{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T02:38:39Z","timestamp":1760150319211,"version":"build-2065373602"},"reference-count":55,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2023,11,3]],"date-time":"2023-11-03T00:00:00Z","timestamp":1698969600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"FRABA 804\/12 proyect","award":["263127"],"award-info":[{"award-number":["263127"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Computation"],"abstract":"<jats:p>Antioxidants are molecules that neutralize free radicals. In general, the reaction mechanisms of antioxidants are well known. The main reaction mechanisms of antioxidants are electron transfer (ET), hydrogen transfer (HT), and radical adduction formation (RAF). The study of these mechanisms is helpful in understanding how antioxidants control high free radical levels in the cell. There are many studies focused on determining the main mechanism of an antioxidant to neutralize a wide spectrum of radicals, mainly reactive oxygen species (ROS)-type radicals. Most of these antioxidants are polyphenol-type compounds. Some esters, amides, and metal antioxidants have shown antioxidant activity, but there are few experimental and theoretical studies about the antioxidant reaction mechanism of these compounds. In this work, we show the reaction mechanism proposed for two esters, 11, tri-butyl p-coumarate and its tri-butyl-tin p-coumarate counterpart, using Sn(IV). We show how Sn(IV) increases the electron transfer in polar media and the H transfer in non-polar media. Even though the nature of esters could be polar or non-polar compounds, the antioxidant activity is good for the Sn(IV)-p-coumarate complex in non-polar media.<\/jats:p>","DOI":"10.3390\/computation11110220","type":"journal-article","created":{"date-parts":[[2023,11,4]],"date-time":"2023-11-04T14:51:01Z","timestamp":1699109461000},"page":"220","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["How Sn(IV) Influences on the Reaction Mechanism of 11, tri-Butyl p-Coumarate and Its tri-Butyl-tin p-Coumarate Considering the Solvent Effect: A DFT Level Study"],"prefix":"10.3390","volume":"11","author":[{"given":"Rogelio A.","family":"Delgado-Alfaro","sequence":"first","affiliation":[{"name":"Facultad de Ciencias Qu\u00edmicas, Universidad de Colima, Km-9 Carretera Colima-Coquimatl\u00e1n, Colima 28400, Mexico"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6670-6311","authenticated-orcid":false,"given":"Zeferino","family":"G\u00f3mez-Sandoval","sequence":"additional","affiliation":[{"name":"Facultad de Ciencias Qu\u00edmicas, Universidad de Colima, Km-9 Carretera Colima-Coquimatl\u00e1n, Colima 28400, Mexico"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,11,3]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"639","DOI":"10.1016\/0020-711X(88)90158-9","article-title":"Chemoprevention of cancer: Phenolic antioxidants (BHT, BHA)","volume":"20","author":"Hocman","year":"1988","journal-title":"Int. J. Biochem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1547","DOI":"10.1093\/carcin\/9.9.1547","article-title":"Effect of exogenous glutathione on tumor progression in the murine skin multistage carcinogenesis model","volume":"9","author":"Rotstein","year":"1998","journal-title":"Carcinogenesis"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1306","DOI":"10.1021\/jp110400t","article-title":"OH Radical Scavenging Activity of Edaravone: Mechanism and Kinetics","volume":"115","author":"Galano","year":"2011","journal-title":"J. Phys. Chem. B"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"5445","DOI":"10.3390\/molecules15085445","article-title":"Antioxidant Activity of Butyl- and Phenylstannoxanes Derived from 2-, 3- and 4-Pyridinecarboxylic Acids","volume":"15","year":"2010","journal-title":"Molecules"},{"key":"ref_5","first-page":"143","article-title":"Antiradical capacity of a series of organotin(IV) compounds: A chemical reactivity study in the Density Functional Theory framework","volume":"413","year":"2014","journal-title":"ICA"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"875","DOI":"10.1039\/tf9353100875","article-title":"Some applications of the transition state method to the calculation of reaction velocities, especially in solution","volume":"31","author":"Evans","year":"1935","journal-title":"Trans. Faraday. Soc."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"875","DOI":"10.1039\/tf9353100875","article-title":"Further considerations on the thermodynamics of chemical equilibria and reaction rates","volume":"31","author":"Evans","year":"1936","journal-title":"Trans. Faraday Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"107","DOI":"10.1063\/1.1749604","article-title":"The Activated Complex in Chemical Reactions","volume":"3","author":"Eyring","year":"1935","journal-title":"J. Chem. Phys."},{"key":"ref_9","first-page":"279","article-title":"Simple Gas Reaction","volume":"12","author":"Eyring","year":"1931","journal-title":"Phys. Chem. Abt. B"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"155","DOI":"10.1146\/annurev.pc.15.100164.001103","article-title":"Chemical and Electrochemical Electron-Transfer Theory","volume":"15","author":"Marcus","year":"1964","journal-title":"Anu. Rev. Phys. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"864","DOI":"10.1103\/PhysRev.136.B864","article-title":"Inhomogeneous Electron Gas","volume":"136","author":"Hohenberg","year":"1964","journal-title":"Phys. Rev. B"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"A1133","DOI":"10.1103\/PhysRev.140.A1133","article-title":"Self-Consistent Equations Including Exchange and Correlation Effects","volume":"140","author":"Kohn","year":"1965","journal-title":"Phys. Rev. A"},{"key":"ref_13","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Vreven, T., Kudin, K.N., and Burant, J.C. (2004). Gaussian 09, Gaussian, Inc.. Version 09."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"364","DOI":"10.1021\/ct0502763","article-title":"Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions","volume":"2","author":"Zhao","year":"2006","journal-title":"J. Chem. Theory Comput."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"5639","DOI":"10.1063\/1.438980","article-title":"Contracted Gaussian-basis sets for molecular calculations. 1. 2nd row atoms, Z=11\u201318","volume":"72","author":"McLean","year":"1980","journal-title":"J. Chem. Phys."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"299","DOI":"10.1063\/1.448975","article-title":"Ab initio effective core potentials for molecular calculations\u2014Potentials for K to Au including the outermost core orbitals","volume":"82","author":"Hay","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"284","DOI":"10.1063\/1.448800","article-title":"Ab initio effective core potentials for molecular calculations\u2014Potentials for main group elements Na to Bi","volume":"82","author":"Hay","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"270","DOI":"10.1063\/1.448799","article-title":"Ab initio effective core potentials for molecular calculations\u2014Potentials for the transition-metal atoms Sc to Hg","volume":"82","author":"Hay","year":"1985","journal-title":"J. Chem. Phys."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"13913","DOI":"10.1021\/jp906144d","article-title":"OH Radical Gas Phase Reactions with Aliphatic Ethers: A Variational Transition State Theory Study","volume":"113","author":"Merino","year":"2009","journal-title":"J. Phys. Chem. A"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"971","DOI":"10.1002\/poc.1547","article-title":"A computational study of stereospecifity in the thermal elimination reaction of methyl benzoate in the gas phase","volume":"22","author":"Velez","year":"2009","journal-title":"Phys. Org. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5114","DOI":"10.1021\/ol901862h","article-title":"Guanosine + OH radical reaction in aqueous solution: A reinterpretation of the UV-vis data based on thermodynamic and kinetic calculations","volume":"11","author":"Galano","year":"2009","journal-title":"Org. Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1236","DOI":"10.1002\/jcc.21410","article-title":"Barrier heights for H-atom abstraction by H\u022e2 from n-butanol\u2014A simple yet exacting test for model chemistries?","volume":"31","author":"Black","year":"2010","journal-title":"Comput. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1007\/s00214-011-0958-0","article-title":"Mechanism and kinetics of the hydroxyl and hydroperoxyl radical scavenging activity of N-acetylcysteine amide","volume":"130","author":"Galano","year":"2011","journal-title":"Theor. Chem. Acc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvatation Model Based on Solute Electron Densityt and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1002\/chem.19970030208","article-title":"Theoretical investigation of the mechanism of the Baeyer-Villiger reaction in nonpolar solvents","volume":"3","author":"Okuno","year":"1997","journal-title":"Chem.\u2014Eur. J."},{"key":"ref_26","unstructured":"Benson, S.W. (1960). The Foundations of Chemical Kinetics, McGraw-Hill."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"23618","DOI":"10.1021\/jp0540499","article-title":"Relative Gibbs Energies in Solution through Continuum Models:\u2009 Effect of the Loss of Translational Degrees of Freedom in Bimolecular Reactions on Gibbs Energy Barriers","volume":"109","author":"Ardura","year":"2005","journal-title":"J. Phys. Chem. B"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1763","DOI":"10.1021\/ol060261z","article-title":"A New Specific Mechanism for the Acid Catalysis of the Addition Step in the Baeyer\u2212Villiger Rearrangement","volume":"8","author":"Reyes","year":"2006","journal-title":"Org. Lett."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"3682","DOI":"10.1039\/b712608e","article-title":"The mechanism of the Baeyer\u2013Villiger rearrangement: Quantum chemistry and TST study supported by experimental kinetic data","volume":"5","author":"Reyes","year":"2007","journal-title":"Org. Biomol. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1677","DOI":"10.1021\/jp0665271","article-title":"Influence of Silicon Defects on the Adsorption of Thiophene-like Compounds on Polycyclic Aromatic Hydrocarbons:\u2009 A Theoretical Study Using Thiophene + Coronene as the Simplest Model","volume":"111","author":"Galano","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"8922","DOI":"10.1021\/jp801379g","article-title":"Carbon Nanotubes as Free-Radical Antioxidants","volume":"112","author":"Galano","year":"2008","journal-title":"J. Phys. Chem. C"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"732","DOI":"10.1039\/b716024k","article-title":"OH radical reactions with phenylalanine in free and peptide forms","volume":"6","author":"Galano","year":"2008","journal-title":"Org. Biomol. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"87","DOI":"10.1016\/j.chemphys.2008.01.040","article-title":"Reactivity of silicon and germanium doped CNTs toward aromatic sulfur compounds: A theoretical approach","volume":"345","author":"Galano","year":"2008","journal-title":"Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3682","DOI":"10.1039\/b906058h","article-title":"The Baeyer\u2013Villiger reaction: Solvent effects on reaction mechanisms","volume":"7","author":"Keller","year":"2009","journal-title":"Org. Biomol. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"2664","DOI":"10.1021\/j100238a003","article-title":"Current status of transition-state theory","volume":"87","author":"Truhlar","year":"1983","journal-title":"J. Phys. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1840","DOI":"10.1021\/ja00737a002","article-title":"Exact Tunneling Calculations","volume":"93","author":"Truhlar","year":"1971","journal-title":"J. Am. Chem. Soc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"7662","DOI":"10.1039\/b924521a","article-title":"The inactivation of lipid peroxide radical by quercetin. A theoretical insight","volume":"12","author":"Chiodo","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"599","DOI":"10.1103\/RevModPhys.65.599","article-title":"Electron transfer reactions in chemistry. Theory and experiment","volume":"65","author":"Marcus","year":"1993","journal-title":"Rev. Mod. Phys."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1351\/pac199769010013","article-title":"Transfer reactions in chemistry. Theory and experiment","volume":"69","author":"Marcus","year":"1997","journal-title":"Pure Appl. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"425","DOI":"10.1016\/0095-8522(49)90023-9","article-title":"Diffusion-controlled reaction rates","volume":"4","author":"Collins","year":"1949","journal-title":"J. Colloid Sci."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"104","DOI":"10.1021\/ed062p104","article-title":"Nearly Encoun11, tri-Controlled Reactions: The Equivalence of the Steady-State and Diffusional Viewpoints","volume":"62","author":"Truhlar","year":"1985","journal-title":"J. Chem. Ed."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"549","DOI":"10.1002\/andp.19053220806","article-title":"Quantum Effect on Elementary Process of Diffusion and Collective Motion of Brown Particles","volume":"17","author":"Einstein","year":"1905","journal-title":"Ann. Phys."},{"key":"ref_43","unstructured":"Stokes, G.G. (1903). Mathematical and Physical Papers, Cambridge University Press. esp. Sect. IV."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"12534","DOI":"10.1039\/c2cp40651a","article-title":"On the peroxyl scavenging activity of hydroxycinnamic acid derivatives: Mechanisms, kinetics, and importance of the acid\u2013base equilibrium","volume":"14","author":"Galano","year":"2012","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1007\/s00214-009-0667-0","article-title":"A universal approach for continuum solvent pKa calculations: Are we there yet?","volume":"125","author":"Ho","year":"2010","journal-title":"Theor. Chem. Acc."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2017","DOI":"10.1016\/S0006-3495(04)74263-0","article-title":"Finite Element Solution of the Steady-State Smoluchowski Equation for Rate Constant Calculations","volume":"86","author":"Song","year":"2004","journal-title":"Bioph. J."},{"key":"ref_47","first-page":"199","article-title":"A Diagnostic for Determining the Quality of Single-Reference Electron Correlation Methods","volume":"23","author":"Lee","year":"1989","journal-title":"Int. J. Quant. Chem. Quantum Chem. Symp."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"5968","DOI":"10.1063\/1.453520","article-title":"Quadratic configuration interaction. A general technique for determining electron correlation energies","volume":"87","author":"Pople","year":"1987","journal-title":"J. Chem. Phys."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"13101","DOI":"10.1021\/jp208315k","article-title":"Physicochemical Insights on the Free Radical Scavenging Activity of Sesamol: Importance of the Acid\/Base Equilibrium","volume":"115","author":"Galano","year":"2011","journal-title":"J. Phys. Chem. B"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"16077","DOI":"10.1021\/jp907906h","article-title":"Peroxyl-Radical-Scavenging Activity of Garlic: 2-Propenesulfenic Acid versus Allicin","volume":"113","author":"Galano","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1016\/j.molstruc.2009.12.037","article-title":"Synthesis, characterization, spectroscopic and antioxidation studies of Cu(II)\u2013morin complex","volume":"967","author":"Panhwar","year":"2010","journal-title":"J. Mol. Struct. (Theochem)"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"597","DOI":"10.1016\/j.saa.2014.05.071","article-title":"Synthesis, characterization and biological activity of 2-acetylpyridine-a-naphthoxyacetylhydrazone its metal complexes","volume":"135","author":"Bekheit","year":"2015","journal-title":"Spectrochim. Acta Part A Mol. Biomol. Spectrosc."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/j.theochem.2009.07.026","article-title":"Interaction of Mg2+, Ca2+, Zn2+ and Cu+ with cytosine nucleosides: Influence of metal on sugar puckering and stability of N-Glycosidic bond, a DFT study","volume":"913","author":"Tehrani","year":"2009","journal-title":"J. Mol. Struct. (Theochem)"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1016\/S0166-1280(02)00299-3","article-title":"Vitamin E models. Conformational analysis and stereochemistry of tetralin, chroman, thiochroman and selenochroman","volume":"594","author":"Setiadi","year":"2002","journal-title":"J. Mol. Struct. (Theochem)"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"826","DOI":"10.1007\/s10975-005-0046-3","article-title":"Geometric Parameters of the Transition State in Radical Reactions of Antioxidants","volume":"45","author":"Denisova","year":"2004","journal-title":"Kin. Catal."}],"container-title":["Computation"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-3197\/11\/11\/220\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:17:31Z","timestamp":1760131051000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-3197\/11\/11\/220"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,11,3]]},"references-count":55,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2023,11]]}},"alternative-id":["computation11110220"],"URL":"https:\/\/doi.org\/10.3390\/computation11110220","relation":{},"ISSN":["2079-3197"],"issn-type":[{"type":"electronic","value":"2079-3197"}],"subject":[],"published":{"date-parts":[[2023,11,3]]}}}