Sunscreens Part 2: Regulation and Safety.

The second part of this CME article discusses sunscreen regulation and safety considerations for humans and the environment. First, we provide an overview of the history of the United States Food and Drug Administration's regulation of sunscreen. Recent Food and Drug Administration studies clearly demonstrate that organic ultraviolet filters are systemically absorbed during routine sunscreen use, but to date there is no evidence of associated negative health effects. We also review the current evidence of sunscreen's association with vitamin D levels and frontal fibrosing alopecia, and recent concerns regarding benzene contamination. Finally, we review the possible environmental effects of ultraviolet filters, particularly coral bleaching. While climate change has been shown to be the primary driver of coral bleaching, laboratory-based studies suggest that organic ultraviolet filters represent an additional contributing factor, which led several localities to ban certain organic filters.

On-site extraction of benzophenones from swimming pool water using hybrid tapes based on the integration of hydrophilic-lipophilic balance microparticles and an outer magnetic nanometric domain.

An on-site extraction device is presented consisting of scotch tape modified with concentric domains of micrometric hydrophilic-lipophilic balance (HLB) particles surrounded by a ring of nanometric magnetic ones. On the one hand, HLB microparticles are readily available at the surface of the tape, exposed to interact with the target analytes, being responsible for the extraction capacity of the sorptive phase. On the other hand, the presence of magnetic nanoparticles enables the attachment of the modified tape onto a metallic screw via a magnet, which is then coupled to a wireless drill, enabling the stirring of the microextraction device. Both are simply fixed to the cost-effective, flexible, and versatile support, i.e., scotch tape, owing to their adhesive properties. The microextraction device has been applied to the determination of six benzophenones in swimming pool water samples. The variables that may affect the extraction process have been evaluated. Under the optimum conditions and using liquid chromatography-tandem mass spectrometry as the instrumental technique, the method provided a limit of detection of 0.03 µg L-1. The intra-day precision, evaluated at three different concentration levels and expressed as relative standard deviation, was lower than 10%, which also comprises the variability within single-use sorptive tapes. The accuracy, calculated with spiked samples and expressed as relative recovery, ranged from 71 to 138%. The method was applied to the analysis of swimming pool water, revealing the presence of such compounds.

A multiplex approach of MS, 1D-, and 2D-NMR metabolomics in plant ontogeny: A case study on Clusia minor L. organs (leaf, flower, fruit, and seed).

INTRODUCTION: The genus Clusia L. is mostly recognised for the production of prenylated benzophenones and tocotrienol derivatives. OBJECTIVES: The objective of this study was to map metabolome variation within Clusia minor organs at different developmental stages. MATERIAL AND METHODS: In total 15 organs/stages (leaf, flower, fruit, and seed) were analysed by UPLC-MS and 1H- and heteronuclear multiple-bond correlation (HMBC)-NMR-based metabolomics. RESULTS: This work led to the assignment of 46 metabolites, belonging to organic acids(1), sugars(2) phenolic acids(1), flavonoids(3) prenylated xanthones(1) benzophenones(4) and tocotrienols(2). Multivariate data analyses explained the variability and classification of samples, highlighting chemical markers that discriminate each organ/stage. Leaves were found to be rich in 5-hydroxy-8-methyltocotrienol (8.5 µg/mg f.w.), while flowers were abundant in the polyprenylated benzophenone nemorosone with maximum level detected in the fully mature flower bud (43 µg/mg f.w.). Nemorosone and 5-hydroxy tocotrienoloic acid were isolated from FL6 for full structural characterisation. This is the first report of the NMR assignments of 5-hydroxy tocotrienoloic acid, and its maximum level was detected in the mature fruit at 50 µg/mg f.w. Seeds as typical storage organ were rich in sugars and omega-6 fatty acids. CONCLUSION: To the best of our knowledge, this is the first report on a comparative 1D-/2D-NMR approach to assess compositional differences in ontogeny studies compared with LC-MS exemplified by Clusia organs. Results derived from this study provide better understanding of the stages at which maximal production of natural compounds occur and elucidate in which developmental stages the enzymes responsible for the production of such metabolites are preferentially expressed.

The environmental sources of benzophenones: Distribution, pretreatment, analysis and removal techniques.

Benzophenones (BPs) have wide practical applications in real human life due to its presence in personal care products, UV-filters, drugs, food packaging bags, etc. It enters the wastewater by daily routine activities such as showering, impacting the whole aquatic system, then posing a threat to human health. Due to this fact, the monitoring and removal of BPs in the environment is quite important. In the past decade, various novel analytical and removal techniques have been developed for the determination of BPs in environmental samples including wastewater, municipal landfill leachate, sewage sludge, and aquatic plants. This review provides a critical summary and comparison of the available cutting-edge pretreatment, determination and removal techniques of BPs in environment. It also focuses on novel materials and techniques in keeping with the concept of "green chemistry", and describes on challenges associated with the analysis of BPs, removal technologies, suggesting future development strategies.

Benzophenones in the Environment: Occurrence, Fate and Sample Preparation in the Analysis.

The ubiquitous presence of emerging contaminants in the environment is an issue of great concern. Notably, for some of them, no established regulation exists. Benzophenones are listed as emerging contaminants, which have been identified in the environment as well as in human fluids, such as urine, placenta, and breast milk. Their accumulation and stability in the environment, combined with the revealed adverse effects on ecosystems including endocrine, reproductive, and other disorders, have triggered significant interest for research. Benzophenones should be extracted from environmental samples and determined for environmental-monitoring purposes to assess their presence and possible dangers. Numerous sample preparation methods for benzophenones in environmental matrices and industrial effluents have been proposed and their detection in more complex matrices, such as fish and sludges, has also been reported. These methods range from classical to more state-of-the-art methods, such as solid-phase extraction, dispersive SPE, LLE, SBSE, etc., and the analysis is mostly completed with liquid chromatography, using several detection modes. This review critically outlines sample preparation methods that have been proposed to date, for the extraction of benzophenones from simple and complex environmental matrices and for cleaning up sample extracts to eliminate potential interfering components that coexist therein. Moreover, it provides a brief overview of their occurrence, fate, and toxicity.

Constituents of the Stem Bark of Symphonia globulifera Linn. f. with Antileishmanial and Antibacterial Activities.

The chemical investigation of the n-hexane fraction from the methanol extract of the stem bark of Symphonia globulifera Linn f., which displayed good in vitro activity against Leishmania donovani NR-48822 promastigotes (IC50 43.11 µg/mL), led to the isolation of three previously unreported polyprenylated benzophenones, guttiferone U (1), V (2)/W (3), and a new tocotrienol derivative named globuliferanol (4), along with 11 known compounds (5-15). Their structures were elucidated based on their NMR and MS data. Some isolated compounds were assessed for both their antileishmanial and cytotoxic activities against L. donovani and Vero cells, respectively. Guttiferone K (5) exhibited the best potency (IC50 3.30 µg/mL), but with low selectivity to Vero cells. The n-hexane fraction and some compounds were also assessed in vitro for their antibacterial activity against seven bacterial strains. All the samples exhibited moderate to potent antibacterial activity (MICs ≤ 15.6 µg/mL) against at least one of the tested strains.

Assessment of the stability of compounds belonging to neglected phenolic classes and flavonoid sub-classes using reaction kinetic modeling.

Phenolic compounds are known to degrade and/or undergo changes during food production and storage. Reaction kinetic modeling is generally used to define kinetic parameters of a food system and predict changes during thermal processing and storage. Data for phenolic acids and flavonoids, such as anthocyanins and flavan-3-ols, have been reviewed in detail, but the flavonoid sub-classes, dihydrochalcones and flavanones, have been mostly neglected. Other neglected phenolic classes are xanthones and benzophenones. The stability of these types of compounds is important as they are present in fruits and exposed to heat when processed into juice and jam. Other sources of the compounds are herbal teas, which are also subjected to thermal processing, either during the primary processing of the plant material, or the production of extracts for use as food ingredients. The theoretical background is given to understand the review of literature on these classes/sub-classes. Results of research on kinetic modeling are discussed in detail, while research on compound stability without the application of reaction kinetic modeling is briefly mentioned to provide context. The studies discussed included those focusing on heating during the processing and storage of model solutions, liquid foods, plant material, dried extracts, and extracts formulated with other food ingredients.

Photoaffinity labeling and bioorthogonal ligation: Two critical tools for designing "Fish Hooks" to scout for target proteins.

Small molecules remain an important category of therapeutic agents. Their binding to different proteins can lead to both desired and undesired biological effects. Identification of the proteins that a drug binds to has become an important step in drug development because it can lead to safer and more effective drugs. Parent bioactive molecules can be converted to appropriate probes that allow for visualization and identification of their target proteins. Typically, these probes are designed and synthesized utilizing some or all of five major tools; a photoactivatable group, a reporter tag, a linker, an affinity tag, and a bioorthogonal handle. This review covers two of the most challenging tools, photoactivation and bioorthogonal ligation. We provide a historical and theoretical background along with synthetic routes to prepare them. In addition, the review provides comparative analyses of the available tools that can assist decision making when designing such probes. A survey of most recent literature reports is included as well to identify recent trends in the field.

Stability and Removal of Benzophenone-Type UV Filters from Water Matrices by Advanced Oxidation Processes.

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.

Layered Double Hydroxide/Graphene Quantum Dots as a New Sorbent for the Dispersive Solid-Phase Microextraction of Selected Benzophenones, Phenols, and Parabens.

In this study, the synthesis of a layered double hydroxide (LDH) composite with graphene quantum dots (GQDs) and its utilization for the development of a dispersive solid-phase extraction procedure are described. To this end, a carbonate-free Mg-Al LDH was synthesized. The development of the composite material made feasible the use of GQDs in a sample preparation procedure, while the incorporation of the GQDs in the LDH structure resulted in an 80% increase in extraction efficiency, compared to the bare LDH. As a proof of concept, the composite material was used for the development of an analytical method for the extraction, and preconcentration, of benzophenones, phenols, and parabens in lake water using high-performance liquid chromatography, coupled to a diode array detector. The analytical method exhibits low limits of quantification (0.10-1.33 µg L-1), good recoveries (92-100%), and satisfactory enrichment factors (169-186). Due to the abovementioned merits, the easy synthesis and simple extraction, the developed method can be used for the routine analysis of the target compounds.

Cosmetic and personal care product use, urinary levels of parabens and benzophenones, and risk of endometriosis: results from the EndEA study.

AIM: To explore the relationship of urinary concentrations of different congeners of benzophenones and parabens with the utilization of cosmetics and personal care products (PCPs) and their impact on the risk of endometriosis, and to evaluate the influence of oxidative stress on associations found. METHODS: This case-control study comprised a subsample of 124 women (35 cases; 89 controls). Endometriosis was confirmed (cases) or ruled out (controls) by laparoscopy, with visual inspection of the pelvis and biopsy of suspected lesions (histological diagnosis). Urinary concentrations of benzophenone-1 (BP-1), benzophenone-3 (BP-3), 4-hydroxibenzophenone (4-OH-BP), methyl- (MeP), ethyl- (EtP), propyl- (PrP), and butyl-paraben (BuP), and biomarkers of oxidative stress [lipid peroxidation (TBARS) and total antioxidant power (TAP)] were quantified. Information was gathered on the frequency of use of cosmetics and PCPs. Associations between the frequency of cosmetics/PCP use, urinary concentrations of benzophenones and parabens, oxidative stress, and endometriosis risk were explored in logistic and linear multivariable regression analyses. RESULTS: The frequency of utilization of certain cosmetics and PCPs was significantly associated with urinary concentrations of benzophenones and parabens. After adjustment for potential confounders, the risk of endometriosis was increased in women in the second versus first terciles of MeP (OR = 5.63; p-value<0.001), BP-1 (OR = 5.12; p-value = 0.011), BP-3 (OR = 4.98; p-value = 0.008), and Æ©BPs (OR = 3.34; p-value = 0.032). A close-to-significant relationship was observed between TBARS concentrations and increased endometriosis risk (OR = 1.60, p-value = 0.070) and an inverse association between TAP concentrations and this risk (OR = 0.15; p-value = 0.048). Oxidative stress results did not modify associations observed between benzophenone/paraben exposure and endometriosis risk. CONCLUSIONS: Our findings indicate that the frequency of cosmetics and PCP utilization is a strong predictor of exposure to certain benzophenone and paraben congeners. These compounds may increase the risk of endometriosis in an oxidative stress-independent manner. Further studies are warranted to corroborate these findings.

Serum levels of non-persistent environmental pollutants and risk of incident hypertension in a sub-cohort from the EPIC study.

BACKGROUND: The prevalence of arterial hypertension (AHT), a well-known risk factor for cardiovascular disease, has considerably increased over last decades. Non-persistent environmental pollutants (npEPs) are a group of ubiquitous chemicals, widely used in consumer products such as food packaging and cosmetics, which have been identified as endocrine disrupting chemicals and obesogens. The aim of this study was to assess the potential associations of serum levels of three groups of npEPs with the risk of incident AHT. METHODS: Cohort study within a sub-cohort of Granada EPIC-Spain center (n = 670). We quantified serum concentrations of three groups of npEPs, i.e., bisphenol A (BPA), four parabens: methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP), and two benzophenones: benzophenone 1 (BP1), benzophenone 3 (BP3), in samples collected at recruitment. Statistical analyses were performed by means of Cox Proportional Hazard Models. RESULTS: Median follow-up time was 23 years. BPA and MP were found in >80% of the study population. Individuals within the 4th PP quartile (0.53-9.24 ng/ml) showed a statistically significant increased risk of AHT (HR = 1.40, p = 0.015). No associations were found for the rest of pollutants. CONCLUSIONS: Overall, we evidenced no associations of most npEPs with AHT risk, with the exception of an increased risk in the highest PP percentiles. Considering the limitations of using one spot serum sample for exposure characterization, further research on the potential contribution of npEPs on the development of AHT risk is warranted.

Comparative acute toxicity of benzophenone derivatives and bisphenol analogues in the Asian clam Corbicula fluminea.

Among UV-filters, benzophenones are one of the most abundantly used and detected groups in the environment. Bisphenols are also one of the most widely used chemicals in plastics, but their demonstrated deleterious effects on several organisms and humans have led to the production of alternative analogues. However, few comparative studies on the ecotoxicological effects of these derivatives or analogues have been carried out. The present study aimed to investigate the effects of two benzophenones (BP-3 and BP-4) and two bisphenols (BPA and BPS) in a short-term exposure of the freshwater endobenthic bivalve Corbicula fluminea. Clams were exposed for 96 h to several concentrations of the four pollutants: BP-3 (0.63; 1.25; 2.5; 5 mg l-1), BP-4 (4.75; 9.5; 19; 38 mg l-1), BPA (3.75; 7.5; 15; 30 mg l-1), and BPS (2.5; 5; 10; 20 mg l-1). The comparative acute toxicity of these pollutants was evaluated by the analysis of the post-exposure filtering capacity of clams, lipid peroxidation (LP) levels and the activity of the antioxidant enzymes catalase (CAT) and glutathione reductase (GR). After the exposure period, except for BP-4, the chemicals tested seemed to be detected by clams and provoked valve closure, decreasing filter-feeding in a concentration-dependent manner. Furthermore, C. fluminea exposed to the highest concentrations of BP-3, BP-4 and BPA showed a significant increase in LP, CAT and GR activities with respect to their controls. BP-3 and BPA were the most toxic compounds showing significant differences in all the parameters analysed at the highest concentrations assayed. However, clams exposed to BPS showed only significant alterations in filtration parameters and in GR activity, in the two highest concentrations tested, indicating that this compound was the least toxic to clams. Obtained results highlight the importance of investigating the effects that emerging pollutants have on aquatic organisms.

Determination of Benzophenones in Water and Cosmetics Samples: A Comparison of Solid-Phase Extraction and Microextraction by Packed Sorbent Methods.

Benzophenones (BPs) are extensively used in a wide variety of cosmetic products and other materials (e.g., textiles or plastics) to avoid damaging effects of UV radiation. In the present work, we compared two extraction methods for the determination of BPs, namely, 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3) and 2,2-dihydroxy-4-methoxybenzophenone (BP-8), in water and cosmetics samples. The following extraction methods were used for the research: solid-phase extraction (SPE) and microextraction by packed sorbent (MEPS), whereas analysis was performed by gas chromatography with mass spectrometric detection. A comparison between the methods indicates that the MEPS technique(s) can be reliably used for analysis of BPs (sunscreen residue) in water samples and cosmetic samples with satisfactory results. This microextraction technique is cheap, easy, quick to implement, and consumes small amounts of solvents. On the other hand, the main advantage of the SPE method are low detection limits for the determination of BPs in water samples, i.e., from 0.034 to 0.067 µg L-1, while, for the MEPS method, LODs were at the level of 1.8-3.2 µg L-1. For both methods, the recoveries of BPs were 96-107% and 44-70% for water and cosmetics samples, respectively. The presented methods are suitable for use in cosmetics quality control and environmental pollution assessment.

Prenylated xanthones and benzophenones from the fruits of Garcinia bracteata and their potential antiproliferative and anti-inflammatory activities.

Ten previously undescribed compounds, including five prenylated xanthones (1-5), two caged xanthones (16-17) and three rearranged benzophenones (27-29), together with nineteen known compounds were isolated from the fruits of Garcinia bracteata. Their structures were established on the basis of spectroscopic analysis, electronic circular dichroism calculations, and X-ray crystallographic data. Compound 17 was a caged xanthone bearing a rare 8, 8a-epoxy moiety. Compound 28 belonged to the rearranged benzophenones with rare 2, 7-dioxabicyclo-[2.2.1] heptane moiety fused at C-2 and C-3 respectively. The antiproliferative and anti-inflammatory activities of all isolated compounds were evaluated. Compounds 23 and 24 exhibited remarkable inhibitory activities against three human cancer cell lines (HepG2, T98, MCF-7) with IC50 values ranging from 3.21 ± 1.00 to 6.27 ± 1.03 µM. Moreover, compounds 20 and 24 also displayed significant inhibitory effects against NO production with IC50 values of 1.22 ± 0.01 and 1.77 ± 0.23 µM respectively. These results enrich the structural diversities of xanthones and benzophenones from Garcinia plants. Neobractatin (24) due to its anti-tumor and anti-inflammatory effects is worth further investigation in anticancer research.

Menstrual blood concentrations of parabens and benzophenones and related factors in a sample of Spanish women: An exploratory study.

AIM: To evaluate concentrations of parabens (PBs) and benzophenones (BzPs) in menstrual blood and explore related sociodemographic/lifestyle factors, and to compare between menstrual and peripheral blood concentrations in a subset of samples. MATERIAL AND METHODS: Concentrations of 4 PBs [methyl- (MeP), ethyl- (EtP), propyl- (PrP) and butyl-paraben (BuP)] and 6 BzPs [BzP-1, BzP-2, BzP-3, BzP-6, BzP-8 and 4-OH-BzP] were determined in menstrual blood from 57 women and in both menstrual and peripheral blood samples from 12 women, all healthy Spanish women of reproductive age. Socio-demographic characteristics and lifestyle habits [diet and use of cosmetics and personal care products (PCPs)] were gathered using an online questionnaire. Spearman correlation analysis was performed to examine the relationship between menstrual and peripheral blood concentrations, while multivariable linear regression was used to identify potential explanatory variables for menstrual PB and BzP concentrations. RESULTS: Globally, all menstrual blood samples had detectable levels of ≥3 compounds, and 52.6% of the samples contained ≥6 compounds. MeP, PrP, and BzP-3 were the most frequently detected compounds (detection frequencies >90.0%), with median concentrations of 1.41, 0.63, and 1.70 ng/mL of menstrual blood, respectively. Age, the use of PCPs, and consumption of some food items (meat, pasta, cheese, or dairy products) were related to the menstrual blood concentrations of some PBs/BzPs. Serum:menstrual blood ratios of PBs/BzPs ranged from 1.7 to 3.6, with no inter-matrix correlations. CONCLUSIONS: This study reveals, to our knowledge for the first time, the widespread presence of several PBs and BzPs in intimate contact with gynecological tissues, although their concentrations in menstrual blood were not correlated with those in peripheral blood from the same women. These results shed light on the information provided by the menstrual blood as a potential matrix for characterizing exposure to PBs and BzPs, whose consequences for women's reproductive health need to be addressed.

Historical exposure to non-persistent environmental pollutants and risk of type 2 diabetes in a Spanish sub-cohort from the European Prospective Investigation into Cancer and Nutrition study.

BACKGROUND: Environmental factors are believed to account for a substantial burden of type 2 diabetes mellitus (T2DM). Non-persistent environmental pollutants (npEPs) are a group of widely-used chemicals identified as endocrine/metabolic disrupting chemicals and obesogens. The aim of this study was to analyse the potential associations of serum levels of three groups of npEPs with the risk of incident T2DM. METHODS: This is a longitudinal study within a sub-sample of Granada EPIC-Spain cohort (n = 670). We quantified serum concentrations of 7 npEPs: four parabens (Methylparaben (MP) ethylparaben (EP), propylparaben (PP) and butilparaben (BP); two benzophenones: Benzophenone 1 (BP1), Benzophenone 3 (BP3); and Bisphenol A (BPA). Exposure was assessed by means of chemical analyses of serum samples collected at recruitment, and information on potential confounders was gathered by using validated questionnaires at baseline. Follow-up was performed by review of patients' clinical records. Cox Proportional Hazards Models were used for the statistical analyses. RESULTS: Median follow-up time was 23 years. There were 182 (27%) incident T2DM diagnoses in our sub-cohort. MP was the most frequently detected npEP, 88.42% samples above the limit of detection, and BP showed the lowest percentage of detection (19.21%). Those individuals within the fourth PP quartile (0.53-9.24 ng/ml) showed a statistically significant increased risk of T2DM (HR = 1.668 p = 0.012), while BP1 concentrations showed an inverse non-significant trend with the risk. CONCLUSIONS: We evidenced a potential contribution of npEP exposure on T2DM, but no clear trend was observed. However, limitations in relation to exposure estimation might influence our findings and further research is warranted to confirm our results.

Dalbergia ecastaphyllum (L.) Taub. and Symphonia globulifera L.f.: The Botanical Sources of Isoflavonoids and Benzophenones in Brazilian Red Propolis.

The Brazilian red propolis (BRP) constitutes an important commercial asset for northeast Brazilian beekeepers. The role of Dalbergia ecastaphyllum (L.) Taub. (Fabaceae) as the main botanical source of this propolis has been previously confirmed. However, in addition to isoflavonoids and other phenolics, which are present in the resin of D. ecastaphyllum, samples of BRP are reported to contain substantial amounts of polyprenylated benzophenones, whose botanical source was unknown. Therefore, field surveys, phytochemical and chromatographic analyses were undertaken to confirm the botanical sources of the red propolis produced in apiaries located in Canavieiras, Bahia, Brazil. The results confirmed D. ecastaphyllum as the botanical source of liquiritigenin (1), isoliquiritigenin (2), formononetin (3), vestitol (4), neovestitol (5), medicarpin (6), and 7-O-neovestitol (7), while Symphonia globulifera L.f. (Clusiaceae) is herein reported for the first time as the botanical source of polyprenylated benzophenones, mainly guttiferone E (8) and oblongifolin B (9), as well as the triterpenoids ß-amyrin (10) and glutinol (11). The chemotaxonomic and economic significance of the occurrence of polyprenylated benzophenones in red propolis is discussed.

Sunscreen-induced expression and identification of photosensitive marker proteins in human keratinocytes under UV radiation.

Solar ultraviolet (UV) radiation is the main factor of photocarcinogenesis, photoaging, and photosensitivity; thus protection from biological damaging UV radiation is a concern. Sunscreens containing UV filters are the most preferred means of photoprotection but the safety and efficacy of UV filters are in question. Benzophenone (BP) and its derivatives, namely, benzophenone 1 (BP1), is commonly used in sunscreens as a UV blocker. The aim of this study was to assess the effects of BP and BP1 on the differential expression of proteins in human keratinocytes (HaCaT cells) under exposure to ultraviolet A radiation. Photosensitive proteins were screened from HaCaT cells by two-dimensional (2-D) gel electrophoresis, and identification of these differentially expressed proteins was performed by matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF)/TOF mass spectrometry. Protein identification was performed using the search program MASCOT and a database made of SUMO and GhJMJ12 amino acid sequences. Our results showed that the proteins involved directly or indirectly in apoptosis are 70 kDa heat shock protein, long-chain specific acyl-CoA dehydrogenase, serine/threonine-protein kinase, and FAM78A protein, which were upregulated in comparison to control HaCaT cells. The expressions of binding immunoglobulin protein, podocalyxin-like protein, actin, cytoplasmic, and calreticulin precursors were downregulated. The altered protein expression indicated that cell growth arrest and apoptosis were potential mechanisms of cytotoxicity and genotoxicity of BPs. The results of 2-D gel electrophoresis followed by mass spectrometry showed expression of novel proteins involved in promoting or initiating apoptotic pathways. Hence, we conclude that BPs should be avoided as a UV blocker from sunscreens because of its potential to promote apoptotic proteins in human skin keratinocytes.

Magnetic Polyamide Nanocomposites for the Microextraction of Benzophenones from Water Samples.

In this article, the influence of the monomers on the extraction efficiency and the effect of the addition of surfactants during the synthesis have also been considered. The sorption capacity of the resulting nanocomposites has been evaluated, in the dispersive micro-solid phase extraction format, by determining that of six benzophenones in water using ultra performance liquid chromatography (UPLC) combined with photodiode array detection. Under the optimum conditions, the limits of detection were in the range of 0.5⁻4.3 ng/mL and the repeatability, expressed as the relative standard deviation (RSD), varied between 1.5% and 5.6%. The proposed method has been applied for the analysis of real water samples, providing relative recoveries in the interval of 84⁻105.