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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: sujihu@ustc.edu.cn

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

(1) Solomon, E. I.; Sundaram, U. M.; Machonkin, T. E. Chem. Rev.1996, 96, 2563. doi: 10.1021/cr950046o
(2) Solomon, E. I.; Heppner, D. E.; Johnston, E. M.; Ginsbach, J.W.; Cirera, J.; Qayyum, M.; Kieber-Emmons, M. T.; Kjaergaard, C. H.; Hadt, R. G.; Tian, L. Chem. Rev.2014, 114, 3659. doi: 10.1021/cr400327t
(3) ten Have, R.; Teunissen, P. J. M. Chem. Rev.2001, 101, 3397. doi: 10.1021/cr000115l
(4) Jiang, B.; Xu, X. Y.; Li, Z. Y. Chin. J. Org. Chem.2008, 28, 1715.[姜标, 徐向亚, 李祖义. 有机化学, 2008, 28, 1715.]
(5) Lee, S. K.; George, S. D.; Antholine, W. E.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. J. Am. Chem. Soc.2002, 124, 6180. doi: 10.1021/Ja0114052.
(6) Hua, J. L.; Song, C. S.; Wang, G. H.; Cai, M. Z. Acta Phys.-Chim. Sin.1999, 15, 173.[花建丽, 宋才生, 王光辉, 蔡明中. 物理化学学报, 1999, 15, 173.] doi: 10.3866/PKU.WHXB19990215
(7) Ma, G. X.; Zhong, Q. D.; Lu, T. H. Sci. China Chem.2010, 53, 1332. doi: 10.1007/s11426-010-3186-x
(8) Zeng, H.; Liao, L.W.; Li, M. F.; Tao, Q.; Kang, J.; Chen, Y. X.Acta Phys.-Chim. Sin.2010, 26, 3217.[曾涵, 廖铃文, 李明芳, 陶骞, 康婧, 陈艳霞. 物理化学学报, 2010, 26, 3217.] doi: 10.3866/Pku.Whxb20101208
(9) Zhang, Q.; Zhang, Y. Q.; Liu, X. Z.; Liang, Y. X.; Zhang, R. F.; Long, N. B. Chin. J. Inorg. Chem.2013, 29, 2065.[张群, 张育淇, 刘晓贞, 梁云霄, 张瑞丰, 龙能兵. 无机化学学报, 2013, 29, 2065.] doi: 10.3969/j.issn.1001-4861.2013.00.324
(10) Li, Y.; Jiang, G. X.; Niu, J. F.; Wang, Y.; Hu, L. J. Prog. Chem.2009, 21, 2028.[李阳, 蒋国翔, 牛军峰, 王颖, 呼丽娟.化学进展, 2009, 21, 2028.]
(11) Gupta, A.; Aartsma, T. J.; Canters, G.W. J. Am. Chem. Soc.2014, 136, 2707. doi: 10.1021/ja411078b
(12) Drauz, K.; Gröger, H.; May, O. Enzyme Catalysis in Organic Synthesis, 3rd ed.; Drauz, K., Gröger, H., May, O. Eds.; Wiley-VCH:Weinheim, 2012.
(13) Polaina, J.; MacCabe, A. P. Industrial Enzymes:Structure,Function, and Applications; Springer:Dordrecht, 2007.
(14) Xu, F.; Damhus, T.; Danielsen, S.; Østergaard, L. H. CatalyticApplications of Laccase. In Modern Biooxidation, Wiley-VCHVerlag GmbH & Co. KGaA, 2007; pp 43-75.
(15) Heppner, D. E.; Kjaergaard, C. H.; Solomon, E. I. J. Am. Chem.Soc.2013, 135, 12212. doi: 10.1021/ja4064525
(16) Heppner, D. E.; Kjaergaard, C. H.; Solomon, E. I. J. Am. Chem.Soc.2014, 136, 17788. doi: 10.1021/ja509150j.
(17) Wan, Y. Y.; Du, Y. M.; Miyakoshi, T. S. Sci. China Ser. B 2008, 51, 669. doi: 10.1007/s11426-008-0071-y
(18) Rappoport, Z. The Chemistry of Phenols;Wiley:Hoboken, NJ, 2003.
(19) Weinshilboum, R. M.; Otterness, D. M.; Szumlanski, C. L.Annu. Rev. Pharmacol. Toxicol 1999, 39, 19. doi: 10.1146/annurev.pharmtox.39.1.19
(20) Brown, C. K.; Vetting, M.W.; Earhart, C. A.; Ohlendorf, D. H.Annu. Rev. Microbiol.2004, 58, 555. doi: 10.1146/annurev.micro.57.030502.090927
(21) Kovaleva, E. G.; Lipscomb, J. D. Science 2007, 316, 453. doi: 10.1126/science.1134697
(22) Zard, S. Z. Advances in Free Radical Chemistry, Vol. 2; JaiPress:Stamford, Conn., 1999.
(23) Chatgilialoglu, C.; Studer, A. Encyclopedia of Radicals in Chemistry, Biology and Materials;Wiley-Blackwell:Oxford, 2012.
(24) Gerson, F.; Huber, W. Electron Spin Resonance Spectroscopy of Organic Radicals;Wiley-VCH:Weinheim, Great Britain, 2003.
(25) Buettner, G. R. Free Radic Biol. Med.1987, 3, 259. doi: 10.1016/S0891-5849(87)80033-3
(26) Alberti, A.; Macciantelli, D. Spin Trapping. In Electron Paramagnetic Resonance, JohnWiley & Sons, Inc.:Hoboken, New Jersey, 2008; pp 285-324.
(27) Sanvoisin, J.; Langley, G. J.; Bugg, T. D. H. J. Am. Chem. Soc.1995, 117, 7836. doi: 10.1021/Ja00134a041
(28) Spence, E. L.; Langley, G. J.; Bugg, T. D. H. J. Am. Chem. Soc.1996, 118, 8336. doi: 10.1021/ja9607704
(29) Lin, G.; Reid, G.; Bugg, T. D. H. J. Am. Chem. Soc.2001, 123, 5030. doi: 10.1021/ja004280u
(30) Xin, M.; Bugg, T. D. H. J. Am. Chem. Soc.2008, 130, 10422. doi: 10.1021/ja8029569
(31) Brivio, M.; Schlosrich, J.; Ahmad, M.; Tolond, C.; Bugg, T. D.H. Org. Biomol. Chem.2009, 7, 1368. doi: 10.1039/b821559f
(32) Mander, L. N.; Williams, C. M. Tetrahedron 2003, 59, 1105. doi: 10.1016/S0040-4020(02)01492-8
(33) Spirkova, K.; Kada, R. Chem. Pap.1987, 41, 787.
(34) Babij, N. R.; McCusker, E. O.; Whiteker, G. T.; Canturk, B.; Choy, N.; Creemer, L. C.; De Amicis, C. V.; Hewlett, N. M.; Johnson, P. L.; Knobelsdorf, J. A.; Li, F. Z.; Lorsbach, B. A.; Nugent, B. M.; Ryan, S. J.; Smith, M. R.; Yang, Q. Org.Process. Res. Dev.2016, 20, 661. doi: 10.1021/acs.oprd.5b00417
(35) Fulmer, G. R.; Miller, A. J. M.; Sherden, N. H.; Gottlieb, H. E.; Nudelman, A.; Stoltz, B. M.; Bercaw, J. E.; Goldberg, K. I.Organometallics 2010, 29, 2176. doi: 10.1021/om100106e
(36) Gunther, H. A. Nmr Spectroscopy:Basic Principles, Concepts and Applications in Chemistry, 3rd ed.; completely revised andupdated edition.
(37) Pietruszka, J.; Wang, C. Green Chemistry 2012, 14, 2402. doi: 10.1039/C2GC35662G
(38) Abdel-Mohsen, H. T.; Conrad, J.; Beifuss, U. J. Org. Chem.2013, 78, 7986. doi: 10.1021/jo401193e
(39) Su, Y. J.; Jia, W.; Jiao, N. Synthesis-Stuttgart 2011, 1678. doi: 10.1055/s-0030-1260028

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