Abstract
Enzymatic polymerization of phenolic compounds (catechol, resorcinol, and hydroquinone) was carried out using laccase. The mechanism of polymerization and the structures of the polymers were evaluated in terms of UV–Vis and Fourier transform infrared spectroscopy. The molecular weights of the produced polyphenols were determined with GPC. The results showed that the phenolic monomers firstly turned into quinone intermediates by laccase catalysis. Through further oxidation, the intermediates formed covalent bonds. Finally, catechol units were linked together with ether bonds, and both resorcinol and hydroquinone units were linked together with C-C bonds. The number-average molecular weights of the polyphenols ranged from 1,000 to 1,400 Da (corresponding to the degree of polymerization that varied from 10 to 12) with a lower polydispersity value of about 1.10, showing selective polymerization of phenolic compounds catalyzed by laccase.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Cavaco-Paulo, A., & Gübitz, G. M. (2003). Textile processing with enzymes (pp. 23–38). Cambridge: Woodhead Publishing Limited.
Hudlicky, T. (2011). Introduction to enzymes in synthesis. Chem Rev, 111, 3995–3997.
Galante, Y. M., & Formantici, C. (2003). Enzyme applications in detergency and in manufacturing industries. Current Organic Chemistry, 7, 1399–1422.
Riva, S. (2006). Laccases: blue enzymes for green chemistry. Trends Biotechnol, 24, 119–226.
Desai, S. S., & Nityanand, C. (2011). Microbial laccases and their applications: a review. Asian Journal of Biotechnology, 3, 98–124.
Polak, J., & Jarosz-Wilkolazka, A. (2012). Fungal laccases as green catalysts for dye synthesis. Process Biochem, 2012(47), 1295–1307.
Liqiang, T., Branford-White, C., Wang, W., et al. (2012). Laccase-mediated system pretreatment to enhance the effect of hydrogen peroxide bleaching of cotton fabric. Int J Biol Macromol, 50, 782–787.
Claus, H., Faber, G., & König, H. (2002). Redox-mediated decolorization of synthetic dyes by fungal laccasse. Appl Microbiol Biotechnol, 59, 672–678.
Montazer, M., Dadashian, F., Hemmatinejad, N., et al. (2009). Treatment of wool with laccase and dyeing with madder. Appl Biochem Biotechnol, 158, 685–693.
Campos, R., & Cavaco-Paulo, A. (2001). Indigo degradation with laccases from Polyporus sp. and Sclerotium rolfsii. Textile Research Journal, 71, 420–424.
Kim, S., Silva, C., Zille, A., et al. (2009). Characterization of enzymatically oxidized lignosulfonates and their application on lignocellulosic fabrics. Polymer International, 58, 863–868.
Kim, S., López, C., Güebitz, G., et al. (2008). Biological coloration of flax fabrics with flavonoids using laccase from trametes hirsute. Engineering in Life Sciences, 8, 324–330.
Guimarães, C., Kim, S., Silva, C., et al. (2011). In situ laccase-assisted overdyeing of denim using flavonoids. J Biotechnol, 6, 1272–1279.
Kim, S., Silva, C., Evtuguin, D. V., et al. (2011). Polyoxometalate/laccase-mediated oxidative polymerization of catechol for textile dyeing. Appl Microbiol Biotechnol, 89, 981–987.
Aktas, N., & Tanyolac, A. (2003). Kinetics of laccase-catalyzed oxidative polymerization of catechol. J Mol Catal B: Enzym, 2003(22), 61–69.
Aktas, N., & Tanyolac, A. (2003). Reaction conditions for laccase catalyzed polymerization of catechol. Bioresour Technol, 87, 209–214.
Aktas, N., Sahiner, N., Kantoglu, O., et al. (2003). Biosynthesis and characterization of laccase-catalyzed polycatechol. Journal of Polymers and the Environment, 11, 123–128.
Božič M, Štrancar J, Kokol V. (2013). Laccase-initiated reaction between phenolic acids and chitosan. Reactive and Functional Polymers. doi:10.1016/j.reactfunctpolym. 2013.01.005.
Johannes, C., & Majcherczyk, A. (2000). Natural mediators in the oxidation of polycyclic aromatic hydrocarbons by laccase mediator systems. Appl Environ Microbiol, 66, 524–528.
Uyama, H., & Kobayashi, S. (2002). Enzyme-catalyzed polymerization to functional polymers. J Mol Catal B: Enzym, 19–20, 117–127.
Kobayashi, S., & Higashimura, H. (2003). Oxidative polymerization of phenols revisited. Prog Polym Sci, 28, 1015–1048.
Shin, H., Gübitz, G., & Cavaco-Paulo, A. (2001). "In situ" enzymatically prepared polymers for wool coloration. Macromolecular Materials and Engineering, 286, 691–694.
Kurisawa, M., Chung, J. E., Uyama, H., et al. (2003). Laccase-catalyzed synthesis and antioxidant property of poly(catechin). Macromol Bioscience, 3, 758–764.
Niku-Paavola, M. L., Karhunen, E., et al. (1988). Ligninolytic enzymes of the white-rot fungus Phlebia radiata. Biochemical Journal, 254, 877–884.
Wang, P., Martin, B. D., Parida, S., et al. (1995). Multienzymic synthesis of poly(hydroquinone) for use as a redox polymer. J Am Chem Soc, 117, 12885–12886.
Saha, B., Taylor, K., Bewtra, J., et al. (2011). Laccase-catalyzed removal of phenol and benzenediols from wastewater. Journal of Hazardous, Toxic, and Radioactive Waste, 15, 13–20.
Acknowledgments
Authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (51173071,21274055), Program for New Century Excellent Talents in University (NCET-12-0883), The Natural Science Foundation of Jiangsu Province (BK2011157), Ph.D. Programs Foundation of Ministry of Education of China (20110093110003), the Fundamental Research Funds for the Central Universities (JUSRP51312B), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and the Program for Changjiang Scholars and Innovative Research Team in University (IRT1135).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sun, X., Bai, R., Zhang, Y. et al. Laccase-Catalyzed Oxidative Polymerization of Phenolic Compounds. Appl Biochem Biotechnol 171, 1673–1680 (2013). https://doi.org/10.1007/s12010-013-0463-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12010-013-0463-0