Human dermal exposure to galaxolide from personal care products

Musks are synthetic fragrances applied on personal care and household products as fixatives, by retarding the release of other fragrances with higher volatility. Galaxolide is the most used polycyclic musk since the 90th decade, and it has been detected in several environmental and biological matrices, particularly in human tissues and fluids. For exposure assessment purposes, large‐monitoring data need to be obtained and rapid but reliable analytical techniques are requested. The main objective of this study is to develop and validate a new and fast analytical methodology to quantify galaxolide in personal care products and to apply this method to real matrices like skin care products (creams and lotions), shower products (soap bar), hair care products (shampoo and hair conditioner) and oral care products (toothpaste), to evaluate the human dermal exposure risk. A dispersive solid‐phase extraction is proposed, using QuEChERS methodology, followed by HPLC with fluorescence detection. Some extraction parameters were studied, like the ratio of sample/solvent amounts, the homogenization time, the salt addition effect and the used sorbents. The validation parameters of the developed method were the following: a linearity range of 0.005–1.002 mg kg^?1 sample, a limit of detection of 0.001 mg kg^?1 sample, repeatability between 0.7% and 11.3% (variation coefficient of six standard injections), an intermediate precision of 2.5% (variation coefficient of six independent analysis of the same sample), mean recoveries ranging from 65% (soap bar) to 95% (body cream) and 3% of global uncertainty in most of the working range. The time of analysis, including the extraction steps, is 60 min, allowing a throughput of 4 samples h^?1. Galaxolide was detected in all of the seven analysed products in concentrations ranging from 0.04 ± 0.01 mg kg^?1 sample (toothpaste) to 280.78 ± 8.19 mg kg^?1 sample (perfumed body cream), which may correspond to a significant estimated daily human dermal exposure of 904 μg day^?1.     

Survival of Lactobacillus delbrueckii UFV H2b20 in ice cream produced with different fat levels and after submission to stress acid and bile salts

The survival of Lactobacillus delbrueckii UFV H2b20 in three ice cream formulations (low fat, fat free and high fat) was evaluated after the processing and storage at ?16 °C. The survival of L. delbrueckii UFV H2b20 was not significantly affected (P > 0.05) in three ice cream formulations after processing. The same result was observed during storage for 40 days at ?16 °C. Cells of L. delbrueckii UFV H2b20 incorporated in three ice cream formulation survived when exposed to acid stress and bile salts. The results demonstrate that L. delbrueckii UFV H2b20 has potential for being used in ice cream and capacity to resist acid stress and to grow in the presence of bile salts. This demonstrates that reduction of fat in ice cream does not compromise the viability of L. delbrueckii UFV H2B20.     

Effect of Cleaning Treatment on Adhesion of Streptococcus agalactiae to Milking Machine Surfaces

Streptococcus agalactiae is a common subclinical mastitis agent in dairy cattle. In this study, the influence of hygiene procedure time on the adhesion of S. agalactiae to rubber and silicone surfaces used in milking machines was evaluated. The effect of hygiene practices on the thermodynamic and microscopic features of both surfaces was also evaluated. The hydrophobicity of milking machines and bacterial surfaces was investigated by measuring the contact angle with a goniometer 0, 30, 90, and 180 days after a full hygiene procedure simulated using rubber and silicone coupons. As the time of cleaning procedures enhanced, there was a reduction in the adhesion of S. agalactiae to both surfaces. The rubber and silicone surfaces were hydrophobic in all treatments $ \left( {\Delta G_{\text{sws}}^{\text{TOT}}\; < \;0} \right) $ , while the bacterial surface presented hydrophilic behavior $ \left( {\Delta G_{\text{sws}}^{\text{TOT}}\; > \;0} \right) $ , which makes the adhesion process difficult. Photomicrographs showed rapid wear of both surfaces, pointing to damages caused by cleaning agents. However, the silicone was more resistant to cleaning and sanitizing treatments. Thus, this work shows that changes caused by hygiene procedures in the thermodynamic and in the morphology of milking surfaces have an enormous importance in the S. agalactiae adhesion and, consequently, in mastitis transmission between cattle herd.     

Application of Mid- and Near-Infrared Spectroscopy for the Control and Chemical Evaluation of Brine Solutions and Traditional Sea Salts

Mid- and near-infrared spectroscopy methodologies were explored for the analysis of brine solutions and traditional sea salt samples. Brine solutions from different salt pans, corresponding to different stages of sodium chloride crystallisation, were collected. A total of 61 dried and non-dried traditional sea salts were also analysed. Partial least squares regression with leave-one-out cross-validation strategy was applied for the calibration of inorganic constituents Ca²⁺, Mg²⁺ and K⁺, alkalinity as HCO ₃ ^? , SO ₄ ^2? , NO ₂ ^? and NO ₃ ^? and phosphate in brine solutions. Promising results were obtained with the near-infrared (NIR) methodology for brine solutions with coefficients of determination R ²?>?0.90 for Mg⁺², K⁺, HCO ₃ ^? and SO ₄ ^2? . Using mid-infrared, the calibration for H₂PO ₄ ^? was R ²?=?0.85. In relation to the sea salt samples, the strategy adopted was the re-sampling based cross-validation using different spectral pre-processing treatments. In this case, the calibrations using the two IR methodologies fell bellow acceptable levels for the techniques; however, by comparing the R ² coefficient, the results were slightly better when using the NIR spectra of dried sea samples. In general, these results open a new possibility for the IR applications and also bring an opportunity for continuing with the NIR characterization for dried sea salt samples.     

Validation of a Single-Extraction Procedure for Sequential Analysis of Vitamin E, Cholesterol, Fatty Acids, and Total Fat in Seafood

Food lipid major components are usually analyzed by individual methodologies using diverse extractive procedures for each class. A simple and fast extractive procedure was devised for the sequential analysis of vitamin E, cholesterol, fatty acids, and total fat estimation in seafood, reducing analyses time and organic solvent consumption. Several liquid/liquid-based extractive methodologies using chlorinated and non-chlorinated organic solvents were tested. The extract obtained is used for vitamin E quantification (normal-phase HPLC with fluorescence detection), total cholesterol (normal-phase HPLC with UV detection), fatty acid profile, and total fat estimation (GC-FID), all accomplished in <40 min. The final methodology presents an adequate linearity range and sensitivity for tocopherol and cholesterol, with intra- and inter-day precisions (RSD) from 3 to 11 % for all the components. The developed methodology was applied to diverse seafood samples with positive outcomes, making it a very attractive technique for routine analyses in standard equipped laboratories in the food quality control field.     

Evaluation of Sample Preparation Procedures for Trace Element Determination in Brazilian Propolis by Inductively Coupled Plasma Optical Emission Spectrometry and Their Discrimination According to Geographic Region

Propolis is a complex mixture of substances collected by honeybees from buds or exudates of plants, beeswax, and other constituents, as pollen and sugars. The main purpose of this study was to evaluate two digestion procedures for determination of major, minor, and trace elements (Ba, Ca, Cd, Cr, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn) in natura propolis samples by inductively coupled plasma optical emission spectrometry (ICP OES). The first procedure studied was an open-vessel digestion using HNO₃ + H₂SO₄ + H₂O₂ in a heating block and the second one was a microwave-assisted concentrated acid digestion using HNO₃ + H₂O₂. Both digestion procedures led to similar results and quantitative recoveries. The residual carbon contents (RCCs) for propolis sample digests were 0.269?±?0.012 % when using the first procedure with conventional heating and 0.458?±?0.023 % by microwave-assisted closed vessel digestion, demonstrating high efficiency of both procedures. Accuracy of the results was demonstrated using a certified reference material and by comparison with a recommended official method. The t test (unpaired) at 95 % confidence level showed that there was no significant difference between determined and certified values of all analytes under investigation, except Ca concentration employing conventional procedure. The optimized microwave-assisted digestion procedure led to recoveries around 89–103 % and precision better than 5 % for most samples. The second procedure was faster, safer, and more accurate than the one based on conductive heating. Additionally, principal component analysis (PCA) was applied for checking if there was correlation between inorganic composition and source of propolis samples collected around Bahia State in the Northeast of Brazil.     

Bromine, Chlorine, and Iodine Determination in Soybean and its Products by ICP-MS After Digestion Using Microwave-Induced Combustion

A method for bromine, chlorine, and iodine determination in soybean and related products was developed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Samples were pressed as pellets and combusted using pressurized oxygen (20 bar) and ammonium nitrate solution (50 μL of 6 mol L^?1) as the igniter. Analytes were absorbed in alkaline solution (100 mmol L^?1 NH₄OH), and a reflux step of 5 min, microwave power of 1,400 W, was applied after combustion in order to improve analyte recoveries. For Cl determination by ICP-MS, a dynamic reaction cell was used with ammonia as the reaction gas. The accuracy was evaluated using certified reference materials (CRMs) and spiked samples. Using MIC, the agreement with CRM values and spike recoveries was higher than 95 % for all analytes for certified reference materials of a similar composition (National Institute of Standards and Technology (NIST), corn bran and NIST, whole milk). Limits of detection were 0.03, 1.2, and 0.002 μg g^?1 for Br, Cl, and I, respectively. The residual carbon content in the digests obtained after MIC procedure was lower than 0.5 %. Blanks were always negligible and no memory effects were observed. Digestion by MIC allowed processing up to eight samples by each run in 25 min with high efficiency of digestion providing a suitable medium for further bromine, chlorine, and iodine determination by ICP-MS.     

Hormonal manipulations in the 5-day timed artificial insemination protocol to optimize estrous cycle synchrony and fertility in dairy heifers

Objectives were to determine the effects of GnRH at the initiation of the 5-d timed artificial insemination (AI) program combined with 2 injections of PGF_2α on ovarian responses and pregnancy per AI (P/AI) in dairy heifers, and the role of progesterone concentrations on LH release and ovulation in response to GnRH. In study 1, heifers received a controlled internal drug release (CIDR) insert containing 1.38 g of progesterone on d 0, an injection of 25 mg of PGF_2α and CIDR removal on d 5, and an injection of 100 μg GnRH concurrently with AI on d 8. Heifers were assigned to receive no additional treatment (control; n = 559) or an injection of GnRH on d 0 and a second injection of PGF_2α on d 6 (G2P; n = 547). In study 2, all heifers were treated as described for the control in study 1, and were allocated to receive no additional treatment (control; n = 723), an injection of PGF_2α on d 6 (NG2P; n = 703), or an injection of GnRH on d 0 and an injection of PGF_2α on d 6 (G2P; n = 718). In study 3, heifers received a CIDR on d 7 after ovulation and were assigned randomly to a low-progesterone (LP; n = 6) treatment in which 2 injections of 25 mg of PGF_2α each were administered 12 h apart, on d 7 and 7.5 after ovulation, or to a high-progesterone (HP; n = 12) treatment in which no PGF_2α was administered. On d 8, heifers received 100 μg of GnRH and blood was sampled at every 15 min from −30 to 180 min relative to the GnRH for assessment of LH concentrations. Additionally, 94 heifers were assigned to LP or HP and ovulation in response to GnRH was evaluated. In study 1, P/AI was greater for G2P than for the control on d 32 (59.4 vs. 53.5%) and 60 after AI (56.6 vs. 51.3%). In study 2, administration of GnRH on d 0 increased the proportion of heifers with a new corpus luteum on d 5 (control = 21.9 vs. NG2P = 20.1 vs. G2P = 34.4%). Administration of a second PGF_2α increased the proportion of heifers with progesterone <0.5 ng/mL at AI (control = 83.1 vs. NG2P = 93.0 and G2P = 87.2%). Pregnancy per AI was greater for G2P than for control and NG2P on d 32 (control = 52.9 vs. NG2P = 55.0 vs. G2P = 61.7%) and 60 (control = 49.0 vs. NG2P = 51.6 vs. G2P = 59.1%). In study 3, HP attenuated LH release and reduced ovulation (19.0 vs. 48.4%) in response to GnRH compared with LP. Combining GnRH and 2 doses of PGF_2α in the 5-d timed AI protocol improved follicle turnover, luteolysis, and P/AI in heifers. Elevated concentrations of progesterone suppressed LH release and are linked with the low ovulatory response to the initial GnRH treatment of the protocol.     

Modulatory effects of yerba maté (Ilex paraguariensis) on the PI3K‐AKT signaling pathway

The aim of this study was to evaluate the effects of yerba maté (YM) extract on the phosphatidylinositol 3‐kinase (PI3K)‐AKT signaling pathway in vivo. The mice were introduced to either standard‐ or high‐fat diet (HFD). After 8 weeks on an HFD, mice were randomly assigned to one of the two treatment conditions, water or yerba maté extract at 1.0 g/kg. After treatment, glucose blood level and hepatic insulin response were evaluated. Liver tissue was examined to determine the mRNA levels using the PI3K‐AKT PCR array. The nuclear translocation of forkhead box O1 (FOXO1) was determined by an electrophoretic mobility‐shift assay. Our data demonstrated that yerba maté extract significantly decreased the final body weight, glucose blood levels, and insulin resistance of mice. Molecular analysis demonstrated that an HFD downregulated Akt2, Irs1, Irs2, Pi3kca, Pi3kcg, and Pdk1; after yerba maté treatment, the levels of those genes returned to baseline. In addition, an HFD upregulated Pepck and G6pc and increased FOXO1 nuclear translocation. The intervention downregulated these genes by decreasing FOXO1 nuclear translocation. The results obtained demonstrate for the first time the specific action of yerba maté on the PI3K‐AKT pathway, which contributed to the observed improvement in hepatic insulin signaling.     

Structural Modification of TiO2 Nanorod Films with an Influence on the Photovoltaic Efficiency of a Dye-Sensitized Solar Cell (DSSC)

TiO₂ nanorod films have been deposited on ITO substrates by dc reactive magnetron sputtering technique. The structures of these nanorod films were modified by the variation of the oxygen pressure during the sputtering process. Although all these TiO₂ nanorod films deposited at different oxygen pressures show an anatase structure, the orientation of the nanorod films varies with the oxygen pressure. Only a very weak (101) diffraction peak can be observed for the TiO₂ nanorod film prepared at low oxygen pressure. However, as the oxygen pressure is increased, the (220) diffraction peak appears and the intensity of this diffraction peak is increased with the oxygen pressure. The results of the SEM show that these TiO₂ nanorods are perpendicular to the ITO substrate. At low oxygen pressure, these sputtered TiO₂ nanorods stick together and have a dense structure. As the oxygen pressure is increased, these sputtered TiO₂ nanorods get separated gradually and have a porous structure. The optical transmittance of these TiO₂ nanorod films has been measured and then fitted by OJL model. The porosities of the TiO₂ nanorod films have been calculated. The TiO₂ nanorod film prepared at high oxygen pressure shows a high porosity. The dye-sensitized solar cells (DSSCs) have been assembled using these TiO₂ nanorod films prepared at different oxygen pressures as photoelectrode. The optimum performance was achieved for the DSSC using the TiO₂ nanorod film with the highest (220) diffraction peak and the highest porosity.