Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) d...

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Autores principales: Javier Morales, Germán Günther, Antonio L Zanocco, Else Lemp
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Publicado: Public Library of Science (PLoS) 2012
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spelling oai:doaj.org-article:1d8a757e0b4f4588a1a0c047ec31314d2021-11-18T07:13:00ZSinglet oxygen reactions with flavonoids. A theoretical-experimental study.1932-620310.1371/journal.pone.0040548https://doaj.org/article/1d8a757e0b4f4588a1a0c047ec31314d2012-01-01T00:00:00Zhttps://www.ncbi.nlm.nih.gov/pmc/articles/pmid/22802966/pdf/?tool=EBIhttps://doaj.org/toc/1932-6203Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.Javier MoralesGermán GüntherAntonio L ZanoccoElse LempPublic Library of Science (PLoS)articleMedicineRScienceQENPLoS ONE, Vol 7, Iss 7, p e40548 (2012)
institution DOAJ
collection DOAJ
language EN
topic Medicine
R
Science
Q
spellingShingle Medicine
R
Science
Q
Javier Morales
Germán Günther
Antonio L Zanocco
Else Lemp
Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
description Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.
format article
author Javier Morales
Germán Günther
Antonio L Zanocco
Else Lemp
author_facet Javier Morales
Germán Günther
Antonio L Zanocco
Else Lemp
author_sort Javier Morales
title Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
title_short Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
title_full Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
title_fullStr Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
title_full_unstemmed Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
title_sort singlet oxygen reactions with flavonoids. a theoretical-experimental study.
publisher Public Library of Science (PLoS)
publishDate 2012
url https://doaj.org/article/1d8a757e0b4f4588a1a0c047ec31314d
work_keys_str_mv AT javiermorales singletoxygenreactionswithflavonoidsatheoreticalexperimentalstudy
AT germangunther singletoxygenreactionswithflavonoidsatheoreticalexperimentalstudy
AT antoniolzanocco singletoxygenreactionswithflavonoidsatheoreticalexperimentalstudy
AT elselemp singletoxygenreactionswithflavonoidsatheoreticalexperimentalstudy
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