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Acta Physico-Chimica Sinca  2017, Vol. 33 Issue (3): 620-626    DOI: 10.3866/PKU.WHXB201612011
ARTICLE     
Radical Mechanism of Laccase-Catalyzed Catechol Ring-Opening
Ming CHEN1,Lin WANG2,Tian TAN1,Xue-Cai LUO2,Zai ZHENG2,Ruo-Chun YIN2,Ji-Hu SU1,*(),Jiang-Feng DU1
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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Abstract  

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.



Key wordsLaccase      Radical oxidation      Aromatic ring cleavage      Electron paramagnetic resonance spectroscopy      Spin trapping     
Received: 29 September 2016      Published: 01 December 2016
MSC2000:  O643  
Fund:  the National Key Basic Research Program of China (973)(2013CB921802);Fundamental Research Funds for the Central Universities, China, State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources, China(KSL-CUSAb-2012-03)
Corresponding Authors: Ji-Hu SU     E-mail: sujihu@ustc.edu.cn
Cite this article:

Ming CHEN,Lin WANG,Tian TAN,Xue-Cai LUO,Zai ZHENG,Ruo-Chun YIN,Ji-Hu SU,Jiang-Feng DU. Radical Mechanism of Laccase-Catalyzed Catechol Ring-Opening. Acta Physico-Chimica Sinca, 2017, 33(3): 620-626.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201612011     OR     http://www.whxb.pku.edu.cn/Y2017/V33/I3/620

 
 
 
 
 
 
 
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