THEORETICAL STUDY OF THE REACTIVITY OF MONURON AND ITS PROTONATED FORMS
DOI:
https://doi.org/10.4314/jfas.v12i2.3Keywords:
DFT; Monuron; Proton affinity; Global and local reactivity descriptors; Solvation.Abstract
A theoretical study of 3-(4-Chlorophenyl)-1,1-dimethylurea and its protonated isomers has been carried out, to emphasize the experimental results of the electrostatic interactions in the herbicide models, for investigating the implications taking place on the structural parameters starting from the gaseous phase to the aqueous one. It has been found that its functionalized structure gives us three protonated targets. The calculations has been performed on both neutral and protonated forms using Density Functional Theory (DFT) with the hybrid functional B3LYP. Many molecular parameters have been studied. To identify the reactive sites, our study has focused on the local and the global reactivity descriptors explaining the chemical reactivity. The calculations have demonstrated that the attacks on the aliphatic branched exocyclic positions are privileged to those of the aromatic ring. Studying the solvent effect has revealed that there is a change in the hierarchy of the electrophilicity. Various vibrational modes have been exploited to discuss the literary spectroscopic data.
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References
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[29] Dupuy, N., et al., Characterization of aqueous and solid inclusion complexes of diuron and isoproturon with β-cyclodextrin. Applied spectroscopy. 2004, 58 (6): 711-718.
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[36] Downs, R.T. and M. Hall-Wallace, The American Mineralogist crystal structure database. American Mineralogist. 2003, 88 (1): 247-250.
[37] Mendoza-Huizar, L.H., Chemical reactivity of isoproturon, diuron, linuron, and chlorotoluron herbicides in aqueous phase: A theoretical quantum study employing global and local reactivity descriptors. Journal of Chemistry. 2015, 2015.
[38] Gázquez, J.L., Perspectives on the density functional theory of chemical reactivity. Journal of the Mexican Chemical Society. 2008, 52 (1): 3-10.
[39] Liu, S.-B., Conceptual density functional theory and some recent developments. Acta Physico-Chimica Sinica. 2009, 25 (3): 590-600.
[40] Ayers, P.W. and M. Levy, Perspective on “Density functional approach to the frontier-electron theory of chemical reactivity”. Theoretical Chemistry Accounts. 2000, 103 (3-4): 353-360.
[41] Chermette, H., Chemical reactivity indexes in density functional theory. Journal of Computational Chemistry. 1999, 20 (1): 129-154.
[42] Parr, R.G., L.v. Szentpaly, and S. Liu, Electrophilicity index. Journal of the American Chemical Society. 1999, 121 (9): 1922-1924.
[43] Parr, R.G., Density functional theory of atoms and molecules, in Horizons of Quantum Chemistry. 1980, Springer. p. 5-15.
[44] Ayers, P.W. and R.G. Parr, Variational principles for describing chemical reactions: the Fukui function and chemical hardness revisited. Journal of the American Chemical Society. 2000, 122 (9): 2010-2018.
[45] Otero, N., et al., Establishing the pivotal role of local aromaticity in the electronic properties of boron-nitride graphene lateral hybrids. Physical Chemistry Chemical Physics. 2016, 18 (36): 25315-25328.
[46] Yang, W. and R.G. Parr, Hardness, softness, and the fukui function in the electronic theory of metals and catalysis. Proceedings of the National Academy of Sciences. 1985, 82 (20): 6723-6726.
[47] Tazi, R., et al., Theoretical Approach of the Adsorption of Herbicide Amitrole on the Soil using DFT Method. Oriental Journal of Chemistry. 2018, 34 (3): 1240-1248.
[48] Gunasekaran, S., et al., Vibrational spectra and molecular structural investigation of quiniodochlor. 2004.
[2] Witkowski, P.T., et al., Phylogenetic analysis of a newfound bat-borne hantavirus supports a laurasiatherian host association for ancestral mammalian hantaviruses. Infection, Genetics and Evolution. 2016, 41 113-119. https://doi.org/10.1016/j.meegid.2016.03.036
[3] Kin, C.M. and T.G. Huat, Simultaneous Determination of Nine Commercial Pesticide Formulations by Gas Chromatography Multi-Pesticide with an Internal Standard Method. MALAYSIAN JOURNAL OF CHEMISTRY (MJChem). 2011, 13 (1): 57-62.
[4] Ihlaseh, S.M., et al., Transcriptional Profile of Diuron-Induced Toxicity on the Urinary Bladder of Male Wistar Rats to Inform Mode of Action. Toxicological Sciences. 2011, 122 (2): 330-338. 10.1093/toxsci/kfr108
[5] Yin, X.L., et al., Toxic reactivity of wheat (Triticum aestivum) plants to herbicide isoproturon. Journal of agricultural and food chemistry. 2008, 56 (12): 4825-4831.
[6] Wolf, A., et al., Occurrence and distribution of organic trace substances in waters from the Three Gorges Reservoir, China. Environmental Science and Pollution Research. 2013, 20 (10): 7124-7139.
[7] Četkauskaité, A., U. Grigonis, and J. Beržinskiené, Biodegradation: selection of suitable model. Ecotoxicology and environmental safety. 1998, 40 (1-2): 19-28.
[8] Upchurch, R.P. and W. Pierce, The leaching of monuron from Lakeland sand soil. Part II. The effect of soil temperature, organic matter, soil moisture, and amount of herbicide. Weeds. 1958, 6 (1): 24-33.
[9] Tanaka, F.S., R.G. Wien, and B.L. Hoffer, Investigation of the mechanism and pathway of biphenyl formation in the photolysis of monuron. Journal of Agricultural and Food Chemistry. 1982, 30 (5): 957-963.
[10] Booij, P., et al., Toxic pressure of herbicides on microalgae in Dutch estuarine and coastal waters. Journal of Sea Research. 2015, 102 48-56. https://doi.org/10.1016/j.seares.2015.05.001
[11] Hussain, S., et al., Abiotic and biotic processes governing the fate of phenylurea herbicides in soils: a review. Critical Reviews in Environmental Science and Technology. 2015, 45 (18): 1947-1998.
[12] Chu, W., et al., Removal of phenylurea herbicide monuron via riboflavin-mediated photosensitization. Chemosphere. 2007, 69 (2): 177-183.
[13] Chu, W., et al., Removal of phenylurea herbicide monuron via riboflavin-mediated photosensitization. Chemosphere. 2007, 69 (2): 177-183. https://doi.org/10.1016/j.chemosphere.2007.04.055
[14] Monuron.
[15] Mulliken, R.S., A new electroaffinity scale; together with data on valence states and on valence ionization potentials and electron affinities. The Journal of Chemical Physics. 1934, 2 (11): 782-793.
[16] Cook, M. and M. Karplus, Electron correlation and density-functional methods. Journal of Physical Chemistry. 1987, 91 (1): 31-37.
[17] Miranda-Quintana, R.A., Density functional theory for chemical reactivity. Conceptual density functional theory and its applications in the chemical domain. Apple Academic Press, Hamilton. 2018.
[18] Levandowski, B.J., et al., Role of orbital interactions and activation strain (distortion energies) on Reactivities in the normal and inverse electron-demand cycloadditions of strained and unstrained cycloalkenes. The Journal of organic chemistry. 2017, 82 (16): 8668-8675.
[19] Ciraci, S., A study on the tight-binding method. Journal of Physics and Chemistry of Solids. 1975, 36 (6): 557-561. https://doi.org/10.1016/0022-3697(75)90141-9
[20] Geldart, D. and M. Rasolt, Exchange and correlation energy of an inhomogeneous electron gas at metallic densities. Physical Review B. 1976, 13 (4): 1477.
[21] Becke, A.D., Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals. The Journal of chemical physics. 1997, 107 (20): 8554-8560.
[22] Boese, A.D., Assessment of coupled cluster theory and more approximate methods for hydrogen bonded systems. Journal of chemical theory and computation. 2013, 9 (10): 4403-4413.
[23] Frisch, M.J., et al., Gaussian 16 Rev. C.01. 2016: Wallingford, CT.
[24] Van Leeuwen, R. and E. Baerends, Exchange-correlation potential with correct asymptotic behavior. Physical Review A. 1994, 49 (4): 2421.
[25] Stewart, J.J., Optimization of parameters for semiempirical methods II. Applications. Journal of computational chemistry. 1989, 10 (2): 221-264.
[26] Cammi, R., Quantum cluster theory for the polarizable continuum model. I. The CCSD level with analytical first and second derivatives. The Journal of chemical physics. 2009, 131 (16): 164104.
[27] Fedorov, D.G., et al., The polarizable continuum model (PCM) interfaced with the fragment molecular orbital method (FMO). Journal of computational chemistry. 2006, 27 (8): 976-985.
[28] Khadrani, A., et al., Degradation of three phenylurea herbicides (chlortoluron, isoproturon and diuron) by micromycetes isolated from soil. Chemosphere. 1999, 38 (13): 3041-3050.
[29] Dupuy, N., et al., Characterization of aqueous and solid inclusion complexes of diuron and isoproturon with β-cyclodextrin. Applied spectroscopy. 2004, 58 (6): 711-718.
[30] Mendoza-Huizar, L.H., Global and local reactivity descriptors for picloram herbicide: a theoretical quantum study. Química Nova. 2015, 38 (1): 71-76.
[31] Gražulis, S., et al., Computing stoichiometric molecular composition from crystal structures. Journal of applied crystallography. 2015, 48 (1): 85-91.
[32] Gražulis, S., et al., Crystallography Open Database–an open-access collection of crystal structures. Journal of applied crystallography. 2009, 42 (4): 726-729.
[33] Gražulis, S., et al., Crystallography Open Database (COD): an open-access collection of crystal structures and platform for world-wide collaboration. Nucleic acids research. 2012, 40 (D1): D420-D427.
[34] Quirós, M., et al., Using SMILES strings for the description of chemical connectivity in the Crystallography Open Database. Journal of cheminformatics. 2018, 10 (1): 1-17.
[35] Merkys, A., et al., COD:: CIF:: Parser: an error-correcting CIF parser for the Perl language. Journal of applied crystallography. 2016, 49 (1): 292-301.
[36] Downs, R.T. and M. Hall-Wallace, The American Mineralogist crystal structure database. American Mineralogist. 2003, 88 (1): 247-250.
[37] Mendoza-Huizar, L.H., Chemical reactivity of isoproturon, diuron, linuron, and chlorotoluron herbicides in aqueous phase: A theoretical quantum study employing global and local reactivity descriptors. Journal of Chemistry. 2015, 2015.
[38] Gázquez, J.L., Perspectives on the density functional theory of chemical reactivity. Journal of the Mexican Chemical Society. 2008, 52 (1): 3-10.
[39] Liu, S.-B., Conceptual density functional theory and some recent developments. Acta Physico-Chimica Sinica. 2009, 25 (3): 590-600.
[40] Ayers, P.W. and M. Levy, Perspective on “Density functional approach to the frontier-electron theory of chemical reactivity”. Theoretical Chemistry Accounts. 2000, 103 (3-4): 353-360.
[41] Chermette, H., Chemical reactivity indexes in density functional theory. Journal of Computational Chemistry. 1999, 20 (1): 129-154.
[42] Parr, R.G., L.v. Szentpaly, and S. Liu, Electrophilicity index. Journal of the American Chemical Society. 1999, 121 (9): 1922-1924.
[43] Parr, R.G., Density functional theory of atoms and molecules, in Horizons of Quantum Chemistry. 1980, Springer. p. 5-15.
[44] Ayers, P.W. and R.G. Parr, Variational principles for describing chemical reactions: the Fukui function and chemical hardness revisited. Journal of the American Chemical Society. 2000, 122 (9): 2010-2018.
[45] Otero, N., et al., Establishing the pivotal role of local aromaticity in the electronic properties of boron-nitride graphene lateral hybrids. Physical Chemistry Chemical Physics. 2016, 18 (36): 25315-25328.
[46] Yang, W. and R.G. Parr, Hardness, softness, and the fukui function in the electronic theory of metals and catalysis. Proceedings of the National Academy of Sciences. 1985, 82 (20): 6723-6726.
[47] Tazi, R., et al., Theoretical Approach of the Adsorption of Herbicide Amitrole on the Soil using DFT Method. Oriental Journal of Chemistry. 2018, 34 (3): 1240-1248.
[48] Gunasekaran, S., et al., Vibrational spectra and molecular structural investigation of quiniodochlor. 2004.
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Published
2020-03-21
How to Cite
MASMOUDI, R.; KHETTAF, S.; BOUKHATEM, I. M.; ABERKANE, R.; KAHLAT, C.; SOLTANI, A.; DIBI, A. THEORETICAL STUDY OF THE REACTIVITY OF MONURON AND ITS PROTONATED FORMS. Journal of Fundamental and Applied Sciences, [S. l.], v. 12, n. 2, p. 538–562, 2020. DOI: 10.4314/jfas.v12i2.3. Disponível em: https://jfas.info/index.php/JFAS/article/view/581. Acesso em: 30 jan. 2025.
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