{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,15]],"date-time":"2026-08-15T19:12:52Z","timestamp":1786821172623,"version":"build-2736575974"},"reference-count":41,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2023,12,22]],"date-time":"2023-12-22T00:00:00Z","timestamp":1703203200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22178141"],"award-info":[{"award-number":["22178141"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["21978059"],"award-info":[{"award-number":["21978059"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["2022J01328"],"award-info":[{"award-number":["2022J01328"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["23YYST063QCA17"],"award-info":[{"award-number":["23YYST063QCA17"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Natural Science Foundation of Fujian Province of China","award":["22178141"],"award-info":[{"award-number":["22178141"]}]},{"name":"Natural Science Foundation of Fujian Province of China","award":["21978059"],"award-info":[{"award-number":["21978059"]}]},{"name":"Natural Science Foundation of Fujian Province of China","award":["2022J01328"],"award-info":[{"award-number":["2022J01328"]}]},{"name":"Natural Science Foundation of Fujian Province of China","award":["23YYST063QCA17"],"award-info":[{"award-number":["23YYST063QCA17"]}]},{"name":"Youth Science and Technology Innovation Program of Xiamen Ocean and Fisheries Development Special Funds","award":["22178141"],"award-info":[{"award-number":["22178141"]}]},{"name":"Youth Science and Technology Innovation Program of Xiamen Ocean and Fisheries Development Special Funds","award":["21978059"],"award-info":[{"award-number":["21978059"]}]},{"name":"Youth Science and Technology Innovation Program of Xiamen Ocean and Fisheries Development Special Funds","award":["2022J01328"],"award-info":[{"award-number":["2022J01328"]}]},{"name":"Youth Science and Technology Innovation Program of Xiamen Ocean and Fisheries Development Special Funds","award":["23YYST063QCA17"],"award-info":[{"award-number":["23YYST063QCA17"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Antioxidants"],"abstract":"<jats:p>The free radical trapping capacities of multiple pyranoanthocyanins in wine storage and ageing were theoretically explored by density functional theory (DFT) methods. Intramolecular hydrogen bonds were detected in all pyranoanthocyanins, and the planarity of the compounds worsened with an increasing dielectric constant in the environment. Solvents significantly influenced the reaction enthalpies; thus, the preferred thermodynamic mechanisms of the free radical scavenging reactions were modified in different phases. This study incorporates hydrogen atom transfer (HAT), proton loss (PL), electron transfer (ET) reactions, and demethylation (De) of methoxy group mechanisms. The three pyranoanthocyanins have the capacity to capture n1+1 free radicals, where n1 represents the number of methoxy groups. In the gas phase, they prefer employing the n1-De-HAT mechanism on the guaiacyl moiety of the B ring, resulting in the formation of a stable quinone or a quinone radical to scavenge free radicals. In the benzene phase, pyranoanthocyanins trap free radicals via a PL\u2212n1\u2212De\u2212HAT mechanism. In the water phase, the targeted pyranoanthocyanins may dissociate in the form of carboxylate and tend to utilize the n2\u2212PL\u2212n1\u2212De\u2212ET mechanism, where n2 and n1 represent the number of phenolic groups and methoxy groups, respectively, facilitating multiple H+\/e\u2212 reactions.<\/jats:p>","DOI":"10.3390\/antiox13010033","type":"journal-article","created":{"date-parts":[[2023,12,22]],"date-time":"2023-12-22T08:53:01Z","timestamp":1703235181000},"page":"33","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Theoretical Study on the Multiple Free Radical Scavenging Reactions of Pyranoanthocyanins"],"prefix":"10.3390","volume":"13","author":[{"given":"Yapeng","family":"Du","sequence":"first","affiliation":[{"name":"College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Chai","sequence":"additional","affiliation":[{"name":"College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoping","family":"Zheng","sequence":"additional","affiliation":[{"name":"College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanzhen","family":"Zheng","sequence":"additional","affiliation":[{"name":"College of Ocean Food and Biological Engineering, Jimei University, Xiamen 361021, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,12,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Andersen, O.M., and Markham, K.R. (2005). Flavonoids: Chemistry, Biochemistry and Applications, CRC Press.","DOI":"10.1201\/9781420039443"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"859","DOI":"10.1016\/j.foodchem.2008.09.001","article-title":"Chemical Studies of Anthocyanins: A Review","volume":"113","year":"2009","journal-title":"Food Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"555","DOI":"10.1039\/b718040n","article-title":"Flavonoids and Their Glycosides, Including Anthocyanins","volume":"25","author":"Veitch","year":"2008","journal-title":"Nat. Prod. Rep."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"884","DOI":"10.1039\/b800165k","article-title":"Blue Flower Color Development by Anthocyanins: From Chemical Structure to Cell Physiology","volume":"26","author":"Yoshida","year":"2009","journal-title":"Nat. Prod. Rep."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1111\/j.1749-6632.2002.tb02903.x","article-title":"Wine Phenolics","volume":"957","author":"Waterhouse","year":"2002","journal-title":"Ann. N. Y. Acad. Sci."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1416","DOI":"10.1021\/acs.chemrev.1c00399","article-title":"Natural and Synthetic Flavylium-Based Dyes: The Chemistry behind the Color","volume":"122","author":"Cruz","year":"2022","journal-title":"Chem. Rev."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1919","DOI":"10.1021\/jf020943a","article-title":"A New Class of Blue Anthocyanin-Derived Pigments Isolated from Red Wines","volume":"51","author":"Mateus","year":"2003","journal-title":"J. Agric. Food Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1102","DOI":"10.1016\/S0891-5849(02)00826-2","article-title":"Free Radical-Induced Damage to DNA: Mechanisms and Measurement 1, 2","volume":"32","author":"Dizdaroglu","year":"2002","journal-title":"Free. Radical Biol. Med."},{"key":"ref_9","first-page":"541","article-title":"Editors\u2019 Biographies","volume":"Volume 1200","author":"Andreescu","year":"2015","journal-title":"Oxidative Stress: Diagnostics, Prevention, and Therapy Volume 2"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"44","DOI":"10.1016\/j.biocel.2006.07.001","article-title":"Free Radicals and Antioxidants in Normal Physiological Functions and Human Disease","volume":"39","author":"Valko","year":"2007","journal-title":"Int. J. Biochem. Cell Biol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"331","DOI":"10.1016\/0891-5849(95)02047-0","article-title":"Structural Aspects of Antioxidant Activity of Flavonoids","volume":"20","author":"Tromp","year":"1996","journal-title":"Free. Radic. Biol. Med."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1033","DOI":"10.1016\/0006-2952(96)00421-2","article-title":"Inhibition of Lipid Peroxidation and the Active Oxygen Radical Scavenging Effect of Anthocyanin Pigments Isolated from Phaseolus vulgaris L.","volume":"52","author":"Tsuda","year":"1996","journal-title":"Biochem. Pharmacol."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"288","DOI":"10.1016\/j.foodchem.2010.08.012","article-title":"The Molecular Basis of Working Mechanism of Natural Polyphenolic Antioxidants","volume":"125","author":"Leopoldini","year":"2011","journal-title":"Food Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"506","DOI":"10.1016\/j.foodres.2015.06.040","article-title":"Radical Scavenging Activity Characterization of Synthetic Isochroman-Derivatives of Hydroxytyrosol: A Gas-Phase DFT Approach","volume":"76","author":"Nenadis","year":"2015","journal-title":"Food Res. Int."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"31","DOI":"10.1016\/j.comptc.2014.10.020","article-title":"Reaction Enthalpies of OH Bonds Splitting-off in Flavonoids: The Role of Non-Polar and Polar Solvent","volume":"1050","author":"Lengyel","year":"2014","journal-title":"Comput. Theor. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"131975","DOI":"10.1016\/j.foodchem.2021.131975","article-title":"Theoretical Study on the Radical Scavenging Activity and Mechanism of Four Kinds of Gnetin Molecule","volume":"378","author":"Shang","year":"2022","journal-title":"Food Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1562","DOI":"10.1016\/j.foodchem.2013.03.072","article-title":"Bond Dissociation Free Energy as a General Parameter for Flavonoid Radical Scavenging Activity","volume":"141","year":"2013","journal-title":"Food Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1016\/j.comptc.2015.01.014","article-title":"Study of the Molecular Structure and Chemical Reactivity of Pinocembrin by DFT Calculations","volume":"1058","year":"2015","journal-title":"Comput. Theor. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1173","DOI":"10.1021\/ja002455u","article-title":"Predicting the Activity of Phenolic Antioxidants:\u2009 Theoretical Method, Analysis of Substituent Effects, and Application to Major Families of Antioxidants","volume":"123","author":"Wright","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"198","DOI":"10.1016\/j.foodchem.2013.11.064","article-title":"Density Functional Theory Study of the Structure\u2013Antioxidant Activity of Polyphenolic Deoxybenzoins","volume":"151","author":"Xue","year":"2014","journal-title":"Food Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1016\/j.foodchem.2017.07.133","article-title":"Theoretical Studies on the Antioxidant Activity of Pinobanksin and Its Ester Derivatives: Effects of the Chain Length and Solvent","volume":"240","author":"Zheng","year":"2018","journal-title":"Food Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"7002","DOI":"10.1021\/jf404735j","article-title":"Antioxidant Features of Red Wine Pyranoanthocyanins: Experimental and Theoretical Approaches","volume":"62","author":"Azevedo","year":"2014","journal-title":"J. Agric. Food Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"8862","DOI":"10.1021\/jf101693k","article-title":"Pyranoanthocyanins: A Theoretical Investigation on Their Antioxidant Activity","volume":"58","author":"Leopoldini","year":"2010","journal-title":"J. Agric. Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1073","DOI":"10.1021\/ct2000974","article-title":"A Computational Study (TDDFT and RICC2) of the Electronic Spectra of Pyranoanthocyanins in the Gas Phase and Solution","volume":"7","author":"Quartarolo","year":"2011","journal-title":"J. Chem. Theory Comput."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"144","DOI":"10.1016\/j.foodchem.2016.09.018","article-title":"Free Radical Scavenging Potency of Quercetin Catecholic Colonic Metabolites: Thermodynamics of 2H+\/2e\u2212 Processes","volume":"218","year":"2017","journal-title":"Food Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"481","DOI":"10.1016\/j.foodchem.2017.11.100","article-title":"Theoretical Study of the Thermodynamics of the Mechanisms Underlying Antiradical Activity of Cinnamic Acid Derivatives","volume":"246","author":"Klein","year":"2018","journal-title":"Food Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"9706","DOI":"10.1021\/jp1041266","article-title":"A Computational Study on the Acidity Dependence of Radical-Scavenging Mechanisms of Anthocyanidins","volume":"114","author":"Otero","year":"2010","journal-title":"J. Phys. Chem. B"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"109877","DOI":"10.1016\/j.dyepig.2021.109877","article-title":"Multiple Free Radical Scavenging Reactions of Flavonoids","volume":"198","author":"Zheng","year":"2022","journal-title":"Dye. Pigment."},{"key":"ref_29","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2016). Gaussian 16, Revision C.01, Gaussian Inc."},{"key":"ref_30","unstructured":"Dennington, R., Keith, T.A., and Millam, J.M. (2016). Gaussview 6, Semichem Inc."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-functional thermochemistry. III. The role of exact exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"157","DOI":"10.1021\/ar700111a","article-title":"Density functionals with broad applicability in chemistry","volume":"41","author":"Zhao","year":"2008","journal-title":"Acc. Chem. Res."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"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","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"527","DOI":"10.1021\/ct200866d","article-title":"Charge model 5: An extension of Hirshfeld population analysis for the accurate description of molecular interactions in gaseous and condensed phases","volume":"8","author":"Marenich","year":"2012","journal-title":"J. Chem. Theory Comput."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"115732","DOI":"10.1016\/j.fuel.2019.115732","article-title":"Density functional study on the thermal stabilities of phenolic bio-oil compounds","volume":"255","author":"Shaw","year":"2019","journal-title":"Fuel"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"730","DOI":"10.1080\/10715762.2023.2170880","article-title":"Guaiacol oxidation: Thermochemistry of radical processes involving methoxy group demethylation","volume":"56","author":"Biela","year":"2022","journal-title":"Free Radic. Res."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1007\/s00253-012-3954-y","article-title":"Peculiarities of brown-rot fungi and biochemical Fenton reaction with regard to their potential as a model for bioprocessing biomass","volume":"94","author":"Arantes","year":"2012","journal-title":"Appl. Microbiol. Biot."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"6420","DOI":"10.1021\/j100076a029","article-title":"Thermodynamics of the Electron and the Proton","volume":"98","author":"Bartmess","year":"1994","journal-title":"J. Phys. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"7458","DOI":"10.1021\/ja00045a018","article-title":"Homolytic Bond (H-A) Dissociation Free Energies in Solution. Applications of the Standard Potential of the (H+\/H.Bul.) Couple","volume":"114","author":"Parker","year":"1992","journal-title":"J. Am. Chem. Soc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"25","DOI":"10.1016\/j.theochem.2010.04.002","article-title":"Study of the Solvent Effect on the Enthalpies of Homolytic and Heterolytic N\u2013H Bond Cleavage in p-Phenylenediamine and Tetracyano-p-Phenylenediamine","volume":"952","author":"Klein","year":"2010","journal-title":"J. Mol. Struct. THEOCHEM"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"3225","DOI":"10.1021\/ja01360a004","article-title":"The Nature of the Chemical Bond. II. The One-Electron Bond and the Three-Electron Bond","volume":"53","author":"Pauling","year":"1931","journal-title":"J. Am. Chem. Soc."}],"container-title":["Antioxidants"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2076-3921\/13\/1\/33\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:40:35Z","timestamp":1760132435000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2076-3921\/13\/1\/33"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,22]]},"references-count":41,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2024,1]]}},"alternative-id":["antiox13010033"],"URL":"https:\/\/doi.org\/10.3390\/antiox13010033","relation":{},"ISSN":["2076-3921"],"issn-type":[{"value":"2076-3921","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,22]]}}}