Background: To explain observed differences during SPF determination using either an in vivo or in vitro method, we hypothesized on the presence of ingredients having anti-inflammatory properties. Methodology/Principal Findings: To research our hypothesis, we studied the 21 UV filters both available on the market and authorized by European regulations and subjected these filters to the phorbol-myristate-acetate test using mice. We then catalogued the 13 filters demonstrating a significant anti-inflammatory effect with edema inhibition percentages of more than 70%. The filters are: diethylhexyl butamido triazone (92%), benzophenone-5 and titanium dioxide (90%), benzophenone-3 (83%), octocrylene and isoamyl p-methoxycinnamate (82%), PEG-25 PABA and homosalate (80%), octyl triazone and phenylbenzimidazole sulfonic acid (78%), octyl dimethyl PABA (75%), bis-ethylhexyloxyphenol methoxyphenyl triazine and diethylamino hydroxybenzoyl hexylbenzoate (70%). These filters were tested at various concentrations, including their maximum authorized dose. We detected a dose-response relationship. Conclusions/Significance: The anti-inflammatory effect of a sunscreen ingredient may affect the in vivo SPF value. Citation: Couteau C, Chauvet C, Paparis E, Coiffard L (2012) UV Filters, Ingredients with a Recognized Anti-Inflammatory Effect. PLoS ONE 7(12): e46187. doi:10.1371/journal.pone.0046187
The results from recent studies show that some benzophenones (BPs) and their hydroxylated metabolites can function as weak estrogens (E2) in the environment. However, little is known about the structure-activity relationship of these molecules. We have examined the effects of exposure to ten different BPs on the proliferation of estrogen receptor (ER)positive breast cancer cells and on the transcriptional activity of E2-target genes. We analyzed two genes that are tightly linked with estrogen-mediated proliferation, the CXCL12 and amphiregulin genes and two classical estrogen-responsive genes, the pS2 and progesterone receptor. Significant differences in the BPs efficiency to induce cell proliferation and endogenous E2-target gene expressions were observed. Using ERE-, Sp1-, AP1- and C3-reporter genes that contain different ER-binding sites in their promoter, we also showed significant differences in the BPs efficiency in activation of the ER transactivation. Together, our analyzes showed that the most active molecule is 4-hydroxy-BP. Docking analysis of the interaction of BPs in the ligand-binding pocket of ER alpha suggests that the minimum structural requirement for the estrogenic activity of BPs is a hydroxyl (OH) group in the phenyl A-ring that allows interaction with Glu-353, Arg-394 or Phe-404, which enhances the stability between BPs and ER alpha. Our modeling also indicates a loss of interaction between the OH groups of the phenyl B-ring and His-524. In addition, the presence of some OH groups in the phenyl B-ring can create repulsion forces, which may constrain helix 12 in an unfavorable position, explaining the differential estrogenic effects of BPs. These results, together with our analysis of BPs for their potency in activation of cell proliferation and ER-mediated transcription, report an improved understanding of the mechanism and structure-activity relationship of BPs.
A methodology based on solid-phase-microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in water. The extraction parameters (the extraction mode and temperature, the fibre coating, and the addition of salt) were optimised by means of experimental designs in order to select the best extraction conditions. The final proposed conditions were 10 mL of water sample with 35% NaCl added, extracted in the headspace mode with a polyacrylate (PA) fibre at 100 °C for 20 minutes. The SPME-GC-MS/MS method was validated in terms of linearity ( R 2 ≥ 0.9937), accuracy and precision, obtaining LODs in the range of 0.068-12 ng L −1 . The validated methodology was then applied to the analysis of different bathing water samples including sea, river, spa, swimming pool, and aquapark water, allowing the detection of 10 of the 14 target compounds; some of them were found at concentrations up to 692 ng mL −1 . A headspace SPME-GC-MS/MS method for the analysis of 14 UV filters in different types of bathing water samples has been developed.
Six UV filters - benzophenone-3 (BP-3), octocrylene (OC), ethylhexyl dimethyl p-aminobenzoate (OD-PABA), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (EHS) and homosalate (HMS) - with endocrine disrupting potential were monitored in different wastewater treatment plants (WWTPs) located in Genoa, Italy. The influent and effluent samples were collected once a month from April to September 2011. The analytes were determined by stir bar sorptive extraction followed by liquid desorption (SBSE-LD) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Quantitative analysis was performed in triggered MRM (tMRM), which allowed improvement of specificity without compromising sensitivity. In the inlet samples four analytes were detected; in particular BP-3, OC, EHMC, and OD-PABA were in the range of 4-163, 12-390, 23-68, and 2-4 ng L-1, respectively. Measured concentrations indicated variability of UV filter inputs to WWTPs, with higher loads during the warmer months. A highly positive correlation was found between air temperature and the measured concentration of OC and BP-3. Only BP-3 and OC were detected in some effluent samples, with considerably lower concentrations. The removal efficiencies of the plants were in the range of 64 to >99% and 94 to >99% for BP-3 and OC, respectively.
A methodology based on solid-phase-microextraction (SPME) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for the simultaneous analysis of 14 UV filters of different chemical nature in water. The extraction parameters (the extraction mode and temperature, the fibre coating, and the addition of salt) were optimised by means of experimental designs in order to select the best extraction conditions. The final proposed conditions were 10 mL of water sample with 35% NaCl added, extracted in the headspace mode with a polyacrylate (PA) fibre at 100 °C for 20 minutes. The SPME-GC-MS/MS method was validated in terms of linearity (R2 ≥ 0.9937), accuracy and precision, obtaining LODs in the range of 0.068–12 ng L−1. The validated methodology was then applied to the analysis of different bathing water samples including sea, river, spa, swimming pool, and aquapark water, allowing the detection of 10 of the 14 target compounds; some of them were found at concentrations up to 692 ng mL−1.
Background: UVA rays present in sunlight are able to reach the dermal skin layer generating reactive oxygen species (ROS) responsible for oxidative damage, alterations in gene expression, DNA damage, leading to cell inflammation, photoageing/-carcinogenesis. Sunscreens contain UV filters as active ingredients that absorb/reflect/dissipate UV radiation: their efficiency depends on their spectral profile and photostability which should then be reflected in biological protection of underlying skin. Methods: A set of new UV filters was synthesized, and the most photostable one was compared to BMDBM, a widely used UVA filter. Cultured human dermal fibroblasts were exposed to UVA radiation which was filtered by a base cream containing or not UV filters placed above cell culture wells. The endpoints measured were: cell viability (MTT assay), ROS generation (DCFH-DA assay), mitochondrial function (JC-1 assay), DNA integrity (Comet assay) and gene expression (MMP-1, COL1A1) by RT-qPCR. Results: The new UV filter resulted more efficient than BMDBM in preserving cell viability, mitochondrial functionality and oxidative DNA damage, despite similar inhibition levels of intracellular ROS. Moreover, expression of genes involved in dermal photoageing were positively affected by the filtering action of the tested molecules. Conclusions: The experimental model proposed was able to validate the efficacy of the new UV filter, taking into account important cellular events related to UV-induced intracellular oxidative stress, often underestimated in the assessments of these compounds. General Significance: The model may be used to compare the actual biological protection of commercial sunscreens and suncare products aside from their SPF and UVA-PF values.
Benzophenone (BP)-type UV (ultraviolet) filters, especially 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), are widely used in the U S, to protect the skin and hair from UV irradiation Despite human exposures to UV filters through the dermal application of products containing sunscreen aunts, few studies have examined the occurrence of UV filters in humans. Thus far, few sensitive methods are available for the determination of 2OH-4MeO-BP in human urine Furthermore, methods for the determination of other BP derivatives, including 2,4-dihydroxybenzophenone (2,4OH-BP), which is formed from 2OH-4MeO-BP via metabolic activities of the cytochrome P450 enzymes. have not been available In this study, we have developed a method for the analysis of five BP derivatives 2OH-4MeO-BP, 2,4OH-BP, 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP). 2,2'.4,4'-tetrahydroxybenzophenone (2,2'.4,4'OH-BP), and 4-hydroxybenzophenone (4OH-BP) in human urine, using liquid-liquid extraction and liquid chromatograph (LC)-tandem mass spectrometer (MS/MS) analysis The instrumental calibration range for each of the BP derivatives ranged from 0 05 to 100 ng ml(-1), and showed excellent linearity (r > 0 99) The respective limits of detection (LODs) and limits of quantification (LOQs) were determined to be 0 082 and 0 28 ng ml(-1) for both 2,4OH-BP and 4OH-BP; 0.13 and 0 44 ng ml(-1) for 2,2'OH-4MeO-BP, and 0 28 and 0 90 ng ml(-1) for both 2OH-4MeO-BP and 2,2',4,4'OH-BP Recoveries of BP derivatives through the entire analytical procedure were between 85.2 and 99 6%. The coefficients of variation (CVs) of five replicate analyses within I day, and across 5 days, were respectively 1.4 and 3 7% for 2.4OH-BP, 1 7 and 3 0% for 2OH-4MeO-BP, and 2 8 and 4 5% for 4OH-BP When BP derivatives were determined in urine samples from 23 U S (Albany, New York) and 22 Japanese (Matsuyama, Ehime) volunteers, higher concentrations of 2,4OH-BP, 2OH-4MeO-BP, and 4OH-BP were found in samples collected from females in the Albany cohort, probably reflecting great usage by U S. females. The urine sample from a known sunscreen user contained very high concentrations of 2,4OH-BP and 2OH-4MeO-BP. 2,2',4,4'OH-BP and 2,2'OH-4MeO-BP were not detected in any of the urine samples analyzed Our results indicate considerable exposure to highly estrogenic 2,4OH-BP and 2OH-4MeO-BP by females in the U S and suggest the need for further studies on potential health effects.
Benzophenone-2 (BP-2) is an important type of UV filter that has been widely used and detected in the aquatic environment with greater estrogenic toxicity. In our work, the removal of BP-2 with the initial concentration of 25 mg L −1 was first carried out by ozone at different pH (ranging from pH 3.0 to 11.0), and we found a positive correlation between the pH values and the degradation efficiency of BP-2, among which the more rapid removal of BP-2 in alkaline condition was observed than acidic and neutral conditions. For the influence of aqueous humic acid (HA, the concentration ranged from 0 ppm to 100 ppm), the degradation rate of BP-2 by ozonation was first increased with the growth of humic acid concentration (from 0 ppm to 5 ppm), reaching to maximum at 5 ppm of HA and subsequently decreased with the growth of HA concentration (from 5 ppm to 100 ppm). Fourteen intermediate products in the ozonation process were distinguished by an electrospray time-of-flight mass spectrometer and then two degradation pathways were proposed. Through the theoretical calculation, we found the carbanyl group of BP-2 has the most reactivity to be easily attacked by ozone, providing us guides and theoretical basis on the supposed intermediate products. Furthermore, the P. phosphoreum acute toxicity test was conducted to evaluate the potential toxicity during the ozonation process.
In this paper, the ultraviolet/persulfate (UV/PDS) combined oxidation process was used to remove the ethyl 4-aminobenzoate (Et-PABA), one of the typical 4-aminobenzoic acid (PABA)-type UV filters. The effects of various factors on the removal of Et-PABA using the UV/PDS process were investigated, and the degradation mechanisms of Et-PABA were explored. The results showed that the UV/PDS process can effectively remove 98.7% of Et-PABA within 30 min under the conditions: UV intensity of 0.92 mW·cm−2, an initial concentration of Et-PABA of 0.05 mM, and a PDS concentration of 2 mM. The removal rate of Et-PABA increased with the increase in PDS dosage within the experimental range, whereas humic acid (HA) had an inhibitory effect on Et-PABA removal. Six intermediates were identified based on HPLC–MS and degradation pathways were then proposed. It can be foreseen that the UV/PDS oxidation process has broad application prospects in water treatment.