|TU, YI-SHU - Ministry Of Science And Technology|
|TSENG, YUFENG - National Taiwan University|
Submitted to: Structural Chemistry
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 2/2/2019
Publication Date: 3/8/2019
Citation: Tu, Y.-S., Tseng, Y.J., Appell, M. 2019. Quantum chemical investigation of the detection properties of alternariol and alternariol monomethyl ether. Structural Chemistry. https://doi.org/10.1007/s11224-019-01302-3.
Interpretive Summary: Alternariol and alternariol monomethyl ether are toxins produced by fungi that can contaminate cereal grains and fruits. Contaminated food and beverages pose health risks. Reliable detection methods are needed to evaluate exposure to these toxins. To aid in the development of better detection methods, we applied computational methods to characterize the detection properties of alternariol and alternariol monomethyl ether. Chemical information important to accurately detect these toxins are reported. We identified several modifications to certain chemical groups of the toxins that influence properties related to detection. This study serves as a comprehensive resource to design robust analytical methods to monitor exposure to alternariol and alternariol monomethyl ether. This research benefits analytical scientists, regulators, and the food industry.
Technical Abstract: Alternariol and alternariol monomethyl ether are mycotoxins occasionally found in food and beverages that have been contaminated by fungi of the Alternaria genus. Conformers, tautomers, anions, and analogs of alternariol were geometry optimized using the Becke, 3-parameter, Lee-Yang-Parr (B3LYP) density functional. Electronic structural analysis provided frontier orbitals, molecular electronic potential maps, and vibrational assignments. Optimized conformations of alternariol are within 5.2 kilojoule/mole of the most stable conformation and share very similar molecular orbital properties. Vibrational assignments for the calculated infrared and Raman spectra are reported and correspond with experimental spectra. Tautomers are 130-180 kilojoule/mole higher in energy and possess unique molecular orbital properties. Methylated and demethylated analogs shared similar properties to alternariol. Deprotonation of hydroxyl groups of alternariol, alternariol monomethyl ether, and methylated analogs influences the molecular orbital properties and molecular electronic potential maps.