PEGylation Greatly Enhances Laccase Polymerase Activity

Abstract

Laccase catalyzes the oxidation and polymerization of phenolic compounds in the presence of oxygen. Herein, we report for the first time that a previous PEGylation of laccase enhances the polymerase activity 3‐fold compared with the reaction of the native enzyme, as confirmed by UV/Vis spectroscopy. The polymerization of catechol increased only 1.5‐fold if poly(ethylene glycol) (PEG) was added to the medium reaction. Molecular‐dynamics simulations suggest the formation of a miscible complex of polycatechol and PEG, which is responsible to push the reaction forward. In a negative control experiment set, all catalysts were entrapped inside polyacrylamide gels and here the native laccase showed a relatively higher activity. These results suggest that the mobility of PEG is a key feature for the enhancement of the reaction.

Coloured and low conductive fabrics by in situ laccase-catalysed polymerization

“…These findings have been reported previously by us (data not shown) where we found that the chemically modified laccases are able to improve the polymerization of catechol. Moreover, the role of highenergy environments was also previously described as potentiating the enzymatic polymerization to produce higher polymers and convert higher amount of monomer [23,26]. A higher amount of produced oligomers and polymers not always corresponds to a higher deposition onto the fibre substrates used as containers.…”

“…Laccase from Myceliophthora thermophila was PEGylated as previously reported [26] using the procedure of Daly et al [27]. Briefly, 14.0 mL of 12 mg/mL laccase were reacted with 20 kDa, poly(ethylene glycol) methyl ether at pH = 5, 10 mM sodium phosphate buffer with 20 mM sodium cyanoborohydride.…”

Can Laccase-Assisted Processing Conditions Influence the Structure of the Reaction Products?

“…Both free PEG and PEGylation of laccase enzyme accelerate the rate of conversion, leading to an increased yield of poly(catechol) product with a range of different structures (Table 1). Immobilization of laccase in epoxy resins, with or without PEG as a spacer between the resin and the catalyst, leads to the generation of additional structures [11,12]. Processing conditions have also been investigated in the laccase-assisted below, proposed non-linear polymer) (image adapted, with permission, from [12,13]).…”

Catalytic Activation of Esterases by PEGylation for Polyester Synthesis

“…studied the effect of PEGylation of laccase from Myceliophthora thermophila . The authors observed an increment of the conversion and degree of polymerization when the PEGylated laccase was applied for catechol polymerization …”

“…The authors observed an increment of the conversion and degree of polymerization when the PEGylated laccase was applied for catechol polymerization. [8] The use of lipases for the catalysis of polyesters has been presented as an excellent alternative to the chemical approaches, generally involving the use of high temperatures and/or expensive and non-environmentally friendly metal catalysts. [9] Lipases are most often not expensive, reusable, and are associated to green chemistry practices.…”