Search Results (19)

Endocrine disruptors (EDCs) in food pose a significant threat to health. This study developed a method for detecting seven EDCs (triclosan (TCS), triclocarban (TCC), methyltriclosan (MTCS), methylparaben (MeP), propylparaben (PrP), bisphenol F (BPF), and 4-hydroxybenzophenone-3-ethylcarboxylate (4HBP)) in honey. The method combines ultrasonic-assisted dispersive liquid–liquid microextraction with high-performance liquid chromatography. It achieved a recovery rate of 89.70–102.2%, with an RSD value of 1.1–3.9%. Additionally, this study tested 47 honey samples from seven countries, revealing detection rates of TCS at 29.79%, TCC at 19.15%, BPF at 97.87%, 4HBP at 36.17%, MeP at 82.98%, and PrP at 80.85%. Among the 12 nectar sources, citrus flower nectar had the highest TCS detection rate, mother grass nectar had the highest TCC detection rate, and multi-flower nectar had the highest 4HBP detection rate. Moreover, imported honey samples showed higher levels of TCS, BPF, and MeP contamination compared to domestic samples. Honey stored in PET bottles contained the highest levels of EDCs. Finally, health risk assessments indicated that, while the risk for adults is lower, monitoring EDC contamination in food should be strengthened to ensure consumer safety. Full article

Two macromolecular photoinitiators, bis(4-benzoylphenyl) malonate (BPMD) and bis(4-benzoylphenyl) 3,3’-(piperazine-1,4-diyl)bis(3-oxopropanoate) (DBPMD), were successfully synthesized from 4-hydroxybenzophenone (4-BP), malonyl chloride, and anhydrous piperazine. Structural characterization using Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR) confirmed the expected molecular framework. Ultraviolet (UV) absorption spectroscopy revealed that BPMD and DBPMD exhibited enhanced molar extinction coefficients and red-shifted absorption maxima compared to 4-BP. Migration studies in high-density polyethylene (HDPE) demonstrated significantly lower diffusion rates for BPMD and DBPMD than for 4-BP, with DBPMD exhibiting superior photoinitiation efficiency even in the absence of amine-based activators. Photoinitiation performance, photocrosslinking kinetics, and mechanical evaluations indicated that both BPMD and DBPMD enabled efficient UV-initiated crosslinking, leading to improved tensile strength and creep resistance in polyethylene films. These findings highlight the potential of BPMD and DBPMD as advanced photoinitiators for high-performance UV-crosslinked polyethylene systems. Full article

The level of the human body’s burden of benzophenone and camphor ultraviolet (UV) filters can be estimated from their urinary levels. The present study describes the implementations and validation of the sensitive analytical method for the analysis of seven benzophenone and two camphor UV filters in urine. Sample preparation includes overnight enzymatic hydrolysis and ethyl acetate extraction followed by purification by dispersive solid-phase extraction using a sorbent Z-Sep. For the analysis, ultra-high performance liquid chromatography coupled with tandem mass spectrometry was used. Validation was performed using a Standard Reference Material^® 3673 and an artificially contaminated urine sample. Target analyte recoveries ranged from 79–113% with repeatability expressed as a relative standard deviation of 2–15%. The limits of quantification were between 0.001 and 0.100 ng/mL in urine. This method was subsequently applied to examine the urine samples collected from Czech women. The analytes benzophenone-1 and 4-hydroxy-benzophenone were the most common analytes present in 100% of the samples, whereas benzophenone-3 was quantified in only 90% of the urine samples. The other four determined benzophenone derivatives were quantified in ≤33% of the samples. The derivatives of camphor were not detected in any samples. This method could be applied in biomonitoring studies. Full article

Organic sun-blocking agents are recognized as emerging pollutants of the aquatic environment. The consequences and effects of these harmful substances on aquatic organisms are not fully understood, particularly in the context of Romania. This study examines the presence and environmental hazards posed by ten UV filters found in the Danube River. Six of the ten targeted contaminants were detected in surface water samples: 2-hydroxy-4-methoxy-benzophenone (BP-3), 2,4-dihydroxy benzophenone (BP-1), 2,3,4-trihydroxy benzophenone (234HBP), 2,2′-dihydroxy-4-methoxy-benzophenone (BP-8), 2-hydroxy-4-methoxy-4′-methyl-benzophenone (BP-10), and benzyl salicylate (BS). In sediment samples, seven of the ten compounds were identified: BS, BP-3, 4-hydroxybenzophenone (4HBP), BP-1, 234HBP, 2,2′,4,4′-tetrahydroxybenzophenone (BP-2), and BP-10, with different frequencies. The correlation coefficients showed strong relationships between benzophenone derivatives in surface water samples and a common contamination source for BP-3 and BS in sediment samples. In the assessment, the risk quotient (RQ) for BP-1 in fish was determined to be 1.81. Similarly, RQ values for BP-3 were calculated as 1.24 for Daphnia magna and 57 for fish, suggesting that these UV filters could potentially present substantial hazards to the aquatic ecosystem. The study findings indicate that additional research is needed to investigate the presence and potential risks of organic sun-blocking agents in surface waters, with a particular emphasis on densely populated areas in Romania. Full article

Sunscreen compounds are one of the most toxic substances detected in the aqueous environment. However, these molecules are continuously utilized in a various range of products to provide protection against UV radiation. The removal of three sunscreen compounds, 4-hydroxybenzophenone (4-HBP), 2,4-dihydroxybenzophenone (BP-1) and oxybenzone (BP-3), by commercial activated carbon (AC) was investigated using batch adsorption experiments. Different operational characteristics, such as adsorbent dosing, interaction time, solution pH and starting sunscreen compound concentration, were studied. The adsorption capacity of the AC material was assessed using a liquid chromatograph associated with a mass spectrometer detector (LC–MS/MS). Two isotherm models were utilized to explained the target compound adsorption phenomenon (Langmuir and Freundlich), while pseudo-first and -second kinetic orders and thermodynamics were utilized to examine the adsorption mechanism. The maximum adsorption capacities determined from the Langmuir isotherms were established as 43.8 mg/g for 4-HBP, 48.8 mg/g for BP-3 and 41.1 mg/g for BP-1. The thermodynamic parameters revealed the following: a negative ΔG° (<20 KJ/mol) and ΔH° and a positive ΔS° of the targeted sunscreen compounds adsorbed onto AC suggest a spontaneous and exothermic adsorption process, favored by lower temperature, proving that the physical sorption mechanism prevailed. Effective adsorption of 4-HBP, BP-3 and BP-1 from real wastewater samples proved the viability of sunscreen compound removal using commercial AC material. This paper offers promising results on a sustainable, economical and environmentally friendly method for removal of ubiquitous sunscreen compounds from wastewater, as a possible enhancement of treatment processes. Full article

Increasing evidence has been published over recent years on the implication of endocrine-disrupting chemicals (EDCs), including parabens and benzophenones in the pathogenesis and pathophysiology of endometriosis. However, to the best of our knowledge, no study has been published on the ways in which exposure to EDCs might affect cell-signaling pathways related to endometriosis. We aimed to describe the endometriotic tissue expression profile of a panel of 23 genes related to crucial cell-signaling pathways for the development and progression of endometriosis (cell adhesion, invasion/migration, inflammation, angiogenesis, and cell proliferation/hormone stimulation) and explore its relationship with the exposure of patients to parabens (PBs) and benzophenones (BPs). This cross-sectional study included a subsample of 33 women with endometriosis from the EndEA study, measuring their endometriotic tissue expressions of 23 genes, while urinary concentrations of methyl-, ethyl-, propyl-, butyl-paraben, benzophenone-1, benzophenone-3, and 4-hydroxybenzophenone were determined in 22 women. Spearman’s correlations test and linear and logistic regression analyses were performed. The expression of 52.2% of studied genes was observed in >75% of endometriotic tissue samples and the expression of 17.4% (n = 4) of them in 50–75%. Exposure to certain PB and BP congeners was positively associated with the expression of key genes for the development and proliferation of endometriosis. Genes related to the development and progression of endometriosis were expressed in most endometriotic tissue samples studied, suggesting that exposure of women to PBs and BPs may be associated with the altered expression profile of genes related to cellular pathways involved in the development of endometriosis. Full article

The conversion of plant byproducts, which are phenolic-rich substrates, to valuable co-products by implementing non-conventional extraction techniques is the need of the hour. In the current study, ultrasound- (UAE) and microwave-assisted extraction (MAE) were applied for the recovery of polyphenols from peach byproducts. Two-level screening and Box–Behnken design were adopted to optimize extraction efficiency in terms of total phenolic content (TPC). Methanol:water 4:1% v/v was the extraction solvent. The optimal conditions of UAE were 15 min, 8 s ON-5 s OFF, and 35 mL g⁻¹, while MAE was maximized at 20 min, 58 °C, and 16 mL g⁻¹. Regarding the extracts’ TPC and antioxidant activity, MAE emerged as the method of choice, whilst their antiradical activity was similar in both techniques. Furthermore, a liquid chromatography–tandem mass spectrometry (LC-MS/MS) method was developed and validated to determine chlorogenic acid and naringenin in byproducts’ extracts. 4-Chloro-4′-hydroxybenzophenone is proposed as a new internal standard in LC-MS/MS analysis in foods and byproducts. Chlorogenic acid was extracted in higher yields when UAE was used, while MAE favored the extraction of the flavonoid compound, naringenin. To conclude, non-conventional extraction could be considered as an efficient and fast alternative for the recovery of bioactive compounds from plant matrices. Full article

Theoretical investigations by density functional theory (DFT) and time-dependent DFT (TD-DFT) methods shed light on how the type of ligand or attached groups influence the electronic structure, absorption spectrum, electron excitation, and intramolecular and interfacial electron transfer of the Cu(II) complexes under study. The findings provide new insight into the designing and screening of high-performance dyes for dye-sensitized solar cells (DSSCs). Full article

Urinary concentrations of several endocrine disrupting chemicals, including phthalate metabolites, bisphenol A (BPA), and benzophenone (BP)-type ultraviolet (UV) filters, have been associated with a longer time-to-pregnancy (TTP). Potential modification of these associations by couple’s age has not been studied. TTP was defined as the number of prospectively observed menstrual cycles a couple attempted pregnancy until the occurrence of a human chorionic gonadotropic-detected pregnancy. Urinary concentrations of two BP-type UV filters and three phthalate metabolites were measured at baseline. Fecundability odds ratios (FORs) and 95% confidence intervals (CIs) were estimated for each chemical adjusting for age, body mass index, serum cotinine, creatinine, and accounting for right censoring and left truncation. Models evaluated effect modification between EDC concentrations and TTP by partner’s age, dichotomized at 35 years. Separate models were run for male and female partners. No significant effect modification was observed for any EDC for either partner, but data were suggestive of a longer TTP among females aged ≥35 years, particularly for BP-2 (FOR = 0.61, 95% CI 0.36, 1.05) and 4-hydroxybenzophenone (FOR = 0.71, 95% CI: 0.46, 1.09) reflecting 39% and 29% reductions in fecundability, respectively. We saw no evidence of effect modification by couples’ age on associations between TTP and urinary phthalate or BPA metabolite concentrations. Across the EDCs we examined, we found little evidence that age modifies TTP-exposure associations. Full article

We established and validated a sensitive multi-residue analytical method for identifying benzophenone (BP) and nine BP derivatives (2,4-dihydroxybenzophenone [BP-1], 2,2′,4,4′-tetrahydroxydroxybenzophenone, 2-hydroxy-4-methoxy benzophenone, 2,2′-dihydroxy 4-methoxy benzophenone, 2-hydroxybenzophenone [2-OHBP], 4-hydroxybenzophenone, 4-methylbenzophenone [4-MBP], methyl-2-benzoylbenzoate, and 4-benzoylbiphenyl). Solid–liquid extraction pretreatment and ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) were employed in an analysis of 85 packaged cereal-based food samples (25 pastry, 50 rice, and 10 noodle samples). The method had satisfactory linearity (R² ≥ 0.995), low limits of detection (pastry: 0.02–4.2 ng/g; rice and noodle: 0.02–2 ng/g), and favorable precision, with within-run and between-run coefficient of variation ranges of 1–29% and 1–28%, respectively. BP and 4-MBP were detected in 100% of the pastry samples, and BP-1 and 2-OHBP were found in 76% and 56% of the pastry samples, respectively. BP and 2-OHBP were found in 92% and 38% of the rice samples, respectively. BP was found in 50% of the noodle samples. BP contributed the most to the total level of BPs in pastries, with significantly higher mean ± standard deviation (range) levels for pastries (26.8 ± 32.6 [1.8–115.4] ng/g) than rice (1.2 ± 2.0 [0.4–13.4] ng/g) and noodles (0.7 ± 0.7 [0.4–1.9] ng/g); p < 0.0001). The trace levels of 4-MBP identified in the samples demonstrate the need for the development of analytical methods with high sensitivity and specificity; the proposed method satisfies this need. Full article

A fast, robust, and sensitive analytical method was developed and validated for the simultaneous identification of benzophenone (BP) and nine BP analogs (BP-1, BP-2, BP-3, BP-8, 2-hydroxybenzophenone, 4-hydroxybenzophenone, 4-methylbenzophenone [4-MBP], methyl-2-benzoylbenzoate, and 4-benzoylbiphenyl) in 25 samples of rice cereal. Fast pesticide extraction (FaPEx) coupled with ultrahigh-performance liquid chromatography–tandem mass spectrometry was applied. The developed method exhibited satisfactory linearity (r > 0.997), favorable recoveries between 71% and 119%, and a limit of detection ranging from 0.001 to 0.5 ng/g. The detection frequencies of BP, 4-MBP, and BP-3 were 100%, 88%, and 52%, respectively. BP had higher geometric levels, with a mean of 39.8 (19.1–108.9) ng/g, and 4-MBP had low levels, with a mean of 1.9 (1.3–3.3) ng/g. The method can be applied to routine rice cereal analysis at the nanogram-per-gram level. For infants aged 0–3 years, the hazard quotients of BP and 4-MBP were lower than one, and the margin of exposure for BP was higher than 10,000, suggesting that rice cereal consumption poses no health concern for Taiwanese infants. Full article

Photoinitiators used in ultraviolet-cured ink may migrate from food packaging materials into food products. Therefore, we conducted a dietary risk assessment of exposure to benzophenone (BP)-type photoinitiators by quantifying and reducing uncertainties associated with the risk characterization. A total of 362 food packaging samples including 180 cereals, 136 fruit and vegetable juices, and 46 milk samples were subjected to fast pesticides extraction to determine photoinitiator residues. The average daily dose (ADD) of BP was the highest in the age group of zero to three years, with a P97.5 ADD of 2.56 × 10⁻⁴ mg/kg bw/day. The ADD of 2-hydroxybenzophenone (2-OHBP) was the highest in the age group of three to six years, with a P97.5 UB ADD of 3.52 × 10⁻⁵ mg/kg bw/day. The estimated UB P97.5 ADD for each age group was below the toxicological concern threshold of 0.0015 mg/kg bw/day. The cumulative toxicity of all BPs, evaluated using the MOE_T value, was at an acceptable level. Although the MOE_T value of BPs was above the safety limit in the foodstuffs studied herein, this result may be different if Taiwan were to follow regulation guidelines for BP-type photoinitiators based on the specific migration limit for the unmeasured BP residues in other foodstuffs. Full article

There is a growing concern about the occurrence of bisphenols and benzophenone UV filters in natural ecosystems, while data are limited regarding their actual occurrence in wildlife species, especially in raptors. In this study, concentrations of bisphenol and benzophenone UV filter analogues were determined in liver tissue samples (n = 38) from white-tailed eagles (Haliaeetus albicilla) that were found dead in Smøla (2006–2018), which is a Norwegian municipality that holds one of the densest breeding populations of white-tailed eagles in Europe. Bisphenol AF (BPAF; a fluorinated analogue) was the most ubiquitous contaminant since it was detected in 32 liver samples at concentrations ranging from 1.08 to 6.68 ng/g wet weight (w.w.), followed by bisphenol A (BPA, mean 10.4 ng/g w.w.), benzophenone-1 (BzP-1, mean 3.24 ng/g w.w.), and 4-hydroxybenzophenone (4-OH-BzP, mean 0.62 ng/g w.w.). The concentrations found in livers suggested that white-tailed eagles potentially accumulate bisphenols and benzophenone UV filters, which raises concern, as these plastic and personal care product-related emerging contaminants can show endocrine-disrupting properties. The high detection frequency of the fluorinated BPAF warrants further attention as other fluorinated compounds have proven to be extremely persistent and potentially harmful to wildlife. Full article

The ultraviolet (UV) irradiation crosslinking reactions of polyethylene and the electronic properties of photo-initiators and reaction products are theoretically investigated by the first-principles calculations. The crosslinked polyethylene (XLPE) materials are prepared in experiments that employ the UV-initiated crosslinking technique with different photon-initiation systems. Infrared spectrum and the alternating current dielectric breakdown strength of UV-initiated XLPE are tested to explore the effect of reaction products on the breakdown characteristics in combination with the electron structure calculations. The theoretical calculations indicate that the 4-hydroxybenzophenone laurate, which is compatible with polyethylene, can effectively initiate crosslinking reactions of polyethylene molecules under UV photon excitation and will produce reaction by-products from carbonyl radicals; as a macromolecular auxiliary crosslinker, the monomer or homopolymer of dioleyl-2,2′,4,4′-tetraallyl isocyanurate can form chemical connections with multiple polyethylene molecules acting as a crosslinking node in a photon-initiated reaction process. The carbonyl, hydroxyl, or ester groups of reaction by-products are capable of capturing hot electrons to prevent polyethylene molecules from impact ionization, and thus will increase the breakdown electric field. The macromolecular auxiliary crosslinker and the macromolecular photon initiator as well as its reaction by-product can convert the energy of their captured high-energy electrons into heat, which can act as a voltage stabilizer. The molecule characterization of infrared spectra demonstrates that the characteristic absorption peaks of the carbonyl in the macromolecular photon initiator and the allyl in the macromolecular auxiliary crosslinking agent are gradually decreasing in intensity as the crosslinking reaction proceeds, which is consistent with the conclusion from theoretical calculations. Compared with the small molecular photon-initiation system generally used in the photon-initiated crosslinking process, the higher dielectric breakdown field of XLPE being prepared by utilizing a macromolecular photon-initiation system is in good agreement with the calculation results of electronic affinity and ionization potential. The consistent results of the experiments and first-principles calculations elucidate the fundamental mechanism of the UV-initiation crosslinking technique and suggest a prospective routine to improve the insulation strength for developing high-voltage XLPE insulating materials. Full article

Magnetite nanoparticles (Fe₃O₄) functionalized with graphene oxide (GO) have been synthesized through a silanization process of the magnetic nanoparticles with tetraethyl orthosilicate and (3-aminopropyl)triethoxysilane and further coupling of GO. The synthesized nanomaterials have been characterized by several techniques, such as transmission electron microscopy (TEM), and infrared and Raman spectroscopy, which enabled the evaluation of the different steps of the functionalization process. The hybrid nanomaterial has been employed for the extraction of five benzophenones (benzophenone-1, benzophenone-3, 4-hydroxybenzophenone, benzophenone-6 and benzophenone-8) in aqueous samples by dispersive micro-solid phase extraction, combining the magnetic properties of magnetite nanoparticles with the excellent sorption capacity of graphene oxide via hydrophobic interactions with the analytes. The subsequent separation and quantification of the analytes was performed by liquid chromatography with tandem mass spectrometric detection, achieving limits of detection (LODs) in the range 2.5 to 8.2 μg·L⁻¹, with relative standard deviations ranging from 1.3–9.8% and relative recovering in the range 86 to 105%. Positive swimming pool water samples analysed following the developed method revealed the presence of benzophenones in from 14.3 to 39 μg·L⁻¹. Full article