Dispersive liquid-liquid microextraction and Monte Carlo simulation of margin of safety for octocrylene, EHMC, 2ES, and homosalate in sunscreens.

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.

Deep Eutectic Solvent Based Reversed-Phase Dispersive Liquid-Liquid Microextraction and High-Performance Liquid Chromatography for the Determination of Free Tryptophan in Cold-Pressed Oils.

A fast and straightforward reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) using a deep eutectic solvent (DES) procedure to determine free tryptophan in vegetable oils was developed. The influence of eight variables affecting the RP-DLLME efficiency has been studied by a multivariate approach. A Plackett-Burman design for screening the most influential variables followed by a central composite response surface methodology led to an optimum RP-DLLME setup for a 1 g oil sample: 9 mL hexane as the diluting solvent, vortex extraction with 0.45 mL of DES (choline chloride-urea) at 40 °C, without addition of salt, and centrifugation at 6000 rpm for 4.0 min. The reconstituted extract was directly injected into a high-performance liquid chromatography (HPLC) system working in the diode array mode. At the studied concentration levels, the obtained method detection limits (MDL) was 11 mg/kg, linearity in matrix-matched standards was R2 ≥ 0.997, relative standard deviations (RSD) was 7.8%, and average recovery was 93%. The combined use of the recently developed DES -based RP-DLLME and HPLC provides an innovative, efficient, cost-effective, and more sustainable method for the extraction and quantification of free tryptophan in oily food matrices. The method was employed to analyze cold-pressed oils from nine vegetables (Brazil nut, almond, cashew, hazelnut, peanut, pumpkin, sesame, sunflower, and walnut) for the first time. The results showed that free tryptophan was present in the range of 11-38 mg/100 g. This article is important for its contributions to the field of food analysis, and for its development of a new and efficient method for the determination of free tryptophan in complex matrices, which has the potential to be applied to other analytes and sample types.

Development of New Accelerated Aging Test for Comparison of the Quality of Different Insulating Papers Based on Cellulose.

The aim of this study is to propose a test method for the determination of the quality of transformer paper insulation. For this purpose, the oil/cellulose insulation systems were exposed to various accelerated aging tests. The results of the aging experiments of normal Kraft and thermally upgraded papers, two different types of transformer oil (mineral and natural ester), and copper are shown. Aging was carried out in various experiments at 150 °C, 160 °C, 170 °C, and 180 °C with dry (initial values ≤ 0.5%) and moistened cellulose insulation (initial values 3-3.5%). Following insulating oil and paper, degradation markers were measured: the degree of polymerization, tensile strength, furan derivates, methanol/ethanol, acidity, interfacial tension, and dissipation factor. It was found that the aging of cellulose insulation in cycles was 1.5-1.6 times faster in comparison to continuous aging, due to the more pronounced effect of hydrolytic mechanism in cyclic aging owing to the produced and absorbed water. Furthermore, it was observed that the high initial water content in cellulose increases the aging rate two to three times more than in the dry experimental setup. The proposed aging test in cycles can be used to achieve faster aging and to compare the quality of different insulating papers.

Isotherm, Thermodynamic and Kinetic Studies of Elemental Sulfur Removal from Mineral Insulating Oils Using Highly Selective Adsorbent.

Elemental sulfur (S8) is a corrosive sulfur compound which was found to be extremely reactive to silver, causing intensive silver sulfide (Ag2S) deposition on on-load tap changer (OLTC) contacts in power transformers. A highly selective adsorbent (HSA), called Tesla'Ssorb, for the removal of S8 from mineral insulating oils was prepared from raw material (RM) using the novel procedure. In this study, the adsorption properties of HSA for the removal of S8 from the oil were determined. RM and HSA were characterized using various techniques, such as field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). The performance of HSA was determined by adsorption equilibrium, thermodynamic, and kinetic study through batch experiments, at various temperatures and initial concentrations of S8. The obtained results were analyzed by Langmuir and Freundlich adsorption isotherms and it was found that equilibrium data were fitted better with the Langmuir isotherm model. The maximum adsorption capacity was 4.84 mg of S8/g of HSA at 353 K. Thermodynamic parameters, such as enthalpy (ΔH°), Gibbs free energy (ΔG°), and entropy (ΔS°), were calculated and it was found that the sorption process was spontaneous (ΔG° < 0) and endothermic in nature (ΔH° > 0). It was found that the adsorption of S8 follows pseudo-second-order kinetic model, and the activation energy indicated the activated chemisorption process.

Protective Role of Maternal P.VAL158MET Catechol-O-Methyltransferase Polymorphism against Early-Onset Preeclampsia and its Complications.

BACKGROUND: Up until now there have been contradictory data about the association between p.Val158Met catechol-O-methyltransferase (COMT) polymorphism and risk of preeclampsia (PE). The goal of this study was to assess the potential correlation between p.Val158Met COMT polymorphism and risk of early-onset PE, risk of a severe form of early-onset PE, as well as risk of small-for-gestational-age (SGA) complicating PE. METHODS: The study included 47 early-onset PE patients and 47 control cases. Forty-seven early-onset PE patients were grouped by disease severity (33 patients with a severe form and 14 patients without severe features) and secondly by size for gestational age (12 patients with appropriate-for-gestational-age (AGA) and 35 patients with SGA size). p.Val158Met polymorphism was genotyped by PCR-RFLP analysis. RESULTS: Allele analysis showed significant difference in COMT allele distribution between early-onset PE and control group as well as early-onset PE SGA and controls (p=0.04057 and p=0.0411 respectively). A statistically significant distribution difference between the severe form and form without severe features of early-onset PE patients was not observed (p>0.05). The highest difference observed was in the allele recessive model where COMT MetMet genotype was associated with decreased risk of early-onset PE (OR=0.281; 95%CI = 0.092-0.7836) and PE complications including severe early-onset PE (OR= 0.304; 95%CI=0.086-0.944) and SGA early-onset PE (OR=0.284; 95%CI=0.081-0.874). CONCLUSIONS: COMT may be used as a candidate gene for early-onset PE and its severe form and SGA complications.

Intestinal type of lung adenocarcinoma in younger adults.

Intestinal type of lung adenocarcinoma (ILADC) was initially described by Tsao and Fraser in 1991. Morphology and immunophenotype of ILADC are the same as in colorectal adenocarcinoma. Rectocolonoscopy must be performed to exclude colorectal origin of adenocarcinoma. Colorectal adenocarcinoma claimed to be genetically similar to an ILADC. Patients. We describe 24- and 26-year-old patients of both genders who went under surgery because of a lung tumor mass detected on CT scan. ILADC was diagnosed on resected lung specimens. According to positivity of Cytokeratin20, CDX-2, and Villin, respectively, and negativity of Cytokeratin7, TTF-1, Napsin-A, SurfactantB, MUC-1, and MUC-2, respectively, ILADC was diagnosed. KRAS mutation was detected in tumor tissue of the male patient. Conclusion. Rectocolonoscopy is the only relevant method for distinguishing the intestinal type of lung adenocarcinoma from metastatic colorectal carcinoma because immunohistochemistry and detection of mutation status are frequently the same in both types of adenocarcinoma. More investigations are needed for further understanding of ILADC in purpose of personalized lung carcinoma therapy particularly introducing detection of mutation status, especially in younger patients.