Antioxidants for the Stabilization of Sunscreen
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COSMETICS SUNSCREEN K. Jung, M. Seifert, Th. Herrling* Antioxidants for the Stabilization of Sunscreen ■ Introduction However, these inorganic UV filters also Minerals such as titanium dioxide, TiO2, absorb considerable UV-radiation. and zinc oxide, ZnO, are well known ac- To preclude sunburns and protect people tive semiconductor photocatalysts used from serious skin damage, sunscreens extensively in heterogeneous photo- must possess several attributes. They catalysis to destroy environmental pol- have to be photostable (ideally 100%) lutants that are organic in nature. They and they have to dissipate the absorbed are also extensively used in sunscreen lo- energy efficiently through photophysi- Abstract tions as active broadband sunscreens cal and photochemical pathways that that screen both UVB (290-320 nm) and rule out the formation of singlet oxygen, ifferent sunscreen formula- UVA (320-400 nm) sunlight radiation and other reactive oxygen species, and other as high SPF makers. When so photoacti- tions have been investigated harmful reactive intermediates (Fig. 1). vated by UV light, however, these two Dregarding their radical gen- particular metal oxides are known to eration under UV radiation. Organic generate highly oxidizing radicals (•OH -• and inoraganic UV-filter molecules and O2 ) and other reactive oxygen can generate free radicals during species (ROS) such as H2O2 and singlet oxygen, 1O , which are known to be cy- UV-radiation. Whereas organic UV- 2 totoxic and/or genotoxic. Hydroxyl(•OH) filters are marked by their degrada- radicals photogenerated from photoac- tion under UV-light, inorganic filters tive TiO2 specimens extracted from com- are marked by their photocatalytic mercial sunscreen) induce damage to DNA reactions. The generation of free plasmids in vitro and to whole human radicals inside a cosmetic formula- skin cells in cultures. tion leads to the de-stabilization of In contrast to the physical UV-blockers, Fig. 1 The generation of free radicals chemical UV absorbers have to convert the entire cosmetic preparation. by adsorption of an electron the UV light into chemical energy. During Antioxidants can help to overcome this conversion and the following molec- They should not penetrate the skin, and this problem, neutralizing the UV- ular re-arrangements, the excited mole- should not be transported into the hu- induced free radicals. Polyphenolic cules formed by absortion of UV radiation man cells where they can cause delete- compounds, as Green tea extracts, return to the basal state by different ra- rious damage to DNA. Sunscreens should are efficient radical quenchers. The diative and non-radiative decay mecha- also minimize the extent of UVB and UVA nisms. Some of these mecanisms can af- amount of radicals generated with radiation that might reach DNA in cell fect their activity, leading to the forma- nuclei (1-4). With few exceptions, sun- and without the addition of anti- tion of new compounds by photoaddition, screens contain chemical filters (organ- oxidants can be quantified by Elec- substitution, cycloaddition, isomerization, ic; absorb mostly UVB radiation) and tron Spin Resonance (ESR) spec- photofragmentation reactions, etc. The physical filters (e.g., TiO2 and ZnO). The troscopy and is expressed by the molecular re-arrangements are strongly latter have been said to blockUVB/UVA Radical Generationg Factor (RGF). depending on the chemical environment sunlight through reflection and scatter- of the UV-blockers, on their solvent com- ing (5, 6). If this were so, since reflection pounds, purity, and concentration. and scattering are physical phenomena, These new compounds can be inactive the term physical UV filters was coined. (they do not absorb the UV radiation) or 2 SOFW-Journal | 138 | 10-2012 COSMETICS SUNSCREEN favor the degradation of other com- ■ Materials and Methods (2,2,5,5 tetrametylpyrrolidine-N-oxyl - pounds present inside the formulation. PCA). The RGF (Radical Generating Fac- In both cases, the photoprotective effect Chemicals tor) shows the increase of generated free of the sunscreen is compromised. The nitroxide 2,2,5,5 tetrametylpyrroli- radicals indicated as a percentage (%). Eleven commercial sunscreen were test- dine-N-oxyl (PCA) was obtained from ed (7, 8) for their free radical generation Sigma-Aldrich (Germany). A final con- UV irradiation during UV-radiation. The results are ex- centration of 1 mM PCA solution was The UV-irradiation was performed with pressed in percentage as Radical Gener- used. xenon arc lamp Solar Simulator from ating Factor (RGF). The aim of the pre- Eleven different sunscreens (market prod- Newport-ORIEL Product Line 81260 (US, sent study was the characterization of ucts) were used. The content of the UV- Newport Solar Simulators – product speci- the radical generation inside the formu- filter is indirect proportional to the or- fications) equipped with a 300W Xenon lations and the radical reduction due to dinal number. All containing UV-filters lamp supplying an irradiance in the plane antioxidants. Therefore, five antioxida- in an unknown concentration and are of the sample of 16,5 mW/ cm2 for UVA tive raw materials (tocopherol, green tea marked in the INCI declaration (Table 1). (330-400 nm) and 5,0 mW/cm2 for UVB extract, honeybush extract, pomegran- Antioxidants green tea, pomegranate, (290-330 nm). The 81260 has a UVB/UVA ate extract, and rooibos extract) typical- honeybush, and rooibos extract ido- dichroic mirror as a standard device. It ly used in cosmetic formulations (9), were neous for cosmetic preparations were passes 280 to 400 nm and greatly re- added to the tested sunscreens and the purchased from different suppliers. D-α- duces the VIS and IR output of the lamp. radical formation during UV-exposure tocopherol was purchased from Sigma- The measurements were performed with was determined. The antioxidative pow- Aldrich (Munich, Germany) at the high- an UV-Meter-BASIC (hönle UV technolo- er (AP) of the cosmetics was determined est purity grade available. gy, Germany). The UV solar simulator by an ESR spectroscopy method (10). The emits a continuous spectrum with no comparison between the amounts of Free radical indicator gaps or extreme peaks of emission in the free radicals generated with and without Oxygen and carbon centered free radi- UV region. The output from the solar antioxidants led to a rating of antiox- cals generated in skin during UV irra- simulator is stable, uniform across the idative actives that might be useful for diation were detected by using a radical whole output beam and suitable filtered the stabilization of sunscreen products. trap on the basis of nitroxyl compounds to create a spectral quality that complies Code SPF TiO2 BMDBM OC EHS BEMT EHT TDSA HS PBSA DHHB EHMC A 25 3 4 1 2 B 25 3 2 1 4 5 C 30 3 4 1 2 D 30 3 4 1 2 E 30 2 1 3 F 50+ 2 3 1 G 20 3 2 1 H202431567 I 15 3 4 1 2 J 30 3 2 1 4 K 50+ 5 2 1 3 4 6 7 8 List of abbreviation BEMT Bis-Ethylhexyloxyphenolmethoxyphenyl triazine EHT Ethylhexyl triazone BMDM Butyl methoxydibenzoylmethane HS Homosalate DHHB Diethylamino Hydroxybenzoyl Hexyl Benzoate OC Octocrylene EHMC Ethylhexyl methoxycinnamate PBSA Phenylbenzimidazole sulfonic acid EHS Ethylhexyl salicylate TDSA Terephtalylidene dicamphorsulfonic acid Table 1 UV-ilter content for eleven assorted sunscreen 4 SOFW-Journal | 138 | 10-2012 COSMETICS SUNSCREEN with the required acceptance limits. The RCEE% values are in the acceptance lim- Unpaired Electron its. Antioxidant ESR Spectrometer A X-band ESR spectrometer Miniscope 300 Magnettech GmbH, Berlin, Germany was used for in vitro detection of free Electron radicals. A conventionel quartz tube with Donation a inner diameter of 1 mm from Mag- nettech for aques measurements was applied. Experimental process 500 mg of the sunscreen were solved in Free Radical 1000 mg of distilled water. 15 µl of 10 mM PCA were mixed under continuous stir- ring during UV-irradiation with the so- Fig. 2 The effect of antioxidants for neutralizing of free radicals lar simulator. The PCA signal is measured before and after the UV irradiation of 5 minutes. The signal is reduced if free radicals are reduce the amount of UV-induced free Different antioxidants were used which generated. If the signal is not reduced radicals. have a dfferent AP (10). (RGF = 0), there is no generation of free 50 mg of the antioxidant stock solutions radicals. (10% concentrated in water) were added ■ Results The addition of antioxidants (9) can give to 450 mg of the sunscreen. This prepa- the atom the missing electron back to fill ration was added to 1000 mg of water. Table 2 shows the RGF values (%) of 11 in the electrons (Fig. 2). Adding antioxi- The final antioxidant concentration in products, which can be divided into two dants to the sunscreen formulation can the samples was 0.3 %. main groups concerning their radical RGF (%) Antioxidants added to the final formulations Code SPF Pure Honey Bush Vit. E Green Tea Pomegranate Rooibos product Extract (Toco.) Extract Extract Extract 1% 1% 1% 1% 1% AP(AU) 0 10.290 40.400 112.400 70.955 10.788 tr(min) - 0,97 0,33 0,33 0,40 0,72 A 25 22 11 20 0 13 10 B 25 28 18 21 0 16 12 C 30 25 12 25 0 14 9 D 30 25 10 25 0 10 5 E 30 26 20 22 0 15 4 F 50+ 25 8 20 0 17 13 G 20 10 2 10 0 10 10 H20000 000 I 15 10 6 10 0 15 10 J 30 3 0 5 0 3 3 K 50+ 5 1 3 0 3 0 Table 2 RGF(%) after 5’ UV and application of antioxidants 6 SOFW-Journal | 138 | 10-2012 COSMETICS SUNSCREEN generation during UV-irradiation. The The three hydrophilic organic antioxi- ic UV blocker, on the combination of or- products in the first group marked by the dants honey bush with AP=102.900; tr= ganic UV-filters, and on the formulation capital letters A-F show a radical gener- 0,97min; pome granate with AP=709.550; properties.