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Studies on the Oxidation of Aromatic Amines Catalyzed by Trametes versicolor Laccase.

ABSTRACT: The bio-oxidation of a series of aromatic amines catalyzed by T. versicolor laccase has been investigated exploiting either commercially available nitrogenous substrates [(E)-4-vinyl aniline and diphenyl amine] or ad hoc synthetized ones [(E)-4-styrylaniline, (E)-4-(prop-1-en-1-yl)aniline and (E)-4-(((4-methoxyphenyl)imino)methyl)phenol]. At variance to their phenolic equivalents, the investigated aromatic amines were not converted into the expected cyclic dimeric structures under T. versicolor catalysis. The formation of complex oligomeric/polymeric or decomposition by-products was mainly observed, with the exception of the isolation of two interesting but unexpected chemical skeletons. Specifically, the biooxidation of diphenylamine resulted in an oxygenated quinone-like product, while, to our surprise, in the presence of T. versicolor laccase (E)-4-vinyl aniline was converted into a 1,2-substited cyclobutane ring. To the best of our knowledge, this is the first example of an enzymatically triggered [2 + 2] olefin cycloaddition. Possible reaction mechanisms to explain the formation of these products are also reported.

SUBMITTER: Bassanini I

PROVIDER: S-EPMC9963649 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Studies on the Oxidation of Aromatic Amines Catalyzed by Trametes versicolor Laccase.

Bassanini Ivan I Grosso Simone S Tognoli Chiara C Fronza Giovanni G Riva Sergio S

International journal of molecular sciences 20230209 4

The bio-oxidation of a series of aromatic amines catalyzed by T. versicolor laccase has been investigated exploiting either commercially available nitrogenous substrates [(E)-4-vinyl aniline and diphenyl amine] or ad hoc synthetized ones [(E)-4-styrylaniline, (E)-4-(prop-1-en-1-yl)aniline and (E)-4-(((4-methoxyphenyl)imino)methyl)phenol]. At variance to their phenolic equivalents, the investigated aromatic amines were not converted into the expected cyclic dime ...[more]

PMID: 36834934

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Project description:Many previous studies have shown that (i) the oxidation of aniline or the aniline dimer p-aminodiphenylamine (PADPA) in a slightly acidic aqueous solution can be catalyzed with heme peroxidases or multicopper laccases and that (ii) subsequent reactions lead to oligomeric or polymeric products, which resemble chemically synthesized polyaniline in its conductive emeraldine salt form (PANI-ES), provided that (iii) an anionic "template" is present in the reaction medium. Good templates are anionic polyelectrolytes, micelles, or vesicles. Under optimal conditions, their presence directs the reactions in a positive way toward the desired formation of PANI-ES-type products. The effect of four different types of anionic templates on the formation of PANI-ES-like products from PADPA was investigated and compared by using Trametes versicolor laccase (TvL) as a catalyst in an aqueous pH 3.5 solution at room temperature. All four templates contain sulfonate groups: the sodium salt of the polyelectrolyte sulfonated polystyrene (SPS), micelles from sodium dodecylbenzenesulfonate (SDBS), vesicles from a 1:1 molar mixture of SDBS and decanoic acid, and vesicles from sodium bis(2-ethylhexyl)sulfosuccinate (AOT). Although with all four templates, stable, inkjet-printable solutions or suspensions consisting of PANI-ES-type products were obtained under optimized conditions, considerably higher amounts of TvL were required with SDBS micelles to achieve comparable monomer conversion to PANI-ES-like products during the same time period when compared to those with SPS or the two types of vesicles. This makes SDBS micelles less attractive as templates for the investigated reaction. In situ UV/vis/near-infrared, electron paramagnetic resonance (EPR), and Raman spectroscopy measurements in combination with an high-performance liquid chromatography analysis of extracted reaction products, which were deprotonated and chemically reduced, showed seemingly small but significant differences in the composition of the mixtures obtained when reaching reaction equilibrium after 24 h. With the two vesicle systems, the content of unwanted substituted phenazine units was lower than in the case of SPS polyelectrolyte and SDBS micelles. The EPR spectra indicate a more localized, narrower distribution of electronic states of the paramagnetic centers of the PANI-ES-type products synthesized in the presence of the two vesicle systems when compared to that of the similar products obtained with the SPS polyelectrolyte and SDBS micelles as templates. Overall, the data obtained from the different complementary methods indicate that with the two vesicle systems structurally more uniform (regular) PANI-ES-type products formed. Among the two investigated vesicle systems, for the investigated reaction (oxidation of PADPA with TvL and O2), AOT appears a somewhat better choice as it leads to a higher content of the PANI-ES polaron form.

Dataset Information

Studies on the Oxidation of Aromatic Amines Catalyzed by Trametes versicolor Laccase.

Publications

Studies on the Oxidation of Aromatic Amines Catalyzed by <i>Trametes versicolor</i> Laccase.

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