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Hydrogen Abstraction from the C15 Position of the Cholesterol Skeleton

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Hydrogen Abstraction from the C15 Position of the Cholesterol Skeleton

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dc.contributor.author Palumbo, Fabrizio es_ES
dc.contributor.author Andreu Ros, María Inmaculada es_ES
dc.contributor.author Brunetti, M. es_ES
dc.contributor.author Schmallegger, Max es_ES
dc.contributor.author Gescheidt, Georg es_ES
dc.contributor.author Neshchadin, Dmytro es_ES
dc.contributor.author Miranda Alonso, Miguel Ángel es_ES
dc.date.accessioned 2021-05-18T03:30:55Z
dc.date.available 2021-05-18T03:30:55Z
dc.date.issued 2019-12-06 es_ES
dc.identifier.issn 0022-3263 es_ES
dc.identifier.uri http://hdl.handle.net/10251/166456
dc.description.abstract [EN] Cholesterol (Ch) is an integral part of cell membrane, where it is prone to oxidation. In humans, oxidation of Ch is commonly linked to various pathologies like Alzheimer's disease, atherosclerosis, and even cancer, which proceed via mechanisms involving enzymatic and free radical pathways. The latter begin with hydrogen abstraction (HA) from Ch by a reactive free radical. It has been established that the most efficient HA from Ch occurs at C7, although HA from C4 by peroxyl radicals has recently been observed. Conversely, HA from Ch positions other than the thermodynamically preferred C7 or C4 has never been reported. We have designed a Ch derivative where a benzophenone moiety is linked to C7 by a covalent bond. This mirrors a specific orientation of Ch within a confined environment. Product analysis and time-resolved spectroscopic studies reveal an unprecedented HA from C15, which is a thermodynamically unfavorable position. This indicates that a specific topology of reactants is crucial for the reactivity of Ch. The relative orientation of the reactants can also be relevant in biological membranes, where Ch, polyunsaturated fatty acids, and numerous oxidizing species are confined in highly restricted and anisotropic environments. es_ES
dc.description.sponsorship This work was supported by the Carlos III Institute of Health (Grants No. PII6/01877, "Miguel Servet fellowship" CPII16/00052 to I.A.), and by the Generalitat Valenciana (Prometeo 2017/075). We would like to thank Dr Fedora Grande for sending an exchange student (M.B.). D.N. and G.G. thank NAWI Graz for support. es_ES
dc.language Inglés es_ES
dc.publisher American Chemical Society es_ES
dc.relation.ispartof The Journal of Organic Chemistry es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Cholesterol es_ES
dc.subject CIDNP es_ES
dc.subject Laser flash photolysis es_ES
dc.subject Radicals es_ES
dc.subject Steady-State Photolysis es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.title Hydrogen Abstraction from the C15 Position of the Cholesterol Skeleton es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1021/acs.joc.9b02181 es_ES
dc.relation.projectID info:eu-repo/grantAgreement/GVA//PROMETEO%2F2016%2F120/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/GVA//PROMETEO%2F2017%2F075/ES/Reacciones fotoquímicas de biomoléculas/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//CPII16%2F00052/ES/CPII16%2F00052/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MECD//AP2012-1693/ES/AP2012-1693/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//PI16%2F01877/ES/Estrategia integrada de fotodiagnóstico combinando evaluación clínica, ensayos biológicos y estudios mecanísticos/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Química - Departament de Química es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Palumbo, F.; Andreu Ros, MI.; Brunetti, M.; Schmallegger, M.; Gescheidt, G.; Neshchadin, D.; Miranda Alonso, MÁ. (2019). Hydrogen Abstraction from the C15 Position of the Cholesterol Skeleton. The Journal of Organic Chemistry. 84(23):15184-15191. https://doi.org/10.1021/acs.joc.9b02181 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1021/acs.joc.9b02181 es_ES
dc.description.upvformatpinicio 15184 es_ES
dc.description.upvformatpfin 15191 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 84 es_ES
dc.description.issue 23 es_ES
dc.identifier.pmid 31675234 es_ES
dc.relation.pasarela S\406764 es_ES
dc.contributor.funder Generalitat Valenciana es_ES
dc.contributor.funder Ministerio de Educación es_ES
dc.contributor.funder Instituto de Salud Carlos III es_ES
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