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  • 1
    Electronic Resource
    Electronic Resource
    Oxford, UK : Chapman and Hall
    International journal of cosmetic science 20 (1998), S. 0 
    ISSN: 1468-2494
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Medicine
    Notes: We present a new method to evaluate the photo-oxidative activity of sunscreening agents based on the photodynamic oxidation of uric acid. Uric acid was selected as the oxidant probe for its high reactivity to singlet oxygen and oxygen radicals, high sensitivity of detection using electrochemical (EC) techniques, low light absorptivity and high photochemical stability in the UVA/B region of interest, and stability to autoxidation. The method is demonstrated by the photodynamic oxidation of uric acid on co-irradiation with Rose Bengal, a highly efficient photosensitizing dye for the production of singlet oxygen (1O2). Using this assay we found that the relative photodynamic oxidation rates of UVB-absorbing sunscreens in 80% methanol on irradiation with 〉290 nm light decreased in the order 2-ethylhexyl 4-dimethylaminobenzoate (DMABA-2EH) ≫ 2-ethylhexyl 4-methoxycinnamate (MCA-2EH) and the experimental sunscreens, 1-(1,1-dimethylethyl)-3-octanoyl-4,4-dimethyl- 1,4,5,6,-tetrahydropyridine (ICI-319) and 1-(2-methylpropyl)-3-propionyl-4,4-dimethyl-1,4,5,6-tetrahydropyridine (ICI-855). The relative photodynamic oxidation rates of UVA-absorbing sunscreens decreased in the order 4-tert-butyl-4'-methoxydibenzoylmethane (BMDBM) and 4-(2-propyl)benzophenone (PB) 〉 2-hydroxy-4'-methoxy-benzophenone (HMB) and 2,2'-dihydroxy-4-methoxybenzophenone (DHMB). We have confirmed the photodynamic activity of DMABA-2EH for the production of singlet oxygen (1O2) using electron paramagnetic resonance (EPR) spectroscopy and the reagent 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP). We failed to detect the photodynamic production of the oxyradicals, superoxide (O2.-) and hydroxyl radical (HO.) using N-tert-butyl-a-phenylnitrone (PBN) and 5,5-dimethyl-1-pyrrolidine-1-oxide (DMPO) as a result of photochemical interference caused by these spin-trapping reagents. The uric acid photo-oxidation assay was also used to compare the photodynamic reactivity of light-reflective, microfine oxides TiO2, ZnO and ZrO2 suspended in aqueous 80% methanol. All of the microfine oxides (uncoated) showed greater photodynamic reactivity in equimolar dispersion than did any of the organic UVA- and UVB-absorbing sunscreens in homogeneous solution. In this assay the photodynamic oxidation rates for the microfine oxides decreased in the order ZnO ≫ TiO2 (anatase) 〉 ZrO2 〉 TiO2 (rutile). Resume Nous presentons un nouveau procede d'evaluation de l'activite photooxydante d'agents pour ecrans solaires base sur l'oxydation photodynamique de l'acide urique. L'acide urique a ete choisi comme test a l'oxydation en raison de sa forte reactivite a l'oxygene singulet et aux radicaux oxygene, sa haute sensibilite a la detection par les techniques electrochimiques (EC), sa faible capacite d'absorption de la lumiere, sa stabilite photochimique elevee dans le domaine UVA/UVB concerne, et sa stabilite a l'autooxydation. La demonstration du procede est effectuee au travers de l'oxydation photodynamique de l'acide urique co-irradie avec du Rose du Bengale, colorant phosensibilisateur tres efficace pour generer de l'oxygene singulet (1O2). En mettant ce test en oeuvre nous avons trouve que les vitesses relatives d'oxydation photodynamique d'ecrans solaires aux UVB dans due methanol a 80%, irradies avec une lumiere 〉 290nm, diminuent dans l'ordre: 2-ethylhexyl 4-dimethylamino-benzoate (DMABA-2EH) ≫ 2-ethylhexyl 4-methoxycinnamate (MCA-2EH) et les ecrans a l'essai: la 1-(1,1-dimethylethyl)-3-octanoyl-4,4-dimethyl-1,4,5,6-tetrahydopyridine (ICI-319) et la 1-(2-methylpropyl)-3-propionyl-4,4-dimethyl-1,4,5,6-tetrahydropyridine (ICI-855). les vitesses relatives d'oxydation photodynamique d'ecrans solaires aux UVA diminuent dans l'ordre: 4-tert-butyl-4'-methoxydibenzoylmethane (BMDBM) et 4-(2-propyl) benzophenone (PB) 〉 2-hydroxy-4'-methoxybenzophenone (HMB) et 2'2'-dihydroxy-4-methoxybenzophenone (DHMB). Nous avons confirme l'activite photdynamique du DMABA-2EH pour la production d'oxygene singulet (1O2) en utilisant la spectroscopie par resonance paramagnetique electronique et le reactif 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP). Nous n'avons pas pu detecter la production photodynamique des oxyradicaux du superoxyde (O2.) et du radical hydroxyle (HO.) a l'aide de la N-ter-butyl-a- phenylnitrone (PBN) en raison d'interferences photochimiques causees par ces reactifs spin-Bloquants. Le test de photooxydation de l'acide urique a aussi ete utilise pour comparer la reactivite photodynamique d'oxydes microfins reflechisseurs de lumiere TiO2, ZnO et ZrO2 en suspension dans du methanol aqueux a 80%. Tous ces oxydes microfins (non enrobes) ont montre une meilleure reactivite photodynamique en dispersion equimolaire que ne l'a fait aucun des ecrans solaires aux UVA et UVB en solution homogene. Lors de ce test les vitesses d'oxydation photodynamique des oxydes microfins ont diminue dans l'ordre ZnO ≫ TiO2 (anatase) 〉 ZrO2 〉 TiO2 (rutile).
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