dc.contributor.author |
Andreu Ros, María Inmaculada
|
es_ES |
dc.contributor.author |
Neshchadin, Dmytro
|
es_ES |
dc.contributor.author |
Rico Inglada, Enrique
|
es_ES |
dc.contributor.author |
Griesser, Markus
|
es_ES |
dc.contributor.author |
Samadi, Abdelouahid
|
es_ES |
dc.contributor.author |
Morera Bertomeu, Isabel María
|
es_ES |
dc.contributor.author |
Gescheidt, Georg
|
es_ES |
dc.contributor.author |
Miranda Alonso, Miguel Ángel
|
|
dc.date.accessioned |
2013-11-11T13:45:01Z |
|
dc.date.issued |
2011-07-26 |
|
dc.identifier.issn |
0947-6539 |
|
dc.identifier.uri |
http://hdl.handle.net/10251/33427 |
|
dc.description.abstract |
A thorough mechanistic study has been performed on the reaction between benzophenone (BZP) and a series of 1,4-dienes, including 1,4-cyclohexadiene (CHD), 1,4-dihydro-2-methylbenzoic acid (MBA), 1,4-dihydro-1,2-dimethylbenzoic acid (DMBA) and linoleic acid (LA). A combination of steady-state photolysis, laser flash photolysis (LFP), and photochemically induced dynamic nuclear polarization (photo-CIDNP) have been used. Irradiation of BZP and CHD led to a cross-coupled sensitizer¿diene product, together with 6, 7, and 8. With MBA and DMBA as hydrogen donors, photoproducts arising from cross-coupling of sensitizer and diene radicals were found; compound 7 was also obtained, but 6 and o-toluic acid were only isolated in the irradiation of BZP with MBA. Triplet lifetimes were determined in the absence and in the presence of several diene concentrations. All three model compounds showed similar reactivity (kq¿108¿m¿1¿s¿1) towards triplet excited BZP. Partly reversible hydrogen abstraction of the allylic hydrogen atoms of CHD, MBA, and DMBA was also detected by photo-CIDNP on different timescales. Polarizations of the diamagnetic products were in full agreement with the results derived from LFP. Finally, LA also underwent partly reversible hydrogen abstraction during photoreaction with BZP. Subsequent hydrogen transfer between primary radicals led to conjugated derivatives of LA. The unpaired electron spin population in linoleyl radical (LA.) was predominantly found on H(1-5) protons. To date, LA-related radicals were only reported upon hydrogen transfer from highly substituted model compounds by steady-state EPR spectroscopy. Herein, we have experimentally established the formation of LA. and shown that it converts into two dominating conjugated isomers on the millisecond timescale. Such processes are at the basis of alterations of membrane structures caused by oxidative stress. |
es_ES |
dc.description.sponsorship |
Financial support from the MICINN (grants CTQ2009-13699 and CTQ2010-14882), from the Generalitat Valenciana (GV/2009/104) and from Carlos III Institute of Health (grant RIRAAF, RETICS program) is gratefully acknowledged. We thank also COST project CM603 for facilitating our collaboration. |
en_EN |
dc.format.extent |
8 |
es_ES |
dc.language |
Inglés |
es_ES |
dc.publisher |
Wiley-VCH Verlag |
es_ES |
dc.relation.ispartof |
Chemistry - A European Journal |
es_ES |
dc.rights |
Reserva de todos los derechos |
es_ES |
dc.subject |
Dienes |
es_ES |
dc.subject |
Hydrogen abstraction |
es_ES |
dc.subject |
Photochemistry |
es_ES |
dc.subject |
Photolysis |
es_ES |
dc.subject |
Transient absorption spectroscopy |
es_ES |
dc.subject.classification |
QUIMICA ORGANICA |
es_ES |
dc.title |
Probing lipid peroxidatin by using linoleic acid and benzophenone |
es_ES |
dc.type |
Artículo |
es_ES |
dc.embargo.lift |
10000-01-01 |
|
dc.embargo.terms |
forever |
es_ES |
dc.identifier.doi |
10.1002/chem.201100983 |
|
dc.relation.projectID |
info:eu-repo/grantAgreement/MICINN//CTQ2010-14882/ES/DIADAS FOTOACTIVAS COMO SONDAS PARA LA GENERACION DE ESPECIES TRANSITORIAS EN SISTEMAS MICROHETEROGENEOS DE TIPO BIOMIMETICO/ |
es_ES |
dc.relation.projectID |
info:eu-repo/grantAgreement/COST//CM0603/EU/Free Radicals in Chemical Biology (CHEMBIORADICAL)/ |
es_ES |
dc.relation.projectID |
info:eu-repo/grantAgreement/Generalitat Valenciana//GV%2F2009%2F104/ES/Estudio de la Fotoperoxidación de Lípidos de Membrana por Fármacos/ |
es_ES |
dc.relation.projectID |
info:eu-repo/grantAgreement/MICINN//CTQ2009-13699/ES/CTQ2009-13699/ |
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 |
Andreu Ros, MI.; Neshchadin, D.; Rico Inglada, E.; Griesser, M.; Samadi, A.; Morera Bertomeu, IM.; Gescheidt, G.... (2011). Probing lipid peroxidatin by using linoleic acid and benzophenone. Chemistry - A European Journal. 17(36):10089-10096. https://doi.org/10.1002/chem.201100983 |
es_ES |
dc.description.accrualMethod |
S |
es_ES |
dc.relation.publisherversion |
http://onlinelibrary.wiley.com/doi/10.1002/chem.201100983/full |
es_ES |
dc.description.upvformatpinicio |
10089 |
es_ES |
dc.description.upvformatpfin |
10096 |
es_ES |
dc.type.version |
info:eu-repo/semantics/publishedVersion |
es_ES |
dc.description.volume |
17 |
es_ES |
dc.description.issue |
36 |
es_ES |
dc.relation.senia |
197850 |
|
dc.contributor.funder |
Generalitat Valenciana |
es_ES |
dc.contributor.funder |
European Cooperation in Science and Technology |
es_ES |
dc.contributor.funder |
Instituto de Salud Carlos III |
es_ES |
dc.description.references |
Girotti, A. W. (1990). PHOTODYNAMIC LIPID PEROXIDATION IN BIOLOGICAL SYSTEMS. Photochemistry and Photobiology, 51(4), 497-509. doi:10.1111/j.1751-1097.1990.tb01744.x |
es_ES |
dc.description.references |
Sevanian, A., & Ursini, F. (2000). Lipid peroxidation in membranes and low-density lipoproteins: similarities and differences. Free Radical Biology and Medicine, 29(3-4), 306-311. doi:10.1016/s0891-5849(00)00342-7 |
es_ES |
dc.description.references |
Montine, T. J., Neely, M. D., Quinn, J. F., Beal, M. F., Markesbery, W. R., Roberts, L. J., & Morrow, J. D. (2002). Lipid peroxidation in aging brain and Alzheimer’s disease1,2 1Guest Editors: Mark A. Smith and George Perry 2This article is part of a series of reviews on «Causes and Consequences of Oxidative Stress in Alzheimer’s Disease.» The full list of papers may be found on the homepage of the journal. Free Radical Biology and Medicine, 33(5), 620-626. doi:10.1016/s0891-5849(02)00807-9 |
es_ES |
dc.description.references |
Shahidi, F., & Zhong, Y. (2010). Lipid oxidation and improving the oxidative stability. Chemical Society Reviews, 39(11), 4067. doi:10.1039/b922183m |
es_ES |
dc.description.references |
Porter, N. A. (1984). [32] Chemistry of lipid peroxidation. Oxygen Radicals in Biological Systems, 273-282. doi:10.1016/s0076-6879(84)05035-7 |
es_ES |
dc.description.references |
Porter, N. A. (1986). Mechanisms for the autoxidation of polyunsaturated lipids. Accounts of Chemical Research, 19(9), 262-268. doi:10.1021/ar00129a001 |
es_ES |
dc.description.references |
Boscá, F., & Miranda, M. A. (1998). New Trends in Photobiology (Invited Review) Photosensitizing drugs containing the benzophenone chromophore. Journal of Photochemistry and Photobiology B: Biology, 43(1), 1-26. doi:10.1016/s1011-1344(98)00062-1 |
es_ES |
dc.description.references |
Velosa, A. C., Baader, W. J., Stevani, C. V., Mano, C. M., & Bechara, E. J. H. (2007). 1,3-Diene Probes for Detection of Triplet Carbonyls in Biological Systems. Chemical Research in Toxicology, 20(8), 1162-1169. doi:10.1021/tx700074n |
es_ES |
dc.description.references |
Encinas, M. V., & Scaiano, J. C. (1981). Reaction of benzophenone triplets with allylic hydrogens. Laser flash photolysis study. Journal of the American Chemical Society, 103(21), 6393-6397. doi:10.1021/ja00411a021 |
es_ES |
dc.description.references |
Nau, W. M., Cozens, F. L., & Scaiano, J. C. (1996). Reactivity and Efficiency of Singlet- and Triplet-Excited States in Intermolecular Hydrogen Abstraction Reactions. Journal of the American Chemical Society, 118(9), 2275-2282. doi:10.1021/ja9535118 |
es_ES |
dc.description.references |
Adam, W., Moorthy, J. N., Nau, W. M., & Scaiano, J. C. (1997). Photoreduction of Azoalkanes by Direct Hydrogen Abstraction from 1,4-Cyclohexadiene, Alcohols, Stannanes, and Silanes. The Journal of Organic Chemistry, 62(23), 8082-8090. doi:10.1021/jo971105w |
es_ES |
dc.description.references |
Boscá, F., Miranda, M. A., Morera, I. M., & Samadi, A. (2000). Involvement of type I and type II mechanisms in the linoleic acid peroxidation photosensitized by tiaprofenic acid. Journal of Photochemistry and Photobiology B: Biology, 58(1), 1-5. doi:10.1016/s1011-1344(00)00102-0 |
es_ES |
dc.description.references |
Samadi, A., Martínez, L. A., Miranda, M. A., & Morera, I. M. (2001). Mechanism of Lipid Peroxidation Photosensitized by Tiaprofenic Acid: Product Studies Using Linoleic Acid and 1,4-Cyclohexadienes as Model Substrates¶. Photochemistry and Photobiology, 73(4), 359. doi:10.1562/0031-8655(2001)073<0359:molppb>2.0.co;2 |
es_ES |
dc.description.references |
Miranda, M. A., Martínez, L. A., Samadi, A., Boscá, F., & Morera, I. M. (2002). Stereoselective intramolecular hydrogen abstraction by a chiral benzophenone derivative. Chemical Communications, (3), 280-281. doi:10.1039/b108858k |
es_ES |
dc.description.references |
Boscá, F., Andreu, I., Morera, I. M., Samadi, A., & Miranda, M. A. (2003). Chiral discrimination in the intramolecular abstraction of allylic hydrogens by benzophenone triplets. Chem. Commun., (13), 1592-1593. doi:10.1039/b303263a |
es_ES |
dc.description.references |
Goez, M., & Frisch, I. (2002). Activation Energy of a Biradical Rearrangement Measured by Photo-CIDNP. The Journal of Physical Chemistry A, 106(35), 8079-8084. doi:10.1021/jp020478k |
es_ES |
dc.description.references |
Goez, M., & Eckert, G. (2006). Photoinduced electron transfer sensitization investigated by chemically induced dynamic nuclear polarizatioin (CIDNP). Physical Chemistry Chemical Physics, 8(45), 5294. doi:10.1039/b609026e |
es_ES |
dc.description.references |
Roth, H. D. (2008). Biradicals by triplet recombination of radical ion pairs. Photochemical & Photobiological Sciences, 7(5), 540. doi:10.1039/b800524a |
es_ES |
dc.description.references |
Neshchadin, D., Levinn, R., Gescheidt, G., & Batchelor, S. N. (2010). Probing the Antioxidant Activity of Polyphenols by CIDNP: From Model Compounds to Green Tea and Red Wine. Chemistry - A European Journal, 16(23), 7008-7016. doi:10.1002/chem.200903238 |
es_ES |
dc.description.references |
CLOSS, G. L. (1974). Chemically Induced Dynamic Nuclear Polarization. Advances in Magnetic and Optical Resonance, 157-229. doi:10.1016/b978-0-12-025507-8.50009-7 |
es_ES |
dc.description.references |
Goez, M. (1995). An introduction to chemically induced dynamic nuclear polarization. Concepts in Magnetic Resonance, 7(1), 69-86. doi:10.1002/cmr.1820070105 |
es_ES |
dc.description.references |
Closs, G. L. (1969). Mechanism explaining nuclear spin polarizations in radical combination reactions. Journal of the American Chemical Society, 91(16), 4552-4554. doi:10.1021/ja01044a043 |
es_ES |
dc.description.references |
Kaptein, R., & Oosterhoff, L. J. (1969). Chemically induced dynamic nuclear polarization III (anomalous multiplets of radical coupling and disproportionation products). Chemical Physics Letters, 4(4), 214-216. doi:10.1016/0009-2614(69)80105-3 |
es_ES |
dc.description.references |
Salikhov, K. M. (1982). Mutual effect of nuclei upon CIDNP in high fields. Violation of the Kaptein rules. Chemical Physics, 64(3), 371-379. doi:10.1016/0301-0104(82)80005-0 |
es_ES |
dc.description.references |
Goez, M. (1992). Pseudo steady-state photo-CIDNP measurements. Chemical Physics Letters, 188(5-6), 451-456. doi:10.1016/0009-2614(92)80847-5 |
es_ES |
dc.description.references |
Kitaguchi, H., Ohkubo, K., Ogo, S., & Fukuzumi, S. (2005). Direct ESR Detection of Pentadienyl Radicals and Peroxyl Radicals in Lipid Peroxidation: Mechanistic Insight into Regioselective Oxygenation in Lipoxygenases. Journal of the American Chemical Society, 127(18), 6605-6609. doi:10.1021/ja044345j |
es_ES |
dc.description.references |
Becke, A. D. (1993). Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98(7), 5648-5652. doi:10.1063/1.464913 |
es_ES |
dc.description.references |
Stephens, P. J., Devlin, F. J., Chabalowski, C. F., & Frisch, M. J. (1994). Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields. The Journal of Physical Chemistry, 98(45), 11623-11627. doi:10.1021/j100096a001 |
es_ES |
dc.description.references |
Schäfer, A., Huber, C., & Ahlrichs, R. (1994). Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. The Journal of Chemical Physics, 100(8), 5829-5835. doi:10.1063/1.467146 |
es_ES |