Laccase- and electrochemically mediated conversion of triclosan: Metabolite formation and influence on antibacterial activity.

Metabolite formation from radical-based oxidation of the environmental pollutant triclosan (TCS) was compared using an ascomycete (Phoma sp. UHH 5-1-03) and a basidiomycete (Trametes versicolor) laccase, laccase-redox mediator systems, and electrochemical oxidation (EC). Laccase oxidation predominantly yielded TCS di- and trimers, but notably also caused TCS ether bond cleavage. The latter was more prominent during EC-catalysed TCS oxidation, which generally resulted in a broader and more divergent product spectrum. By contrast, only quantitative but not qualitative differences in TCS metabolite formation were observed for the two laccases. Application of the presumable natural laccase redox mediator syringaldehyde (SYD) shifted the TCS-transforming reactions of laccase systems from oligomerization more towards ether bond cleavage. However, the observed rapid removal of SYD from reaction systems caused by predominant adduct formation from SYD and TCS, and concomitant conversion of SYD into 2,6-dimethoxy-1,4-benzoquinone (DMBQ) clearly demonstrates that SYD does not function as a "true" laccase redox mediator in the sense of being recycled during TCS oxidation. Laccase treatment of TCS without SYD decreased the anti-bacterial TCS activity more than treatment employing SYD in addition, indicating that SYD and/or its transformation products contribute to bacterial toxicity. DMBQ was found to be about 80% more active in a bacterial growth inhibition test than its parent compound SYD in terms of IC20 values. These observations establish DMBQ as a potential cause of toxicity effects of SYD-laccase systems. They further illustrate that a natural origin of a redox mediator does not automatically qualify its use as environmentally benign or non-hazardous.

Jahangiri E ，Seiwert B ，Reemtsma T ，Schlosser D ... -  《-》

Enhanced transformation of triclosan by laccase in the presence of redox mediators.

Murugesan K ，Chang YY ，Kim YM ，Jeon JR ，Kim EJ ，Chang YS ... -  《-》

Degradation of triclosan by an integrated nano-bio redox process.

In this study, a sequential reduction-oxidation method was developed for complete degradation of triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, TCS) in aqueous solution. Rapid reductive dechlorination of TCS was achieved with palladized zero-valent iron nanoparticles (Pd/nFe), under anaerobic conditions, with generation of 2-phenoxyphenol as the sole dechlorination product. Sequentially, 2-phenoxyphenol was transformed into a non-toxic polymer using laccase (EC:1.10.3.2) derived from Trametes versicolor in the presence of natural redox mediator syringaldehyde (SYD). High performance liquid chromatography combined with electrospray ionization mass spectroscopy (HPLC-ESI-MS) revealed the formation of dimer and trimer products during the laccase-mediated transformation process. The efficiency of the integrated method is critically dependent on the Fe(2+) concentration, which was effectively controlled by optimizing the solution pH. To the best of our knowledge, this is the first report of a redox two-step hybrid system for the complete transformation of TCS into non-toxic products.

Bokare V ，Murugesan K ，Kim YM ，Jeon JR ，Kim EJ ，Chang YS ... -  《-》

A comparison between the oxidation with laccase and horseradish peroxidase for triclosan conversion.

Melo CF ，Dezotti M ，Marques MR 《-》

Laccase-mediated transformation of triclosan in aqueous solution with metal cations and humic acid.

Triclosan (TCS) is a broad-spectrum antimicrobial agent that is found extensively in natural aquatic environments. Enzyme-catalyzed oxidative coupling reactions (ECOCRs) can be used to remove TCS in aqueous solution, but there is limited information available to indicate how metal cations (MCs) and natural organic matter (NOM) influence the environmental fate of TCS during laccase-mediated ECOCRs. In this study, we demonstrated that the naturally occurring laccase from Pleurotus ostreatus was effective in removing TCS during ECOCRs, and the oligomerization of TCS was identified as the dominant reaction pathway by high-resolution mass spectrometry (HRMS). The growth inhibition studies of green algae (Chlamydomonas reinhardtii and Scenedesmus obliquus) proved that laccase-mediated ECOCRs could effectively reduce the toxicity of TCS. The presence of dissolved MCs (Mn2+, Al3+, Ca2+, Cu2+, and Fe2+ ions) influenced the removal and transformation of TCS via different mechanisms. Additionally, the transformation of TCS in systems with NOM derived from humic acid (HA) was hindered, and the apparent pseudo first-order kinetics rate constants (k) for TCS decreased as the HA concentration increased, which likely corresponded to the combined effect of both noncovalent (sorption) and covalent binding between TCS and humic molecules. Our results provide a novel insight into the fate and transformation of TCS by laccase-mediated ECOCRs in natural aquatic environments in the presence of MCs and NOM.

Sun K ，Kang F ，Waigi MG ，Gao Y ，Huang Q ... -  《-》