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220    Advances in textile biotechnology


                                        H O  H O
                                         2  2  2
                     (a)        HRP                 Compound I
                                R •                     RH

                                  RH    Compound II   R •
                     (b)
                                nH O 2nH O
                                       2
                                   2
                                  2
                            n RH         n R •      *   RH   *
                                   HRP                      n
                     (c)


                          OH             O ·           OH

                      2              2
                              HRP/H O 2                        OH
                                  2



                     9.4  (a) Redox cycle of horseradish peroxidase (HRP). (b) Simplifi ed
                     scheme of the HRP-catalysed oxidation of a substrate. Intermediate
                     radical species can undergo polymerisation by radical–radical
                     coupling. (c) HRP-catalysed phenolic coupling of tyrosine residues in
                     proteins with formation of dityrosine.


              range of substrates and efficiency of degradation of the recalcitrant dyes.

              Because soluble enzymes cannot be exploited on a large scale owing to
              limitations such as stability and reusability, immobilised enzyme systems
              are used. Despite great efforts in this field of study, treatment of wastewater

              on a large scale has not yet been implemented.
                The utility of laccases not only for dye degradation but also for the bio-
              synthesis of new dyes suitable for textile and leather coloration has recently
              been demonstrated (Enaud  et al., 2010). A novel azoanthraquinone dye
              called Laccase Acid Red 1 has been synthesised by means of an immobil-
              ised laccase system. The resulting dye preparation was neither toxic nor
              mutagenic, and displayed good dyeing properties on polyamide fi bres. The
              enzyme-catalysed synthesis of dyes represents a promising safer alternative
              to chemical synthesis, which still poses health and environmental problems.
                There have been few studies on the application of laccases and peroxi-
              dases to the functionalisation of protein fi bres. Lantto et al. (2004) reported
              the laccase-mediated oxidation of wool and model compounds (Cys and
              Tyr) with and without the mediators violuric acid (VA) or 1-hydroxybenzo-
              triazole (HBT). Without a mediator, laccase was unable to oxidise wool or
              the amino acids. In the presence of mediators, oxygen consumption was




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