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dc.contributor.author | Jornet Olivé, Mª Dolors | es_ES |
dc.contributor.author | Tormos Faus, Rosa Esperanza | es_ES |
dc.contributor.author | Miranda Alonso, Miguel Ángel | es_ES |
dc.date.accessioned | 2013-04-29T14:10:26Z | |
dc.date.issued | 2011 | |
dc.identifier.issn | 1520-6106 | |
dc.identifier.uri | http://hdl.handle.net/10251/28321 | |
dc.description.abstract | [EN] In the present work, a systematic study on hydrogen abstraction by the excited triplet states of 4-methoxybenzophenone (1) and 4,40-dimethoxybenzophenone (2) from 1,4-cyclohexadiene (3), 4-methylphenol (4), 1,2,3,4-tetrahydroquinoline (5), and 1-methyl-1,2,3,4-tetrahydroquinoline (6) in different media has been undertaken. Laser flash photolysis (LFP) revealed that in nonpolar solvents, 1 and 2 triplets have a n¿* configuration with the typical benzophenone-like T-T absorption spectrum (¿max ca. 525 nm). Conversely, in aqueous solution, transient absorption spectra with maxima at 450 and 680 nm, attributed to the ¿¿* triplet, were obtained. Quenching of 1 or 2 triplet by 3 led to ketyl radical formation with rate constants in the range of 106 108M 1 s 1, being one order of magnitude higher in acetonitrile than in aqueous media. The rate constants of quenching by 4 and 5 were similar in both polar and nonpolar solvents; the highest value was found for 6 in acetonitrile ((6.3 to 6.9) 109M 1 s 1). For mechanistic insight, LFP of 1 or 2 in the presence of dimethoxybenzene as electron donor was performed. The results showed that in this case, triplet quenching is favored in aqueous solution. In addition, 2 included in human serum albumin (HSA) was submitted to LFP. The decay kinetics, monitored at 430 nm, fitted well with three lifetimes of 0.45, 1.4, and 14.4 ¿s assignable to 2 in bulk solution and in site II or in site I of HSA, respectively. This assignment was confirmed by using oleic acid and ibuprofen as selective displacement probes | es_ES |
dc.description.sponsorship | Financial support from the MICINN (grants: CTQ2010-99010) and the Generalitat Valenciana (Prometeo Program) is gratefully acknowledged. | en_EN |
dc.language | Inglés | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation.ispartof | Journal of Physical Chemistry B | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject.classification | QUIMICA ORGANICA | es_ES |
dc.title | Photobehavior of mixed Nn*/nn* triplets. Simultaneous detection of the two transients, solvent-depend hydrogen abstraction and reequilibration upon protein binding | es_ES |
dc.type | Artículo | es_ES |
dc.embargo.lift | 10000-01-01 | |
dc.embargo.terms | forever | es_ES |
dc.identifier.doi | 10.1021/jp2051432 | |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CTQ2010- 99010 | es_ES |
dc.rights.accessRights | Cerrado | 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 | Jornet Olivé, MD.; Tormos Faus, RE.; Miranda Alonso, MÁ. (2011). Photobehavior of mixed Nn*/nn* triplets. Simultaneous detection of the two transients, solvent-depend hydrogen abstraction and reequilibration upon protein binding. Journal of Physical Chemistry B. 115:10768-10774. doi:10.1021/jp2051432 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | http://pubs.acs.org/doi/pdf/10.1021/jp2051432 | es_ES |
dc.description.upvformatpinicio | 10768 | es_ES |
dc.description.upvformatpfin | 10774 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 115 | es_ES |
dc.relation.senia | 196332 | |
dc.contributor.funder | Generalitat Valenciana | es_ES |