Citation: 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 Physico-Chimica Sinica, ;2017, 33(3): 620-626. doi: 10.3866/PKU.WHXB201612011 shu

Radical Mechanism of Laccase-Catalyzed Catechol Ring-Opening

CHEN Ming ^1, ,
WANG Lin ² ,
TAN Tian ¹ ,
LUO Xue-Cai ² ,
ZHENG Zai ² ,
YIN Ruo-Chun ² ,
SU Ji-Hu ¹ ,
DU Jiang-Feng ¹

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

Received Date: 29 September 2016
Revised Date: 1 December 2016

Fund Project: The project was supported by the National Key Basic Research Program of China (973)(2013CB921802)

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.
- Laccase,
- Radical oxidation,
- Aromatic ring cleavage,
- Electron paramagnetic resonance spectroscopy,
- Spin trapping
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