salicylates and homosalate

Today, topical application of sunscreens, containing ultraviolet-filters (UV-filters), is preferred protection against adverse effects of ultraviolet radiation. Evidently, use of sunscreens is effective in prevention of sunburns in various models. However, evidence for their protective effects against melanoma skin cancer is less conclusive. Three important observations prompted us to review the animal data and human studies on possible side effects of selected chemical UV-filters in cosmetics. (1) the utilization of sunscreens with UV-filters is increasing worldwide; (2) the incidence of the malignant disorder for which sunscreens should protect, malignant melanoma, is rapidly increasing and (3) an increasing number of experimental studies indicating that several UV-filters might have endocrine disruptive effects. The selected UV-filters we review in this article are benzophenone-3 (BP-3), 3-benzylidene camphor (3-BC), 3-(4-methyl-benzylidene) camphor (4-MBC), 2-ethylhexyl 4-methoxy cinnamate (OMC), Homosalate (HMS), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA) and 4-aminobenzoic acid (PABA). The potential adverse effects induced by UV-filters in experimental animals include reproductive/developmental toxicity and disturbance of hypothalamic-pituitary-thyroid axis (HPT). Few human studies have investigated potential side effects of UV-filters, although human exposure is high as UV-filters in sunscreens are rapidly absorbed from the skin. One of the UV-filters, BP-3, has been found in 96% of urine samples in the US and several UV-filters in 85% of Swiss breast milk samples. It seems pertinent to evaluate whether exposure to UV-filters contribute to possible adverse effects on the developing organs of foetuses and children.

Topics: 4-Aminobenzoic Acid; Animals; Benzyl Compounds; Camphor; Cinnamates; Endocrine Disruptors; Humans; Hypothalamo-Hypophyseal System; Melanoma; para-Aminobenzoates; Receptors, Estrogen; Salicylates; Skin Neoplasms; Sunburn; Sunscreening Agents; Thyroid Gland; Ultraviolet Rays

A prior pilot study demonstrated the systemic absorption of 4 sunscreen active ingredients; additional studies are needed to determine the systemic absorption of additional active ingredients and how quickly systemic exposure exceeds 0.5 ng/mL as recommended by the US Food and Drug Administration (FDA).. To assess the systemic absorption and pharmacokinetics of the 6 active ingredients (avobenzone, oxybenzone, octocrylene, homosalate, octisalate, and octinoxate) in 4 sunscreen products under single- and maximal-use conditions.. Randomized clinical trial at a clinical pharmacology unit (West Bend, Wisconsin) was conducted in 48 healthy participants. The study was conducted between January and February 2019.. Participants were randomized to 1 of 4 sunscreen products, formulated as lotion (n = 12), aerosol spray (n = 12), nonaerosol spray (n = 12), and pump spray (n = 12). Sunscreen product was applied at 2 mg/cm2 to 75% of body surface area at 0 hours on day 1 and 4 times on day 2 through day 4 at 2-hour intervals, and 34 blood samples were collected over 21 days from each participant.. The primary outcome was the maximum plasma concentration of avobenzone over days 1 through 21. Secondary outcomes were the maximum plasma concentrations of oxybenzone, octocrylene, homosalate, octisalate, and octinoxate over days 1 through 21.. Among 48 randomized participants (mean [SD] age, 38.7 [13.2] years; 24 women [50%]; 23 white [48%], 23 African American [48%], 1 Asian [2%], and 1 of unknown race/ethnicity [2%]), 44 (92%) completed the trial. Geometric mean maximum plasma concentrations of all 6 active ingredients were greater than 0.5 ng/mL, and this threshold was surpassed on day 1 after a single application for all active ingredients. For avobenzone, the overall maximum plasma concentrations were 7.1 ng/mL (coefficient of variation [CV], 73.9%) for lotion, 3.5 ng/mL (CV, 70.9%) for aerosol spray, 3.5 ng/mL (CV, 73.0%) for nonaerosol spray, and 3.3 ng/mL (CV, 47.8%) for pump spray. For oxybenzone, the concentrations were 258.1 ng/mL (CV, 53.0%) for lotion and 180.1 ng/mL (CV, 57.3%) for aerosol spray. For octocrylene, the concentrations were 7.8 ng/mL (CV, 87.1%) for lotion, 6.6 ng/mL (CV, 78.1%) for aerosol spray, and 6.6 ng/mL (CV, 103.9%) for nonaerosol spray. For homosalate, concentrations were 23.1 ng/mL (CV, 68.0%) for aerosol spray, 17.9 ng/mL (CV, 61.7%) for nonaerosol spray, and 13.9 ng/mL (CV, 70.2%) for pump spray. For octisalate, concentrations were 5.1 ng/mL (CV, 81.6%) for aerosol spray, 5.8 ng/mL (CV, 77.4%) for nonaerosol spray, and 4.6 ng/mL (CV, 97.6%) for pump spray. For octinoxate, concentrations were 7.9 ng/mL (CV, 86.5%) for nonaerosol spray and 5.2 ng/mL (CV, 68.2%) for pump spray. The most common adverse event was rash, which developed in 14 participants.. In this study conducted in a clinical pharmacology unit and examining sunscreen application among healthy participants, all 6 of the tested active ingredients administered in 4 different sunscreen formulations were systemically absorbed and had plasma concentrations that surpassed the FDA threshold for potentially waiving some of the additional safety studies for sunscreens. These findings do not indicate that individuals should refrain from the use of sunscreen.. ClinicalTrials.gov Identifier: NCT03582215.

Topics: Acrylates; Adult; Benzophenones; Cinnamates; Female; Humans; Male; Middle Aged; Propiophenones; Salicylates; Skin Absorption; Sunscreening Agents

Dispersive liquid-liquid microextraction (DLLME) using a floating organic drop has been optimized and used for the sample preparation of four commonly used ultraviolet filter (UVF) substances in sunscreens. Plackett-Burman experimental design was used to screen 10 variables in DLLME. The most significant variables were then optimized by using a response surface method with a Box-Behnken design. DLLME followed by an optimized HPLC identified octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate as the frequently found UVFs in commercial sunscreens. The systemic exposure dosage and margin of safety (MoS) for the identified UVFs were estimated using in-use concentrations and application patterns. The average systemic exposure dosage values for octocrylene, 2-ethylhexyl-4-methoxycinnamate, ethylhexyl salicylate, and homosalate were 0.52, 0.61, 0.020, and 0.079 mg/kg body weight per day, respectively. Whereas the average MoS values for individual UVFs ranging from 296 to 3160 were all significantly higher than the limit value of 100, the combined exposure risks were slightly above the limit. The probabilistic health risk assessment using Monte Carlo simulation revealed that the combined MoS values were (mean, 10‰, 90‰) 342, 119, and 441, respectively. Regarding the usage of sunscreen cosmetics containing the UVFs studied, these results indicate a safety concern for those who apply multiple UVF products.

Topics: Liquid Phase Microextraction; Monte Carlo Method; Salicylates; Sunscreening Agents

Eukaryotic cells, including cancer cells, secrete highly heterogeneous populations of extracellular vesicles (EVs). EVs could have different subcellular origin, composition and functional properties, but tools to distinguish between EV subtypes are scarce. Here, we tagged CD63- or CD9-positive EVs secreted by triple negative breast cancer cells with Nanoluciferase enzyme, to set-up a miniaturized method to quantify secretion of these two EV subtypes directly in the supernatant of cells. We performed a cell-based high-content screening to identify clinically-approved drugs able to affect EV secretion. One of the identified hits is Homosalate, an anti-inflammatory drug found in sunscreens which robustly increased EVs' release. Comparing EVs induced by Homosalate with those induced by Bafilomycin A1, we demonstrate that: (1) the two drugs act on EVs generated in distinct subcellular compartments, and (2) EVs released by Homosalate-, but not by Bafilomycin A1-treated cells enhance resistance to anchorage loss in another recipient epithelial tumour cell line. In conclusion, we identified a new drug modifying EV release and demonstrated that under influence of different drugs, triple negative breast cancer cells release EV subpopulations from different subcellular origins harbouring distinct functional properties.

Topics: Dietary Supplements; Extracellular Vesicles; Humans; Salicylates; Triple Negative Breast Neoplasms

While common molecular anions show a strong propensity to undergo electron detachment upon UV excitation, this process often occurs in competition with molecular ion dissociation. The factors that affect the balance between these two major possible decay pathways have not been well understood to date. Laser photodissociation spectroscopy of the deprotonated forms of the UV filter molecules, Homosalate (HS) and Octyl Salicylate (OS),

Topics: Anions; Electrons; Ions; Salicylates

Homosalate (HMS) is an organic UV filter used in sunscreens and personal care products worldwide. It has been detected in various environmental matrices and in humans after application of HMS-containing products. However, sufficient data on the internal HMS exposure in humans is currently not available. Thus, we aimed at providing an analytical method for the sensitive determination of specific HMS metabolites in human urine. We describe the synthesis of analytical standards for the four oxidative HMS metabolites included in this method: 5-((2-hydroxybenzoyl)oxy)-3,3-dimethylcyclohexane-1-carboxylic acid (HMS-CA) and 3-hydroxy-3,5,5-trimethylcyclohexyl 2-hydroxybenzoate (3OH-HMS), as cis- and trans-isomers, respectively. After enzymatic hydrolysis, urine samples were analyzed using liquid chromatography-electrospray ionization-triple quadrupole-tandem mass spectrometry, including turbulent flow chromatography for online sample cleanup and analyte enrichment (online-SPE-LC-MS/MS). Quantification was performed by stable isotope dilution analysis, using deuterium-labeled HMS-CA as internal standards (cis and trans). Limits of quantification of 0.02-0.04 μg L

Topics: Chromatography, Liquid; Humans; Salicylates; Sunscreening Agents; Tandem Mass Spectrometry

Homosalate (HMS) is a salicylate molecule that is commonly included within commercial sunscreen formulations to provide protection from the adverse effects of ultraviolet (UV) radiation exposure. In the present work, the mechanisms by which HMS provides UV photoprotection are unravelled, using a multi-pronged approach involving a combination of time-resolved ultrafast laser spectroscopy in the gas-phase and in solution, laser-induced fluorescence, steady-state absorption spectroscopy, and computational methods. The unique combination of these techniques allow us to show that the enol tautomer of HMS undergoes ultrafast excited state intramolecular proton transfer (ESIPT) upon photoexcitation in the UVB (290-320 nm) region; once in the keto tautomer, the excess energy is predominantly dissipated non-radiatively. Sharp transitions are observed in the LIF spectrum at close-to-origin excitation energies, which points towards the potential presence of a second conformer that does not undergo ESIPT. These studies demonstrate that, overall, HMS exhibits mostly favourable photophysical characteristics of a UV filter for inclusion in sunscreen formulations.

Topics: Molecular Structure; Photochemical Processes; Salicylates; Ultraviolet Rays

UV filters should be determined a strict toxicological safety prior to approval. Homosalate (HMS) is one of the most widely used organic UV filter. HMS accumulates in aquatic biota ecosystems and humans through the food chain; therefore, it is important to consider the effects on health and know its mechanisms of action.. The study aimed to evaluate the cytotoxic and genotoxic effects of HMS in MCF-7 cell line.. Cell viability was examined by the 3-(4,5-dimethylthiazol-2-yl)2,5-diphenyl tetrazolium bromide (MTT) and cell membrane integrity by the lactate dehydrogenase release assays (LDH), and genotoxicity by using the micronucleus test at 250, 500, 750, 1000, 1500, and 2000 µM concentrations with the human breast cell line MCF-7.. Homosalate affected the cell viability dose-dependently at a concentrations of above 1000 µM. Micronucleus formation was significantly induced at 750 and 1000 µM within 24 hours due to an increase in cytostatic effect, the cell viability of HMS decreased to 57% at a concentration of 2000 µM, and a sufficient number of binucleated cells could not be obtained to count. Homosalate was also clastogenic when the cells were incubated at cytotoxic concentrations.. These results suggest that homosalate can be considered as a cytotoxic and genotoxic substance.

Topics: Apoptosis; Cell Survival; DNA Damage; Dose-Response Relationship, Drug; Humans; MCF-7 Cells; Micronucleus Tests; Salicylates; Sunscreening Agents; Toxicity Tests, Acute

The sun protection factor (SPF) is the most important quantity to characterize the performance of sunscreens. As the standard method for its determination is based on clinical trials involving irradiation of human volunteers, calculations of sunscreen performance have become quite popular to reduce the number of in vivo studies. Such simulations imply the calculation of UV transmittance of the sunscreen film using the amounts and spectroscopic properties of the UV absorbers employed, and presuppose the validity of the Beer-Lambert law. As sunscreen films on human skin can contain considerable concentrations of UV absorbers, it is questioned whether the Beer-Lambert law is still valid for these systems. The results of this work show that the validity of the Beer-Lambert law is still given at the high concentrations at which UV absorbers occur in sunscreen films on human skin.

Topics: Absorption, Radiation; Adipates; Benzimidazoles; Humans; ortho-Aminobenzoates; Reproducibility of Results; Salicylates; Skin; Sun Protection Factor; Sunscreening Agents; Ultraviolet Rays; Water

The human population is widely exposed to benzophenone-3 (BP-3), octylmethoxycinnamate (OMC), 4-methylbenzilidenecamphor (4-MBC) and homosalate from their use in consumer goods to absorb ultraviolet (UV) light. Their oestrogenic activity and presence in human milk suggest a potential to influence breast cancer development. In this study, high-performance liquid chromatography-tandem mass spectrometry was used to measure concentrations of these UV filters in human breast tissue from three serial locations across the breast from 40 women undergoing mastectomy for primary breast cancer. One or more of these UV filters were quantifiable in 101 of 120 (84%) of the tissue samples and at least one breast region for 38 of 40 women. BP-3 was measured in 83 of 120 (69%) tissue samples and at least one breast region for 33 of 40 women (range 0-26.0 ng g

Topics: Benzophenones; Breast; Breast Neoplasms; Camphor; Cinnamates; Female; Humans; Mastectomy; Salicylates; Sunscreening Agents

Topics: Cell Line; Cell Movement; Cell Proliferation; Endoplasmic Reticulum Stress; Humans; Mitochondria; Mitogen-Activated Protein Kinases; Phosphatidylinositol 3-Kinase; Phosphatidylinositol 3-Kinases; Proto-Oncogene Proteins c-akt; Reactive Oxygen Species; Salicylates; Signal Transduction; Sunscreening Agents; Toxicity Tests; Trophoblasts

UV light suppresses experimental autoimmune encephalomyelitis (EAE), a widely used animal model of MS, in mice and may be responsible for the decreased incidence of MS in equatorial regions. To test this concept further, we applied commercially available sunblock preparations to mice before exposing them to UV radiation. Surprisingly, some of the sunblock preparations blocked EAE without UV radiation. Furthermore, various sunblock preparations had variable ability to suppress EAE. By examining the components of the most effective agents, we identified homosalate and octisalate as the components responsible for suppressing EAE. Thus, salates may be useful in stopping the progression of MS, and may provide new insight into mechanisms of controlling autoimmune disease.

Topics: Animals; Disease Models, Animal; Encephalomyelitis, Autoimmune, Experimental; Female; Mice; Mice, Inbred C57BL; Multiple Sclerosis; Salicylates; Sunscreening Agents; Ultraviolet Rays

Homosalate (HMS) and 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA) are ultraviolet filters. We aimed to investigate the effects of dermal exposure to HMS and OD-PABA during the prenatal, lactation, and early infancy periods on pubertal development and thyroid function in male and female rats. The thyroid glands, uteri, testes, prostate glands, and seminal vesicles were excised and weighed, the reproductive organs were analyzed histologically, and the serum hormone levels were measured. In the prenatal period, the thyroxine (T4) levels increased in the female rats in the exposed groups ( p < 0.05); the thyroid weights, reproductive organ weights, and gonadal hormone levels were not altered. In males, the testosterone levels decreased ( p < 0.05), but the thyroid weights, T4 levels, prostate, and testis weights were not changed. In the lactation period, the weights of the thyroid glands increased in the exposed female groups ( p < 0.05), but the T4, gonadal hormone levels, and reproductive organ weights were not changed. In the males, the thyroid gland weights, T4 levels, reproductive organ weights, and gonadal hormone levels were not changed. During infancy, the thyroid gland weights increased in the female rats in the exposed groups ( p < 0.05), but the T4 levels, gonadal hormone levels, and reproductive organ weights were not affected. In the male rats in the exposed groups, the T4 levels were increased ( p < 0.05), but the thyroid and reproductive organ weights, gonadal hormone levels were not affected. Organ histopathology was not affected in all groups. HMS and OD-PABA do not have endocrine disruptor effects on thyroid function and the pubertal development of female and male rats.

Topics: Animals; Animals, Newborn; Endocrine Disruptors; Female; Lactation; Male; Ovary; para-Aminobenzoates; Pregnancy; Rats; Salicylates; Testis; Thyroxine; Uterus

Homosalate (HMS) is an ultraviolet (UV) filtering agent used in sunscreens and other cosmetics for skin protection purposes. Despite the widespread use of these products, absorption, disposition, and in vivo endocrine disrupting potential of HMS have not been characterized. Thus, the aim of this study was to examine the percutaneous absorption, disposition, and exposure assessment of HMS in rats. Initially, sunscreen preparations of petrolatum jelly, oily solution, lotion, and gel were prepared and evaluated for in vitro permeation of HMS across excised rat skin. Dermal permeability was greatest for gel, and this preparation was used in subsequent in vivo topical application investigations. After iv injection (0.5, 2, or 5 mg/kg), the pharmacokinetics of HMS was linear and was characterized by a large Vd(ss) (13.2-17 L/kg), high Cl(s) (4.5-6.1 L/h/kg), and long t½ (6.1-8.4 h). After topical application of gel, the bioavailability of HMS was 5.4 ± 1.1 and 4.2 ± 0.6% for high and low doses (10 and 20 mg), respectively. Consistent with the prolonged absorption (Tmax 11.2 ± 1.8 and 12 ± 0 h for low and high doses, respectively), the terminal t½ was longer after topical application (23.6-26.1 h) compared to iv injection. A population pharmacokinetic model was further developed to simultaneously fit the time courses of plasma concentrations and dermal content data after iv injection and topical application. Findings of this study may be useful to further examine the relationship between exposure and endocrine disrupting potential of HMS in risk assessment.

Topics: Administration, Cutaneous; Animals; Biological Availability; Dose-Response Relationship, Drug; Drug Compounding; Gels; Half-Life; In Vitro Techniques; Injections, Intravenous; Male; Metabolic Clearance Rate; Models, Biological; Permeability; Rats; Rats, Sprague-Dawley; Salicylates; Skin; Skin Absorption; Sunscreening Agents; Tissue Distribution

In the present study, a rapid, highly efficient and environmentally friendly sample preparation method named temperature-controlled ionic liquid dispersive liquid-phase microextraction (TC-IL-DLPME), followed by high performance liquid chromatography (HPLC) was developed for the extraction, preconcentration and determination of four benzophenone-type ultraviolet (UV) filters (viz. benzophenone (BP), 2-hydroxy-4-methoxybenzophenone (BP-3), ethylhexyl salicylate (EHS) and homosalate (HMS)) from water samples. An ultra-hydrophobic ionic liquid (IL) 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]), was used as the extraction solvent in TC-IL-DLPME. Temperature served two functions here, the promotion of the dispersal of the IL to the aqueous sample solution to form infinitesimal IL drops and increase the interface between them and the target analytes (at high temperature), and the facilitation of mass transfer between the phases, and achievement of phase separation (at low temperature). Due to the ultra-hydrophobic feature and high density of the extraction solvent, complete phase separation could be effected by centrifugation. Moreover, no disperser solvent was required. Another prominent feature of the procedure was the combination of extraction and centrifugation in a single step, which not only greatly reduced the total analysis time for TC-IL-DLPME but also simplified the sample preparation procedure. Various parameters that affected the extraction efficiency (such as type and volume of extraction solvent, temperature, salt addition, extraction time and pH) were evaluated. Under optimal conditions, the proposed method provided good enrichment factors in the range of 240-350, and relative standard deviations (n=5) below 6.3%. The limits of detection were in the range of 0.2-5.0 ng/mL, depending on the analytes. The linearities were between 1 and 500 ng/mL for BP, 5 and 1000 ng/mL for BP-3, 10 and 1000 ng/mL for HMS and 5 and 1000 ng/mL for EHS. Finally, the proposed method was successfully applied to the determination of UV filters in swimming pool and tap water samples and acceptable relative recoveries over the range of 88.0-116.0% were obtained.

Topics: Benzophenones; Chromatography, High Pressure Liquid; Imidazoles; Ionic Liquids; Liquid Phase Microextraction; Reproducibility of Results; Salicylates; Sodium Chloride; Sunscreening Agents; Temperature; Water Pollutants, Chemical

A simple, sensitive and selective method for the simultaneous determination of five ultraviolet (UV) filters: benzophenone, octyl salicylate, homosalate, 3-(4-methylbenzylidene) camphor, 2-hydroxy-4-methoxybenzophenone in aqueous samples was developed. The analytes were extracted by plunger-in-needle solid-phase microextraction with graphene as sorbent, then silylated on-fiber with N-methyl-N-(trimethylsilyl)trifluoroacetamide, and analyzed by gas chromatography-mass spectrometry. Factors affecting the performance of extraction and derivatization steps were thoroughly evaluated. For the optimization of extraction conditions, six relevant factors (parameters) were investigated, including sample pH, salt concentration, extraction time, extraction temperature, stirring speed and sampling mode. In the first stage, a two-level orthogonal array design OA(8) (2(7)) matrix was employed to study the effect of six factors. Based on the results of the first stage, three factors were selected for further optimization with a univariant approach during the second stage. Under the final optimized conditions, the method limits of detection for the five UV filters were determined to be in the range of 0.5 and 6.8 ng L(-1) (at a signal/noise ratio of 3) and the precision (% relative standard deviation, n=5) was 0.8-5.6% at a concentration level of 1 μg L(-1). The linearities for different analytes were 10-10,000 or 1-5000 ng L(-1). The coefficients of determination for the calibration curves were all greater than 0.994. Finally, the proposed method was successfully applied to the extraction and determination of the UV filters in river water samples.

Topics: Adsorption; Algorithms; Benzophenones; Calibration; Camphor; Fresh Water; Gas Chromatography-Mass Spectrometry; Graphite; Limit of Detection; Phase Transition; Salicylates; Solid Phase Microextraction; Sunscreening Agents; Ultraviolet Rays; Water Pollutants, Chemical

In the present study, a rapid, highly efficient and environmentally friendly sample preparation method named ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-USA-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for the extraction and preconcentration of four benzophenone-type ultraviolet (UV) filters (viz. benzophenone (BP), 2-hydroxy-4-methoxybenzophenone (BP-3), ethylhexyl salicylate (EHS) and homosalate (HMS)) from three different water matrices. The procedure was based on a ternary solvent system containing tiny droplets of ionic liquid (IL) in the sample solution formed by dissolving an appropriate amount of the IL extraction solvent 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) in a small amount of water-miscible dispersive solvent (methanol). An ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution, which markedly increased the extraction efficiency and reduced the equilibrium time. Various parameters that affected the extraction efficiency (such as type and volume of extraction and dispersive solvents, ionic strength, pH and extraction time) were evaluated. Under optimal conditions, the proposed method provided good enrichment factors in the range of 354-464, and good repeatability of the extractions (RSDs below 6.3%, n=5). The limits of detection were in the range of 0.2-5.0 ng mL(-1), depending on the analytes. The linearities were between 1 and 500 ng mL(-1) for BP, 5 and 500 ng mL(-1) for BP-3 and HMS and 10 and 500 ng mL(-1) for EHS. Finally, the proposed method was successfully applied to the determination of UV filters in river, swimming pool and tap water samples and acceptable relative recoveries over the range of 71.0-118.0% were obtained.

Topics: Benzophenones; Chromatography, High Pressure Liquid; Hydrocarbons, Fluorinated; Hydrogen-Ion Concentration; Imidazoles; Ionic Liquids; Liquid Phase Microextraction; Osmolar Concentration; Salicylates; Sonication; Water Pollutants, Chemical

A sensitive procedure for the determination of three UV filters: ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (Homosalate, HMS), 2-hydroxy-4-methoxybenzophenone (BP-3) and two related hydroxylated benzophenones (2,4-dihydroxybenzophenone, BP-1 and 2,2'-dihydroxy-4-methoxybenzophenone, BP-8) in water samples is presented. Analytes were first concentrated on the coating of a solid-phase microextraction (SPME) fibre, on-fibre silylated and then determined using gas chromatography combined with tandem mass spectrometry (GC-MS/MS). Factors affecting the performance of extraction and derivatization steps are thoroughly evaluated and their effects on the yield of the sample preparation discussed. Under final working conditions, a PDMS-DVB coated SPME fibre was exposed directly to 10 mL of water, adjusted at pH 3, for 30 min. After that, the fibre was placed in the headspace (HS) of a 1.5 mL vial containing 20 microL of N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA). On-fibre silylation of hydroxyl groups contained in the structure of target compounds was performed at 45 degrees C for 10 min. The whole sample preparation process was completed in 40 min, providing limits of quantification from 0.5 to 10 ng L(-1) and acceptable precision (RSDs under 13%) for samples spiked at different concentrations. All compounds could be accurately determined in river and treated wastewater (relative recoveries from 89 to 115%) using standards in ultrapure water, whereas standard addition is recommended to quantify their levels in untreated wastewater. Analysis of wastewater revealed the systematic presence of BP-3 and BP-1 in raw samples with maximum concentrations close to 500 and 250 ng L(-1), respectively.

Topics: Benzophenones; Gas Chromatography-Mass Spectrometry; Reproducibility of Results; Rivers; Salicylates; Solid Phase Microextraction; Sunscreening Agents; Tandem Mass Spectrometry; Temperature; Time Factors; Water; Water Pollutants, Chemical

A simple, inexpensive sample preparation procedure, based on the matrix solid-phase dispersion (MSPD) technique, for the determination of six UV filters: 2-ethylhexyl salicylate (EHS), 3,3,5-trimethylcyclohexyl salicylate (Homosalate, HMS), 3-(4-methylbenzylidene) camphor (4-MBC), isoamyl-p-methoxycinnamate (IAMC), 2-ethylhexyl-p-methoxycinnamate (EHMC) and octocrylene (OCR), in dust from indoor environments is presented and the influence of several operational parameters on the extraction performance discussed. Under the final working conditions, sieved samples (0.5 g) were mixed with the same amount of anhydrous sodium sulphate and dispersed with 2 g of octadecyl bonded silica (C18) in a mortar with a pestle. This blend was transferred to a polypropylene solid-phase extraction cartridge containing 2 g of activated silica, as the clean-up co-sorbent. The cartridge was first rinsed with 5 mL of n-hexane and the analytes were then recovered with 4 mL of acetonitrile. This extract was adjusted to 1 mL, filtered and the compounds were determined by gas chromatography combined with tandem mass spectrometry (GC-MS/MS). Recoveries for samples spiked at two different concentrations ranged between 77% and 99%, and the limits of quantification (LOQs) of the method between 10 and 40 ng g(-1). Analysis of settled dust from different indoor areas, including private flats, public buildings and vehicle cabins, showed that EHMC and OCR were ubiquitous in this matrix, with maximum concentrations of 15 and 41 microg g(-1), respectively. Both UV filters were also quantified in dust reference material SRM 2585 for first time. EHS, 4-MBC and IAMC were detected in some of the analyzed samples, although at lower concentrations than EHMC and OCR.

Topics: Acetonitriles; Acrylates; Air Pollution, Indoor; Camphor; Cinnamates; Dust; Gas Chromatography-Mass Spectrometry; Salicylates; Sensitivity and Specificity; Solid Phase Extraction; Sunscreening Agents; Tandem Mass Spectrometry

Given that flavonoids are known for their ultraviolet (UV)B photoprotective properties in plants that contain them, we chose to study quercetin (1) and rutin (2) as agents that could potentially be used in sunscreen products. These two substances proved to behave in similar ways. When incorporated in oil-in-water emulsions, at a concentration of 10% (w/w), 1 and 2 give sun protection factor (SPF) values similar to that of homosalate, a standard substance. These two flavonoids also provided a non-negligible level of photoprotection in the UVA range. When used in association with titanium dioxide, the SPF obtained was around 30.

Topics: Algorithms; Molecular Structure; Quercetin; Rutin; Salicylates; Sunscreening Agents; Titanium; Ultraviolet Rays

Topics: Administration, Oral; Administration, Topical; Age Factors; Animals; Benzophenones; Cinnamates; Cosmetics; Environmental Exposure; Estradiol Congeners; Ethinyl Estradiol; Female; Guidelines as Topic; Humans; No-Observed-Adverse-Effect Level; Rats; Rats, Long-Evans; Rats, Sprague-Dawley; Rats, Wistar; Research Design; Risk Assessment; Salicylates; Sunscreening Agents; Toxicity Tests; Ultraviolet Rays; Uterus

The potential of 3 sunscreens (p-aminobenzoic acid, 4-isopropyldibenzoylmethane and homosalate) and 2 known human photoallergens (musk ambrette and tetrachlorosalicylanilide) to cause photoallergy, phototoxicity, and/or contact sensitization was determined using a guinea pig photoallergy model, as previously described by Harber and associates. The model was slightly modified by employing 6 exposures over 2 weeks and using Hill Top Chambers for application of the test material. Contact photoallergy was detected in guinea pigs treated with musk ambrette or tetrachlorosalicylanilide (TCSA), although with TCSA, a lower incidence of contact sensitivity and phototoxicity was also detected. The results of studies conducted with sunscreens showed that p-aminobenzoic acid was photoallergenic, whereas homosalate and 4-isopropyl-dibenzoylmethane (Eusolex 8020) were not. However, contact sensitization, and to a lesser degree primary irritation, was detected with Eusolex 8020 at the concentrations employed in this study. The results of these studies suggest that this guinea pig model is a suitable model for assessing the photoallergic potential of various compounds, including the sunscreens tested in this study.

Topics: 4-Aminobenzoic Acid; Animals; Benzoates; Chalcones; Disease Models, Animal; Guinea Pigs; Patch Tests; Photosensitivity Disorders; Salicylates; Sunscreening Agents