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Journal of Photochemistry and Photobiology A Chemistry
Article . 2002 . Peer-reviewed
License: Elsevier TDM
Data sources: Crossref
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Determination of chemical rate constants in singlet molecular oxygen reactions by using 1,4-dimethylnaphthalene endoperoxide

Authors: Günther, S.; Lemp Miranda, Else; Zanocco Loyola, Antonio;

Determination of chemical rate constants in singlet molecular oxygen reactions by using 1,4-dimethylnaphthalene endoperoxide

Abstract

Abstract Thermal decomposition of 1,4-dimethylnaphthalene endoperoxide (DMNE) as a source of singlet oxygen was used to measure chemical rate constants, k R , for reactions between singlet oxygen, O 2 ( 1 Δ g ), and various substrates. Time resolved O 2 ( 1 Δ g ) IR luminescence detection and steady-state experiments were used to monitor the decomposition of the endoperoxide and the rate of singlet oxygen production. Only 25% of oxygen from thermal decomposition of DMNE, in acetonitrile at 20 °C, is detected as O 2 ( 1 Δ g ). Values of k R for reactions of O 2 ( 1 Δ g ) with 1,4-diphenylisobenzofurane (DPBF) and rubrene measured by this method are similar to values obtained by photosensitization. Values of k R for the chemical reaction of O 2 ( 1 Δ g ) with the antiinflammatory drugs piroxicam and tenoxicam, of (6.1±0.4)×10 6 and (1.6±0.2)±10 7 M −1 s −1 , respectively, are close to those for the total singlet oxygen deactivation rate. Thermal decomposition of aromatic endoperoxides is a convenient source of singlet oxygen for measurements of rate constants in reactions of O 2 ( 1 Δ g ) where photosensitization cannot be employed. However, experimental conditions and approaches involved determine the method’s limitations and applicability in a given system.

Country
Chile
Related Organizations
Keywords

Actinometry, Oxicams, Chemical reation rate constant, Singlet oxygen, Aromatic endoperoxides

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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
15
Top 10%
Top 10%
Average
Green