Vayá Pérez, I.; Andreu Ros, MI.; Jiménez Molero, MC.; Miranda Alonso, MÁ. (2014). Photooxygenation mechanisms in naproxen-amino acid linked systems. Photochemical & Photobiological Sciences Photochemical and Photobiological Sciences. 13:224-230. doi:10.1039/c3pp50252j
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Title:
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Photooxygenation mechanisms in naproxen-amino acid linked systems
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Author:
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Vayá Pérez, Ignacio
Andreu Ros, María Inmaculada
Jiménez Molero, María Consuelo
Miranda Alonso, Miguel Ángel
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UPV Unit:
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Universitat Politècnica de València. Departamento de Química - Departament de Química
Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química
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Issued date:
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Abstract:
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The photooxygenation of model compounds containing the two enantiomers of naproxen (NPX) covalently
linked to histidine (His), tryptophan (Trp) and tyrosine (Tyr) has been investigated by steady state
irradiation, ...[+]
The photooxygenation of model compounds containing the two enantiomers of naproxen (NPX) covalently
linked to histidine (His), tryptophan (Trp) and tyrosine (Tyr) has been investigated by steady state
irradiation, fluorescence spectroscopy and laser flash photolysis. The NPX–His systems presented the
highest oxygen-mediated photoreactivity. Their fluorescence spectra matched that of isolated NPX and
showed a clear quenching by oxygen, leading to a diminished production of the NPX triplet excited state
(
3
NPX*–His). Analysis of the NPX–His and NPX–Trp photolysates by UPLC-MS–MS revealed in both cases
the formation of two photoproducts, arising from the reaction of singlet oxygen (1
O2) with the amino acid
moiety. The most remarkable feature of NPX–Trp systems was a fast and stereoselective intramolecular
fluorescence quenching, which prevented the efficient formation of 3
NPX*–Trp, thus explaining their
lower reactivity towards photooxygenation. Finally, the NPX–Tyr systems were nearly unreactive and
exhibited photophysical properties essentially coincident with those of the parent NPX. Overall, these
results point to a type II photooxygenation mechanism, triggered by generation of 1
O2 from the 3
NPX*
chromophore
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Subjects:
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Amino acid
,
Naproxen
,
Oxygen
,
Absorption
,
Chemical structure
,
Chemistry
,
Conformation
,
Photolysis
,
Molecular Conformation
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Copyrigths:
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Reserva de todos los derechos
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Source:
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Photochemical & Photobiological Sciences Photochemical and Photobiological Sciences. (issn:
1474-905X
) (eissn:
1474-9092
)
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DOI:
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10.1039/c3pp50252j
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Publisher:
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Royal Society of Chemistry
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Publisher version:
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http://dx.doi.org/10.1039/c3pp50252j
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Project ID:
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Spanish Government (CTQ2010- 14882, JCI-2011-09926, Miguel Servet CP11/00154)
EU (PCIG12-GA-2012-334257)
Universitat Politècnica de València (SP20120757)
Consellería de Educació, Cultura i Esport (PROMETEOII/2013/005, GV/2013/051)
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Thanks:
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Financial support from the Spanish Government (CTQ2010-14882, JCI-2011-09926, Miguel Servet CP11/00154), from the EU (PCIG12-GA-2012-334257), from the Universitat Politecnica de Valencia (SP20120757) and from the Conselleria ...[+]
Financial support from the Spanish Government (CTQ2010-14882, JCI-2011-09926, Miguel Servet CP11/00154), from the EU (PCIG12-GA-2012-334257), from the Universitat Politecnica de Valencia (SP20120757) and from the Conselleria de Educacio, cultura i Esport (PROMETEOII/2013/005, GV/2013/051) is gratefully acknowledged.
[-]
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Type:
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Artículo
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