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1.
This study describes the development, validation and application of a high‐performance liquid chromatography (HPLC) method for the simultaneous determination of the in vitro skin penetration profile of four UV filters on porcine skin. Experiments were carried out on a gel‐cream formulation containing the following UV filters: diethylamino hydroxybenzoyl hexyl benzoate (DHHB), bis‐ ethylhexyloxyphenol methoxyphenyl triazine (BEMT), methylene bis‐ benzotriazolyl tetramethylbutylphenol (MBBT) and ethylhexyl triazone (EHT). The HPLC method demonstrated suitable selectivity, linearity (10.0–50.0 μg/mL), precision, accuracy and recovery from porcine skin and sunscreen formulation. The in vitro skin penetration profile was evaluated using Franz vertical diffusion cells for 24 h after application on porcine ear skin. None of the UV filters penetrated the porcine skin. Most of them stayed on the skin surface (>90%) and only BEMT, EHT and DHHB reached the dermis plus epidermis layer. These results are in agreement with previous results in the literature. Therefore, the analytical method was useful to evaluate the in vitro skin penetration of the UV filters and may help the development of safer and effective sunscreen products.  相似文献   

2.
Four different miniaturized methodologies were developed and applied to the analysis of 11 UV filters in sand samples. These approaches were based on ultrasound and vortex extractions, on‐column lixiviation, and ultrasound extraction followed by solid‐phase microextraction. Gas chromatography with tandem mass spectrometry was used for quantitative analysis. The analytical performance provided by the four methods was evaluated in terms of linearity, accuracy, precision, and limits of quantification. Lixiviation was discarded since it provided the lowest recoveries and the highest limits of quantification. In contrast, ultrasound and vortex extractions, and ultrasound extraction followed by solid‐phase microextraction were suitable, with recoveries in general >85% and limits of quantification at the low ng/g level. Moreover, ultrasound extraction followed by solid‐phase microextraction allowed using external calibration with aqueous standards and it provided higher sensitivity, with limits of quantification in general one order of magnitude lower than those achieved with the other techniques. The methodologies were applied for the analysis of four marine sand samples, and the results were statistically compared performing an analysis of variance. Eight out of the eleven target UV filters were detected. Octocrylene was found at very high concentrations (up to 1000 ng/g) followed by ethylhexyl salicylate, 4‐methylbenzylidene camphor, homosalate, and 2‐ethylhexyl methoxycinnamate.  相似文献   

3.
A screening method for analyzing environmental waters contaminated with UV filters using direct analysis in real-time mass spectrometry (DART-MS) was developed. To demonstrate the suitability of DART-MS a test set of seven organic UV filters, namely benzophenone-3 (BP-3), ethylhexyl dimethyl p-aminobenzoate (OD-PABA), 4-t-butyl-4′-methoxydibenzoylmethane (BM-DBM), homomethyl salicylate (HMS), 2-(ethylhexyl) salicylate (EHS), octocrylene (OC), and 4-methylbenzylidene camphor (4-MBC), was defined. In the first step, standard solutions of the analytes prepared in methanol were investigated in order to determine optimum parameters for the DART-MS. Because of the very low concentrations of UV filters expected in environmental water samples, a pre-concentration step using stir bar sorptive extraction was performed. DART-MS allows the direct, simple and rapid semi-quantitative analysis of the analytes enriched on the surface of the polydimethylsiloxane-coated stir bars. The optimized method provided calibration curves with correlation coefficients R > 0.959, repeatability from 5% (for 4-MBC) to 30% (for BM-DBM) relative standard deviation and limits of detection lower than 40 ng L−1 for all analytes. Finally, real lake water samples from locations with typical leisure activities were analyzed. Results obtained with the developed DART-MS method were cross-checked by confirmatory analysis using thermodesorption gas chromatography mass spectrometry (TD-GC-MS). Thereby, it could be demonstrated that both analytical methods provide comparable concentrations for the UV filters in the lake water samples.  相似文献   

4.
The coencapsulation of two UV filters, butyl‐methoxydibenzoylmethane (BMDBM) and octocrylene (OCT), into lipid nanocarriers was explored to develop stable cosmetic formulations with broad‐spectrum photoprotection and slow release properties. Different types of nanocarriers in various concentrations of the two UV filters were tested to find the combination with the best absorption and release properties. Solid lipid nanoparticles (SLNs) and nanostructured lipid carriers (NLCs) have been the two types of lipid nanocarriers used. The NLCs were based on either medium chain triglycerides (MCT) or squalene (Sq). The following physicochemical properties of the nanocarriers have been evaluated: particle size, morphology, zeta potential (ZP), entrapment efficiency, loading capacity, and thermal behavior. The nanocarriers have been formulated into creams containing low amounts of UV filters (2.5% BMDBM and 1% OCT). The best photoprotection results were obtained with the cream based on NLCs prepared with MCT, having a sun protection factor (SPF) of 17.2 and an erythemal UVA protection factor (EUVA–PF) of 50.8. The photostability of the encapsulated BMDBM filter was confirmed by subjecting the nanocarriers‐based creams to in vitro irradiation. The prolonged UV‐protection efficacy was coupled with a slow in vitro release of the synthetic UV filters, which followed the Higuchi release model.  相似文献   

5.
The UV absorption, phosphorescence and phosphorescence‐excitation spectra of benzophenone (BP) derivatives used as organic UV absorbers have been observed in rigid solutions at 77 K. The triplet–triplet absorption spectra have been observed in acetonitrile at room temperature. The BP derivatives studied are 2,2′,4,4′‐tetrahydroxybenzophenone (BP‐2), 2‐hydroxy‐4‐methoxybenzophenone (BP‐3), 2,2′‐dihydroxy‐4,4′‐dimethoxybenzophenone (BP‐6), 5‐chloro‐2‐hydroxybenzophenone (BP‐7) and 2‐hydroxy‐4‐n‐octyloxybenzophenone (BP‐12). The energy levels and lifetimes of the lowest excited triplet (T1) states of these BP derivatives were determined from the first peak of phosphorescence. The time‐resolved near‐IR emission spectrum of singlet oxygen generated by photosensitization with BP‐7 was observed in acetonitrile at room temperature. BP‐2, BP‐3, BP‐6 and BP‐12 show photoinduced phosphorescence enhancement in ethanol at 77 K. The possible mechanism of the observed phosphorescence enhancement is discussed. The T1 states of 2‐hydroxy‐5‐methylbenzophenone, 4‐methoxybenzophenone and 2,4′‐dimethoxybenzophenone have been studied for comparison.  相似文献   

6.
This paper presents the development of a fast and sensitive analytical method for the simultaneous determination of UV filters and degradation products having quite different polarities (log Kow 2.19–6.88) in sediment, by means of pressurized liquid extraction (PLE) with in-cell purification and analysis by ultra-performance liquid chromatography (UPLC) coupled to tandem mass spectrometry (MS/MS). Analytes were simultaneously concentrated and purified by placing aluminium oxide as clean-up sorbent in the extraction cell for a faster sample pre-treatment. Under optimized conditions, quantitative recoveries (only one compound below 80%) and satisfactory precision (RSD, 5–15%) were obtained. Low limits of detection were achieved of 0.5–15 ng/g dry weight (dw). The use of PLE extraction and purification and UPLC technology enabled all the compounds to be separated chromatographically in less than 9 min, and with a total chromatographic analysis time of 18 min. This method significantly decreased the overall time of analysis as compared to those of previously developed. Finally, the optimized methodology was applied to investigate the occurrence of the target UV filters in sediment samples collected along the Ebro river basin (Spain). UV filters were detected in 95% of the sediment samples analysed. Results revealed a widespread presence of octocrylene (OC), reaching concentrations up to 24 × 102 ng/g dw, the highest reported so far. Ethylhexyl dimethyl PABA (OD-PABA) and benzophenone-3 (BP3) were also frequently detected (60–65%), but at lower concentrations (4.4–27 ng/g dw). 4DHB (an estrogenic degradation product of BP3) was present in three samples at concentrations between 12 and 21 ng/g dw. These results constitute the first data on the occurrence of OD-PABA and 4DHB in sediments.  相似文献   

7.
A method for the determination of 11 UV-filter compounds in sludge has been developed and evaluated. The procedure includes the use of non-porous polymeric membranes in combination with pressurised liquid extraction (PLE). Firstly, the solid sample, wetted with the extraction solvent, was enclosed into tailor-made bags prepared with low density polyethylene. Secondly, these packages were submitted to a conventional PLE (70 °C, 4 cycles of 5 min static time). Finally, the analytes were determined by liquid chromatography–atmospheric pressure photoionisation–tandem mass spectrometry. The main advantage of this procedure is the reduction of time, solvent and labour effort ought to the combination of extraction and clean-up in a single step. Although the extraction is not quantitative (thus, standard addition is recommended for quantification) selectivity is clearly gained using the membrane as a consequence of the differences of permeation and transport through the membrane between the analytes and other sample matrix components. The optimised protocol provides limits of detection ranging from 0.3 ng g−1 (ethylhexyl dimethyl p-aminobenzoate (OD-PABA)) to 25 ng g−1 (ethylhexyl triazone (EHT)) with only 0.5 g of sludge sample. All the studied UV filters were found in the samples at concentration levels between 1.4 and 2479 ng g−1, emphasising the high adsorption potential of this kind of environmental pollutants onto solid samples such as sludge. Also, this method has permitted the determination of seven of the studied UV filters in sludge samples for the first time.  相似文献   

8.
Brompheniramine, an antihistamine drug, was employed as a novel UV probe for capillary electrophoresis with indirect UV detection of adamantane drugs (memantine, amantadine, and rimantadine). The probe possesses high molar absorptivity of 24 × 103 L/mol cm at 6 mM, which enables the measurement of these nonchromophore analytes without derivatization. The simple background electrolyte (10 mM sodium dihydrogen phosphate (pH 5.0) containing 5 mM brompheniramine and 6 mM β‐cyclodextrin) provided the separation of the analytes in a short time (7.5 min). Under these conditions, brompheniramine had similar mobility to that of the analyte ions resulting in symmetric peaks with minimal electrodispersion. The analytes displace the probe at a one‐to‐one ratio with transfer values close to unity. β‐Cyclodextrin played a role in the resolution of the structurally similar adamantane derivatives. Method validation showed good linearity (r 2 > 0.98), precision (%RSD ≤ 3.30), and accuracy (recoveries ranging from 98 to 109%). The proposed method was successfully applied to determine the adamantane content in pharmaceutical products.  相似文献   

9.
It is now well documented that chronic UVA exposure induces damage to human skin. Therefore, modern sunscreens should not only provide protection from both UVB and UVA radiation but also maintain this protection during the entire period of exposure to the sun. UVA filters, however, are rare and not sufficiently photostable. We investigated the effect of the introduction of a new UV filter, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), in oil in water sunscreen formulations on the photostability of butyl methoxydibenzoylmethane (Avobenzone [AVB]) after irradiation with an optically filtered Xenon arc source (UV irradiance adjusted at 1 mean effective dose [MED]/min). With spectrophotometrical methods to assess the sun protection factor (SPF) and UVA ratio and chromatographical methods to determine the amount of UV filters recovered after irradiation we showed that Tinosorb S prevented the photodegradation of AVB in a concentration-dependent way, leading to a sustained SPF and UVA ratio even after irradiation with doses of up to 30 MED. Since AVB was shown to destabilize ethylhexyl methoxycinnamate (EHM) we tested the effect of Tinosorb S in sunscreens containing this UV filter combination. Here too Tinosorb S showed photoprotective properties toward both UV filters. Thus, Tinosorb S can be used successfully to improve the photostability and efficiency of sunscreens containing AVB and EHM.  相似文献   

10.
An in vitro analysis of the effects of photosynthetically active and ultraviolet radiations was executed to assess the photostability of biologically relevant pigments phycocyanin (PC), phycoerythrin (PE) and allophycocyanin (APC) isolated from Lyngbya sp. A09DM. Ultraviolet (UV) irradiances significantly affected the integrity of PC, PE and APC; however, PAR showed least effect. UV radiation affected the bilin chromophores covalently attached to phycobiliproteins (PBPs). Almost complete elimination of the chromophore bands associated with α‐ and β‐subunit of PE and APC occurred after 4 h of UV‐B exposure. After 5 h of UV‐B exposure, the content of PC, PE and APC decreased by 51.65%, 96.8% and 96.53%, respectively. Contrary to PAR and UV‐A radiation, a severe decrease in fluorescence of all PBPs was observed under UV‐B irradiation. The fluorescence activity of extracted PBP was gradually inhibited immediately after 15–30 min of UV‐B exposure. In comparison to the PC, the fluorescence properties of PE and APC were severely lost under UV‐B radiation. Moreover, the present study indicates that UV‐B radiation can damage the structural and functional integrity of phycobiliproteins leading to the loss of their ecological and biological functions.  相似文献   

11.
Ultraviolet light from the sun can produce long-term skin damage and cancer. The use of sunscreen products containing one or more UV filters is encouraged by health professionals for preventing the damaging effects resulting from sun exposure. However, recently there have been increasing concerns about the use of sunscreens and their safety for both humans and the environment. The sunscreen manufacturers should take the initiative in testing of the products for possible short-term skin toxicity and long-term health effects that might occur due to the absorption of UV filters through the skin. Published studies have shed light on this topic by investigating the harmful effects of UV filters such as oxybenzone on the hormone system of aquatic animals and humans. Currently, in vitro and in vivo animal models are being used to determine the mechanistic and cellular effects these products produce. With growing awareness of adverse effects posed by UV filters on the environment and exposed organisms, several jurisdictions are prohibiting their use in sunscreens. To our knowledge, very few reviews summarized the potential toxicities associated with UV filters. Therefore, the current reported findings are rather controversial due to the lack of nonclinical safety assessment data to determine the clinical significance of such exposure.  相似文献   

12.
A simple, rapid and sensitive analytical procedure for the measurement of celecoxib (CXB) levels in skin samples after in vitro penetration studies was developed and validated. In vitro permeability studies in porcine skin were performed for quantification of CXB at different layers of skin, the stratum corneum (SC) and epidermis plus dermis (EP + D) as well as in the acceptor solution (AS) to assess CXB permeation through skin. CXB was quantified by HPLC using a C18 column and UV detection at 251 nm. The mobile phase was methanol–water 72:28 (v/v) and the flow‐rate was 0.8 mL/min. The CXB retention time was 5 min. The assay was linear for CBX in the concentration range of 0.1–3.0 μg/mL in the AS (drug permeated through skin) and 5.0–50.0 μg/mL for drug retained in SC and [EP + D] in vitro. The linear correlation coefficients for the different calibration curves were equal or greater than 0.99. Intra‐ and inter‐assay variabilities were below 8.0%. Extraction of CXB from skin samples showed recoveries higher than 95.0% after 15 min of ultrasonic sound and centrifugation at 2500 rpm for 3 min. The method was considered appropriate for the assay of CXB in skin samples, after in vitro cutaneous penetration studies. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

13.
The photostability of drugs administered topically on unprotected skin is a complex phenomenon that could be connected with the loss of activity or, rather rarely, the occurrence of toxic degradation products. In this study, an in‐depth investigation of the photostability of terbinafine, in both solutions and formulations, was conducted, taking into account the presence of UV absorbers such as TiO2, ZnO, avobenzone, 3‐(4‐methylbenzylidene)camphor, octocrylene, benzophenone‐1 and benzophenone‐2. The clear photocatalytic degradation of terbinafine in ethanol solution was observed in the presence of TiO2 and/or ZnO. In other cases, terbinafine was stable, with the exception of, in the presence of octocrylene. The presumed degradation products of terbinafine were identified for the first time using LC/MS/MS, and transformation pathways were proposed. In the case of a cream formulation, the percentage of initial terbinafine content was almost unchanged in the presence of the UV absorbers benzophenone‐1, benzophenone‐2 and 3‐(4‐methylbenzylidene)camphor. In vitro cytotoxicity risk assessment of terbinafine based on photostability under UVA irradiation was evaluated using the human skin fibroblast BJ (ATCC® CRL‐2522?), and this showed no statistically significant difference in cell viability for all samples analyzed.  相似文献   

14.
Benzophenone (BP) type UV filters are common environmental contaminants that are posing a growing health concern due to their increasing presence in water. Different studies have evidenced the presence of benzophenones (BP, BP-1, BP-2, BP-3, BP-4, BP-9, HPB) in several environmental matrices, indicating that conventional technologies of water treatment are not able to remove them. It has also been reported that these compounds could be associated with endocrine-disrupting activities, genotoxicity, and reproductive toxicity. This review focuses on the degradation kinetics and mechanisms of benzophenone-type UV filters and their degradation products (DPs) under UV and solar irradiation and in UV-based advanced oxidation processes (AOPs) such as UV/H2O2, UV/persulfate, and the Fenton process. The effects of various operating parameters, such as UV irradiation including initial concentrations of H2O2, persulfate, and Fe2+, on the degradation of tested benzophenones from aqueous matrices, and conditions that allow higher degradation rates to be achieved are presented. Application of nanoparticles such as TiO2, PbO/TiO2, and Sb2O3/TiO2 for the photocatalytic degradation of benzophenone-type UV filters was included in this review.  相似文献   

15.
A silica‐based MCM‐41 mesoporous material functionalized with cyanopropyl groups has been synthesized by cocondensation, characterized and applied to preconcentrate six parabens and three UV filters in river and swimming‐pool waters. The analytes were quantified by ultra‐high performance liquid chromatography‐tandem mass spectrometry, according to the Directive 96/23/EC. Even though matrix effect was negligible, quantification in river water samples with the standard addition approach improved the recoveries obtained using solvent‐based and even with matrix‐matched calibration. The method quantification limits in river water samples were 0.05 ng/mL for 2,4‐dihydroxybenzophenone and 0.01 ng/mL for the rest. Recoveries, evaluated for a concentration level of 0.5 ng/L, were in the range 93.5‐107.6% for parabens and in the range 64.2‐85.8% for UV filters, with relative standard deviations intraday ≤10.2 and 10.8%, respectively. This parameter, evaluated for a concentration level of 0.1 ng/L, ranged between 98.3 and 110.4% for parabens and between 61.9 and 89.9% for UV filters, with relative standard deviation intraday ≤15.3 and 15.5%, respectively. The two UV filters with lower recoveries were the most affected by the addition of sodium chloride. River and swimming pool waters were analyzed and all the personal care products were found in the swimming pool water, whereas only methylparaben was detected in the river water.  相似文献   

16.
Graphene oxide based molecularly imprinted polymers modified with β‐cyclodextrin were prepared as solid‐phase extraction column sorbents for specific recognition and sensitive detection of di(2‐ethylhexyl) phthalate in water samples. The morphology and composition of synthesized sorbents were characterized by scanning electron microscopy, thermo‐gravimetric analysis, Raman spectroscopy, and Fourier‐transform infrared spectroscopy. The conditions affecting the performance of extraction procedures such as desorption solvent types and volume, sample pH and volume were investigated. The loading capacity (8.2 μg/mg) of the prepared sorbents increased eight times after modification with β‐cyclodextrin. The developed extraction procedures coupled to high‐performance liquid chromatography exhibited good linearity (0.2–500 μg/L), low limit of detection (0.052 μg/L), and good precision (relative standard deviation?5.7%) under optimized conditions. The developed solid‐phase extraction technique with prepared sorbents has been successfully applied in extracting trace di(2‐ethylhexyl) phthalate from real natural waters with high efficiency, good selectivity, and desirable recoveries.  相似文献   

17.
A portable sample preparation device with a magnetic polymer monolith as the extraction medium was constructed. The monolith was synthesized by polymerizing methacrylic acid and ethylene dimethacrylate around a cylindrical magnet. In this way, the monolith with a magnetic core could be readily attached to the extraction device by magnetism. The constructed device was evaluated for the enrichment of UV filters in water samples, followed by high‐performance liquid chromatographic analysis. The extraction efficiency for the targets was satisfactory with no matrix interference. Good linearities were obtained for the UV filters with the correlation coefficients >0.9986. The limits of detection and quantification for the UV filters were 0.3–0.8 and 1.0–2.4 ng/mL, respectively. The recoveries of the UV filters from the spiked water samples at the concentration of 100 ng/mL were 95.3–101.7%, with relative standard deviations <10%. Accordingly, the proposed portable device was demonstrated to be suitable for on‐site simultaneous sampling, purification, and preconcentration within a single step.  相似文献   

18.
An analytical method based on ion-interaction chromatography with UV detection for simultaneous in-vitro estimation of the percutaneous absorption of the most used water-soluble UV filters in sunscreen cosmetics is proposed. These UV filters were phenylbenzimidazole sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, benzophenone-4, and terephthalylidene dicamphor sulfonic acid. The methodology is based on applying the sunscreen containing the target UV filters to human epidermis in a diffusion cell. Analytes are determined in the receptor solution. To ensure skin integrity, screening of the cells was carried out by analytical determination of a marker. Analytical variables such as percentage ethanol, concentration of ion-pairing agent, pH of the mobile phase, and temperature were studied in order to achieve high resolution of the chromatographic peaks in the lowest possible time of analysis. The conditions selected consisted of a mobile phase composed of 35:65 (v/v) ethanol–ammonium acetate buffer solution (pH 4, containing 50 mmol L−1 tetra-n-butylammonium bromide). The chromatographic determination was carried out with the analytical column at 50 °C. UV detection was carried out at the maximum absorption wavelength for each analyte. The limit of detection (3s y/x /b) ranged from 16 to 65 ng mL−1, depending on the analyte.  相似文献   

19.
The injury and cumulative effects of UV emission from fluorescence lamp were studied. UV intensity from fluorescence lamp was measured, and human skin samples (hips, 10 volunteers) were exposed to low‐dose UV irradiation (three times per week for 13 consecutive weeks). Three groups were examined: control group without UV radiation; low‐dose group with a cumulative dose of 50 J cm?2 which was equivalent to irradiation of the face during indoor work for 1.5 years; and high‐dose group with 1000 J cm?2 cumulative dose equivalent to irradiation of the face during outdoor activities for 1 year. Specific indicators were measured before and after UVA irradiation. The findings showed that extending the low‐dose UVA exposure decreased the skin moisture content and increased the transepidermal water loss as well as induced skin color changes (decreased L* value, increased M index). Furthermore, irradiated skin showed an increased thickness of cuticle and epidermis, skin edema, light color and unclear staining collagen fibers in the dermis, and elastic fiber fragmentation. In addition, MMP‐1, p53 and SIRT1 expression was also increased. Long‐term exposure of low‐dose UVA radiation enhanced skin photoaging. The safety of the fluorescent lamp needs our attention.  相似文献   

20.
UV filters as emerging contaminants are of great concern and their wide detection in aquatic environments indicates their chemical stability and persistence. This review summarized the photolytic and photocatalytic degradation of UV filters in contaminated water. The findings indicated that limited research has been conducted on the photolysis and photocatalysis of UV filters. Photolysis of UV filters through UV irradiation in natural water was a slow process, which was accelerated by the presence of photosensitisers e.g. triplet state of chromaphoric dissolved organic matter (3CDOM*) and nutrients but reduced by salinity, dissolved organic matter (DOM) and divalent cations. UV Photocatalysis of 4-methylbenzylidene camphor and 2-phenylbenzimidazole-5-sulfonic acid was very effective with 100% removal within 30 min and 90 min using medicated TiO2/H2O2 and TiO2, respectively. The radiation source, type of catalyst and oxygen content were key factors. Future research should focus on improved understanding of photodegradation pathways and by-products of UV filters.  相似文献   

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