Reduction of the 2,2'-Azinobis(3-ethylbenzthiazoline-6-sulfonate) cation radical by physiological organic acids in the absence and presence of manganese

Abstract:

:Laccase is a copper-containing phenoloxidase, involved in lignin degradation by white rot fungi. The laccase substrate range can be extended to include nonphenolic lignin subunits in the presence of a noncatalytic cooxidant such as 2, 2'-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS), with ABTS being oxidized to the stable cation radical, ABTS.+, which accumulates. In this report, we demonstrate that the ABTS.+ can be efficiently reduced back to ABTS by physiologically occurring organic acids such as oxalate, glyoxylate, and malonate. The reduction of the radical by oxalate results in the formation of H2O2, indicating the formation of O2.- as an intermediate. O2.- itself was shown to act as an ABTS.+ reductant. ABTS.+ reduction and H2O2 formation are strongly stimulated by the presence of Mn2+, with accumulation of Mn3+ being observed. Additionally, 4-methyl-O-isoeugenol, an unsaturated lignin monomer model, is capable of directly reducing ABTS.+. These data suggest several mechanisms for the reduction of ABTS.+ which would permit the effective use of ABTS as a laccase cooxidant at catalytic concentrations.

journal_name

Appl Environ Microbiol

authors

Collins PJ,Dobson ADW,Field JA

doi

10.1128/AEM.64.6.2026-2031.1998

subject

Has Abstract

pub_date

1998-06-01 00:00:00

pages

2026-31

issue

6

eissn

0099-2240

issn

1098-5336

journal_volume

64

pub_type

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