation-Reduction MH - Oxygen/*metabolism MH - Sordariales/enzymology MH - Spectrum Analysis EDAT- 2009/08/04 09:00 MHDA- 2009/12/30 06:00 CRDT- 2009/08/04 09:00 PHST- 2009/08/04 09:00 [entrez] PHST- 2009/08/04 09:00 [pubmed] PHST- 2009/12/30 06:00 [medline] AID - 10.1021/ja900751c [doi] PST - ppublish SO - J Am Chem Soc. 2009 Aug 26;131(33):11680-2. doi: 10.1021/ja900751c.