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dc.contributor.authorWalton, John C.
dc.identifier.citationWalton , J C 2021 , ' Dissociations of free radicals to generate protons, electrophiles or nucleophiles : role in DNA strand breaks ' , Chemical Society Reviews , vol. 50 , no. 13 , pp. 7496-7512 .
dc.identifier.otherPURE: 274438693
dc.identifier.otherPURE UUID: aedbaf2a-b673-413c-bd71-bdfb58be0311
dc.identifier.otherWOS: 000652636200001
dc.identifier.otherScopus: 85109210881
dc.descriptionThanks to the University of St. Andrews and the EaStCHEM Research Computing Facility for financial and computational support.en
dc.description.abstractThe concept behind the research described in this article was that of marrying the 'soft' methods of radical generation with the effectiveness and flexibility of nucleophile/electrophile synthetic procedures. Classic studies with pulse radiolysis and laser flash photolysis had shown that free radicals could be more acidic than their closed shell counterparts. QM computations harmonised with this and helped to define which radical centres and which structural types were most effective. Radicals based on the sulfonic acid moiety and on the Meldrum's acid moiety (2,2-dimethyl-1,3-dioxane-4,6-dione) were found to be extreme examples in the superacid class. The ethyne unit could be used as a very effective spacer between the radical centre and the site of proton donation. The key factor in promoting acidity was understood to be the thermodynamic stabilisation of the conjugate anion-radicals released on deprotonation. Solvation played a key part in promoting this and theoretical microhydration studies provided notable support. A corollary was that heterolytic dissociations of free radicals to yield either electrophiles or nucleophiles were also enhanced relative to non-radical models. The most effective radical types for spontaneous releases of both these types of reagents were identified. Ethyne units were again effective as spacers. The enhancement of release of phosphate anions by adjacent radical centres was an important special case. Reactive oxygen species and also diradicals from endiyne antibiotics generate C4 '-deoxyribose radicals from nucleotides. Radicals of these types spontaneously release phosphate and triphosphate and this is a contributor to DNA and RNA strand breaks.
dc.relation.ispartofChemical Society Reviewsen
dc.rightsCopyright © 2021 The Author(s). Open Access. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.en
dc.subjectQD Chemistryen
dc.titleDissociations of free radicals to generate protons, electrophiles or nucleophiles : role in DNA strand breaksen
dc.typeJournal itemen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.description.statusPeer revieweden

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