Modification of Deoxynivalenol by a Fungal Laccase Paired with Redox Mediator TEMPO

Hina Shanakhat; Susan P McCormick; Mark Busman; Joseph O Rich; Matthew G Bakker

doi:10.3390/toxins14080548

Modification of Deoxynivalenol by a Fungal Laccase Paired with Redox Mediator TEMPO

Toxins (Basel). 2022 Aug 11;14(8):548. doi: 10.3390/toxins14080548.

Authors

Hina Shanakhat¹, Susan P McCormick², Mark Busman², Joseph O Rich³, Matthew G Bakker⁴

Affiliations

¹ Department of Agricultural Sciences, University of Naples Federico II, 80138 Naples, Italy.
² National Center for Agricultural Utilization Research, Agricultural Research Service, United States Department of Agriculture, Peoria, IL 61604, USA.
³ Plains Area Office, Agricultural Research Service, United States Department of Agriculture, Fort Collins, CO 80526, USA.
⁴ Department of Microbiology, University of Manitoba, Winnipeg, MB R3T 2N2, Canada.

Abstract

Mycotoxins such as deoxynivalenol introduce a health risk to the food supply and are costly to manage or avoid. Technologies for reducing or eliminating the toxicity of deoxynivalenol could be useful in a variety of processes, such as in preserving the value as animal feed of byproducts of ethanol production. We characterized transformation products of deoxynivalenol that were formed by the combination of a fungal laccase paired with the chemical mediator 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), using chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy. Alcohol groups at the C3 and C15 positions of deoxynivalenol were oxidized to ketones, and the chemical mediator became covalently linked to the C4 position. Conditions experienced during gas chromatography led to the dissociation of TEMPO, forming 3,15-diketodeoxynivalenol. Understanding the range of possible modifications to deoxynivalenol and other trichothecenes is a necessary step toward effective remediation of contaminated grain.

Keywords: deoxynivalenol; laccase; mycotoxin; trichothecene.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Animals
Cyclic N-Oxides
Food Contamination / analysis
Laccase
Mycotoxins* / analysis
Oxidation-Reduction
Trichothecenes* / analysis

Substances

Cyclic N-Oxides
Mycotoxins
Trichothecenes
Laccase
deoxynivalenol
TEMPO

Grants and funding

This research was supported by the United States Department of Agriculture—Agricultural Research Service National Program for Food Safety. USDA is an equal opportunity provider and employer. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.