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Impact of Photostability and UVA/UVA-Blue Light Protection On Thannhausen, Germany, August 06, 2019 Thannhausen, Germany, | Volume 145 Volume | 7+8/19 powered by skin whitening Natural Extremolyte Fights Pigmentation Caused by Environmental Stressors 7/8 Impact of Photostability 2019 english solubilizers Effective Natural Alternatives to Synthetic Solubilizers – a Comparison Study sun care and UVA/UVA-Blue Light Impact of Photostability and UVA/UVA-Blue Light Protection on Free Radical Generation Blue Light Induced Hyperpigmentation in Skin and How to Prevent it Photostabilisation: The Key to Robust, Protection on Free Radical Safe and Elegant Sunscreens disinfection Skin and Environmentally Safe and Universally Useable Disinfectant for all Generation Surfaces with Green Technology skin/hair care Natural Oil Metathesis Unveils High-Performance Weightless Cosmetic Emollients M. Sohn, S. Krus, K. Jung, M. Seifert, M. Schnyder SOFW Journal 7+8/19 | Volume 145 | Thannhausen, Germany, August 06, 2019 personal care | sun care Impact of Photostability and UVA/UVA-Blue Light Protection on Free Radical Generation M. Sohn, S. Krus, K. Jung, M. Seifert, M. Schnyder abstract he impact of UV-filter combination on the number of free radicals generated in sunscreen formulations and the skin follow- Ting UV-VIS irradiation was assessed via electron spin resonance spectroscopy using a spin-probing approach. Four UV-filter combinations that differed in their photostability and range of UVA absorbance coverage were investigated. Fewer free radicals were generated in the sunscreen formulation when a photostable UVA filter system was used, compared to a stabilized UVA fil- ter system. Additionally, fewer free radicals were generated in the skin when a sunscreen with long UVA protection extending to the short visible range was used, compared to a sunscreen with minimal UVA protection. This study showed that the photosta- bility of a UV-filter system is central to the generation of free radicals in a formulation, and that long UVA-blue light protection is key for avoiding the generation of free radicals in the skin. A sunscreen product exhibiting both photostable UVA protection and long UVA-blue light protection is therefore the most appropriate choice for protecting against ROS-induced skin damage. Introduction Knowledge of skin and health-related photodamage grows yl radicals that could trigger further chain reactions as well as with each passing decade. Beyond the first visible damage, highly reactive singlet oxygen [7]. The generated free radicals i.e. sunburn, DNA damage occurring immediately after sun can result in additional free radical chain reactions through exposure only becomes visible years later. DNA damage can in- interaction with either photocatalytic formulation ingredients clude nucleus DNA damage related to UVB-induced breakage or, even worse, skin-photosensitizing molecules. Photostabili- of DNA strands [1, 2], as well as mitochondrial DNA damage, zation of BMDBM was shown to be effective in triplet-triplet primarily via UVA-induced free radicals [3]. Zastrow et al. pub- energy transfer from the excited keto form to a quenching lished a spectrum exhibiting the effectiveness of free radical molecule such as the UV filters Octocrylene and Bis-Ethyl- formation from 290 to 700 nm [4] and showed that both UV hexyl oxy phenol Methoxyphenyl Triazine (BEMT) [8, 9]. How- and visible (VIS) radiation account for the generation of free ever, the current trend is to avoid octocrylene due to environ- radicals, with UVA radiation being the biggest contributor. mental or health-related issues [10-12]. The well-known photo-instability of some UV filters used The overall objective of the present study is to evaluate the around the world is problematic due to the formation of impact of UV-filter combination on the generation of free damaging free radicals. This is the case with the UVA filter radicals. In an initial study, we first assessed the influence of Butyl Methoxydibenzoylmethane (BMDBM), which under- the UV-filter system on the number of free radicals generated goes an irreversible photodegradation of its keto isomer in in the sunscreen formulation following UV irradiation; in a the triplet state via a Norrish type I cleavage, resulting in the second study, we assessed the number of free radicals gen- formation of benzoyl and phenacyl radicals [5, 6]. In addition erated in the skin after UV-VIS irradiation. In both studies, to BMDBM, the water-soluble UV filter Phenylbenzimidazole the assessment of the free radicals was performed using elec- Sulfonic Acid (PBSA) has also been shown to convert into an tron spin resonance (ESR) spectroscopy measurements with a organic PBSA* radical and to produce superoxide and hydrox- spin-probing approach. The Latest News from the Cosmetic, Personal & Home Care Ingredients Industry › directly on your mobile device › free › subscribe & unsubscribe anytime 2 sofwjournal | 145 | 7+8/19 sun care | personal care Materials and Methods The formulation chassis is based on emulsifiers and emollients commonly used in the sun care industry; they have been cho- Sunscreen Formulations sen to ensure a stable formulation and full solubilization of the UV-filters, regardless of the combination tested. The investigated sunscreens differed exclusively in their UV- The UV-filter combinations were all designed to provide an filter combinations.Tab. 1 describes the formulation chassis SPF of 30, but to differ in the UVA protection, from low to used for both studies, consisting of a standard oil-in-water very high UVA protection. Sunscreen formulation 214-1-5 emulsion; Tab. 2 describes the investigated UV-filter combi- would not fulfill the European UVA requirement; sunscreens nations. 214-1-1 and 214-1-2 would fulfill it; whereas sunscreen 214-1-3 would provide a much higher UVA protection than the European requirement, Phase Trade Name INCI wt % extending to the blue light spectral range A Emulgade® Sucro ¹ Sucrose Polystearate (and) 3.00 (high energy visible, or HEV). Furthermore, Hydrogenated Polyisobutene the sunscreens differed in the UVA filter employed, which was BMDBM for sun- Eumulgin® Prisma ¹ Disodium Cetearyl 1.00 Sulfosuccinate screens 214-1-5 and 214-1-1 and DHHB for sunscreens 214-1-2 and 214-1-3. In Lanette® O ¹ Cetearyl Alcohol 1.50 addition to the sunscreen formulations, the ® Cetiol CC ¹ Dicaprylyl Carbonate 5.00 study involved a placebo formulation that Cetiol® Sensoft ¹ Propylheptyl Caprylate 5.00 did not contain any UV filters. Cetiol® B ¹ Dibutyl Adipate 12.00 Preservative qs Measurement of Free Radicals UV-filter system qs The free radicals generated under light B Water Qsp 100 % exposure were measured via electron spin Glycerin Glycerin 2.00 resonance (ESR) spectroscopy (MiniScope Rheocare® XGN ¹ Xanthan Gum 0.20 MS300, Magnettech GmbH Berlin, Ger- Edeta BD ¹ Disodium EDTA 0.20 many). For both studies, a spin-probing approach was used to measure the free C UV-filter system qs radicals generated either in the formulation D Cetiol® Ultimate ¹ Undecane, Tridecane 2.00 (study 1) or in the skin (study 2). The organ- ¹ from BASF SE (Ludwigshafen, Germany) ic nitroxide free radical (PCA, (2,2,5,5-tetra- methyl pyrrolidine N-oxyl, Sigma- Aldrich, Tab. 1 Chassis of the sunscreen formulations used in both studies. Munich, Germany) was used as spin probe; Minimally Photo- Photo- Unstable Placebo stabilized stable stable long UVA UVA UVA 1/3 UVA–HVE Formulation ID 214-1-4 214-1-5 214-1-1 214-1-2 214-1-3 UV filters Diethylamino Hydroxybenzoyl Hexyl Benzoate (DHHB) 1 – – – 4.00 4.00 Butyl Methoxydibenzoyl Methane (BMDBM) – 4.00 4.00 – – Ethylhexyl Triazone (EHT) 2 – 2.00 2.00 4.00 0.50 Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (BEMT) 3 – 1.00 2.50 2.20 1.00 Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (MBBT) 4 – – – – 8.00 Tris-Biphenyl Triazine (TBPT) 5 – – – – 3.00 Ethylhexyl Salicylate (EHS) – 5.00 5.00 5.00 3.50 Phenylbenzimidazole Sulfonic Acid (PBSA) – 3.00 2.00 – – SPF calculated 6 – 27 30 30 30 UVA-PF calculated 6 – 7.4 9.9 10.5 26.8 1 Uvinul® A Plus, 2 Uvinul® T150, 3 Tinosorb® S, 4 Tinosorb® M, 5 Tinosorb® A2B, 6 with the BASF sunscreen simulator [13] Tab. 2 Composition of UV-filter combinations in % by weight. 7+8/19 | 145 | sofwjournal 3 personal care | sun care it remains stable over time but readily reacts when free radicals before each measurement. The free radicals induced in the are generated and is reduced to the ESR-silent hydroxylamine. skin after UV-VIS exposure reacted with the PCA probe, re- ducing it to an ESR-silent hydroxylamine. The signal intensity Study 1 decay was measured as a function of UV exposure doses di- For the measurement of free radicals in the formulation, the rectly inside the skin biopsies. The results are expressed as the formulas were diluted 1:10 in water and PCA was added to percentage of free radicals induced after each UV dose. All a final concentration of 0.01 mM. Quartz ESR capillary tubes values were normalized to placebo-treated skin. Each value were filled with 40 µL of the resulting solutions, and the PCA is the result of a minimum 4 independent measurements on signal intensities were determined before and after various 3 – 5 different skin biopsy samples. doses of UV radiation (280-400 nm). UV irradiation of the samples was performed using a UV solar simulator 300 W UV and Blue Light Transmittance Measurements with Oriel (Newport). The irradiances as integrated values over Photostability Assessment the spectral ranges were E (UVB = 280-320) = 23.5 W/m² and E (UVA = 320-400nm) = 180 W/ m². To test the effect The transmittance profile of the investigated sunscreens ap- of different UV doses, the irradiation time was varied and plied on a roughened PMMA plate in an amount of 1.3 mg/cm² the samples exposed to up to 10 minutes of UV irradiation (SB6 from HelioScreen Labs, FR) was measured from 290 to (= 13.9 J/cm²).
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