COMPARAÇÃO DAS PROPRIEDADES ELETRÔNICAS DO TRIADIMEFON E DE SEU METABÓLITO TRIADIMENOL
Keywords:
Fungicides; Triadimefon; Triadimenol; Density Functional Theory.Abstract
Pesticides are widely used in agriculture but present risks associated with their toxicity. Among them, triazole fungicides stand out for their efficacy and broad spectrum of action, acting to inhibit ergosterol biosynthesis in fungi. In this study, the physicochemical and electronic properties of triadimefon (TDF) and its metabolite, triadimenol (TDN), were investigated using Density Functional Theory (DFT) calculations. The molecular structures were optimized using the M06-2X functional and the 6-311++G(d,p) basis set, followed by frequency analysis and determination of reactivity descriptors. The results showed that TDN exhibits greater electronic stability due to its increased HOMO-LUMO gap, while TDF is characterized by greater reactivity and electronic adaptability, favoring its interaction with enzymatic targets. Both compounds were classified as strong electrophiles, suggesting potential for selective interactions with nucleophilic biomolecules. These findings contribute to a better understanding of the structural and reactivity differences between TDF and TDN, providing insights for the safer and more effective use of these fungicides in agriculture.
References
Aliste, M., Pérez-Lucas, G., Garrido, I., Fenoll, J. & Navarro, S. Risk Assessment of 1,2,4-Triazole-Typed Fungicides for Groundwater Pollution Using Leaching Potential Indices. Water Air Soil Pollut 232, (2021).
Botelho, M. G. L. et al. Agrotóxicos na agricultura: agentes de danos ambientais e a busca pela agricultura sustentável. Research, Society and Development 9, e396985806 (2020).
Sun, S. et al. Novel (Z)/(E)-1,2,4-triazole derivatives containing oxime ether moiety as potential ergosterol biosynthesis inhibitors: design, preparation, antifungal evaluation, and molecular docking. Mol Divers 27, 145–157 (2023).
Kong, Z. et al. Stereoselective behaviors of the fungicide triadimefon and its metabolite triadimenol during malt storage and beer brewing. J Hazard Mater 400, (2020).
Zhang, W. et al. Comparison of triadimefon and its metabolite on acute toxicity and chronic effects during the early development of Rana nigromaculata tadpoles. Ecotoxicol Environ Saf 156, 247–254 (2018).
Garrison, A. W., Avants, J. K. & Jones, W. J. Microbial transformation of triadimefon to triadimenol in soils: Selective production rates of triadimenol stereoisomers affect exposure and risk. Environ Sci Technol 45, 2186–2193 (2011).
Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864 (1964).
Kohn, W. & Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects. Phys. Rev. 140, A1133− A1138 (1965).
Frisch, M. J. et al. Gaussian 16, Revision C.01. Preprint at (2016).
Zhao, Y. & Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 120, 215–241 (2008).
Zhang, G. & Musgrave, C. B. Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations. J Phys Chem A 111, 1554–1561 (2007).
Zhang, G. & Musgrave, C. B. Comparison of DFT methods for molecular orbital eigenvalue calculations. Journal of Physical Chemistry A 111, 1554–1561 (2007).
Pearson, R. G. Chemical hardness and density functional theory. Journal of Chemical Sciences 117, 369–377 (2005).
Pearson, R. G. The electronic chemical potential and chemical hardness. Journal of Molecular Structure (Theo&em) 255, 261–270 (1992).
