ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2017,Vol.33>> Issue(3)>> 620-626     doi: 10.3866/PKU.WHXB201612011         中文摘要
Radical Mechanism of Laccase-Catalyzed Catechol Ring-Opening
CHEN Ming1, WANG Lin2, TAN Tian1, LUO Xue-Cai2, ZHENG Zai2, YIN Ruo-Chun2, SU Ji-Hu1, DU Jiang-Feng1
1 CAS Key Laboratory of Microscale Magnetic Resonance, Department of Modern Physics, University of Science and Technology of China, Hefei 230026, P. R. China;
2 Inspiration Center for Bio-manufacture, School of Life Sciences, Anhui University, Hefei 230601, P. R. China
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Enzyme-catalyzed reactions are a prominent field of research in green chemistry. Laccase is a multicopper oxidase, which we used to study the oxidation of catechol. A mechanism for this ring-opening reaction is also proposed. A o-benzosemiquinone radical was the initial nascent product of catechol oxidation during the catalytic reaction. This radical underwent two reaction pathways:(1) formation of an intramolecular adduct, which gave a carbon-centered furan-derived radical trapped by 5,5-dimethyl-1-pyrroline-N-oxide (DMPO); (2) formation of an intermolecular adduct producing dimeric and trimeric oligomers, as resolved by mass spectrometry. Products of the furan-like intermediate were also characterized by 1H-NMR. Simultaneously, a hydroxyl radical (·OH) originating from the water solvent was identified by 17O-isotope tracing. The kinetics of this radical were also evident with substrates including 3-and 4-methyl catechol, but not with resorcinol and hydroquinone isomers, 3-and 4-nitro catechol, and 2,3-dihydroxynaphthalene. The mechanism of selective activation and ring-opening at the C4-C5 site is discussed. This reaction is distinct from intra-and extra-diol ringcleavages catalyzed by catechol dioxygenase. These results are meaningful for mimicking laccase catalysis to further protein design.

Keywords: Laccase   Radical oxidation   Aromatic ring cleavage   Electron paramagnetic resonance spectroscopy   Spin trapping  
Received: 2016-09-29 Accepted: 2016-12-01 Publication Date (Web): 2016-12-01
Corresponding Authors: SU Ji-Hu Email:

Fund: The project was supported by the National Key Basic Research Program of China (973)(2013CB921802);and Fundamental Research Funds for the Central Universities,China,State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources,China (KSL-CUSAb-2012-03)

Cite this article: CHEN Ming, WANG Lin, TAN Tian, LUO Xue-Cai, ZHENG Zai, YIN Ruo-Chun, SU Ji-Hu, DU Jiang-Feng. Radical Mechanism of Laccase-Catalyzed Catechol Ring-Opening[J]. Acta Phys. -Chim. Sin., 2017,33 (3): 620-626.    doi: 10.3866/PKU.WHXB201612011

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