Laccase-catalysed functionalisation of TMP with tyramine

Abstract Modified wood fibres open new perspectives to create value-added products based on renewable raw materials. An interesting option is the targeted modification of fibre surfaces by oxidative enzymes. This two-stage functionalisation method consists of enzymatic activation of fibre surfaces followed by addition of radicalised compounds reacting preferentially by radical coupling. In this work, the activation of bleached and unbleached softwood TMPs with laccase isolated from Trametes hirsuta was studied. The formation and stability of the radicals were studied by EPR spectroscopy. The reaction of the radicals with 3-hydroxytyramine hydrochloride and the type of chemical linkages were investigated. EPR, ESCA and FTIR spectroscopy were used for analysis. Bleached TMP was radicalised more efficiently than unbleached TMP. The radicals were unstable, as 90% of them were quenched within a few hours. Their lifetime was, however, found to be adequately long for performing coupling reactions. Bonding of new compounds to pulps via radical reactions thus seems to be possible.

[1]  M. Niku-Paavola,et al.  Ligninolytic enzymes of the white-rot fungus Phlebia radiata. , 1988, The Biochemical journal.

[2]  L. Viikari,et al.  Effects of laccase/HBT treatment on pulp and lignin structures , 1999 .

[3]  C. Felby,et al.  Enhanced Auto Adhesion of Wood Fibers Using Phenol Oxidases , 1997 .

[4]  M. A. Jermyn Horseradish peroxidase. , 1952, Nature.

[5]  Robin Rowshangohar You say you want a revolution , 2006 .

[6]  R. Farrell,et al.  Enzymatic "combustion": the microbial degradation of lignin. , 1987, Annual review of microbiology.

[7]  Feng Xu,et al.  Laccases: A Useful Group of Oxidoreductive Enzymes , 1999 .

[8]  A. Ragauskas,et al.  Sculpting the molecular weight of lignin via laccase , 2001 .

[9]  C. Thurston The structure and function of fungal laccases , 1994 .

[10]  A. Ragauskas,et al.  Evaluating laccase-facilitated coupling of phenolic acids to high-yield kraft pulps , 2001 .

[11]  J. Buchert,et al.  Activity of laccase on unbleached and bleached thermomechanical pulp , 2003 .

[12]  J. Buchert,et al.  Modification of Spruce Lignans with Trametes hirsuta Laccase , 2002 .

[13]  J. Buchert,et al.  Lignocellulose processing with oxidative enzymes , 2003 .

[14]  I. Kilpeläinen,et al.  Oxidative Coupling of Phenols and the Biosynthesis of Lignin , 1998 .

[15]  P. Widsten,et al.  Radical formation on laccase treatment of wood defibrated at high temperatures , 2002 .

[16]  D. Cullen,et al.  9 Enzymology and Molecular Genetics of Wood Degradation by White-Rot Fungi , 1998 .

[17]  A. Hüttermann,et al.  Modification of lignin for the production of new compounded materials , 2001, Applied Microbiology and Biotechnology.

[18]  C. Felby,et al.  Pilot-scale production of fiberboards made by laccase oxidized wood fibers: board properties and evidence for cross-linking of lignin , 2002 .

[19]  S. Saka Structure and Chemical Composition of Wood as a Natural Composite Material , 1993 .

[20]  A. Ragauskas,et al.  Modification of High Lignin Content Kraft Pulps with Laccase to Improve Paper Strength Properties. 1. Laccase Treatment in the Presence of Gallic Acid , 2008, Biotechnology progress.

[21]  A. Ragauskas,et al.  Improving Laccase‐Facilitated Grafting of 4‐Hydroxybenzoic Acid to High‐Kappa Kraft Pulps , 2005 .

[22]  L. Skibsted,et al.  Identification and quantification of radical reaction intermediates by electron spin resonance spectrometry of laccase-catalyzed oxidation of wood fibers from beech (Fagus sylvatica) , 1997, Applied Microbiology and Biotechnology.

[23]  J. Buchert,et al.  On surface distributions in natural cellulosic fibres , 2004 .

[24]  J. Buchert,et al.  Oxidation of milled wood lignin with laccase, tyrosinase and horseradish peroxidase , 2005, Applied Microbiology and Biotechnology.