Simultaneous determination of bisphenol A and bisphenol B in beverages and powdered infant formula by dispersive liquid–liquid micro-extraction and heart-cutting multidimensional gas chromatography-mass spectrometry

The purpose of this study was to establish a reliable, cost-effective, fast and simple method to quantify simultaneously both bisphenol A (BPA) and bisphenol B (BPB) in liquid food matrixes such as canned beverages (soft drinks and beers) and powdered infant formula using dispersive liquid–liquid micro-extraction (DLLME) with in-situ derivatisation coupled with heart-cutting gas chromatography-mass spectrometry (GC-MS). For the optimisation of the DLLME procedure different amounts of various extractive and dispersive solvents as well as different amounts of the derivative reagent were compared for their effects on extraction efficiency and yields. The optimised procedure consisted of the injection of a mixture containing tetrachloroethylene (extractant), acetonitrile (dispersant) and acetic anhydride (derivatising reagent) directly into an aliquot of beverage samples or into an aqueous extract of powdered milk samples obtained after a pretreatment of the samples. Given the compatibility of the solvents used, and the low volumes involved, the procedure was easily associated with GC-MS end-point determination, which was accomplished by means of an accurate GC dual column (heart-cutting) technique. Careful optimisation of heart-cutting GC-MS conditions, namely pressure of front and auxiliary inlets, have resulted in a good analytical performance. The linearity of the matrix-matched calibration curves was acceptable, with coefficients of determination (r2) always higher than 0.99. Average recoveries of the BPA and BPB spiked at two concentration levels into beverages and powdered infant formula ranged from 68% to 114% and the relative standard deviation (RSD) was <15%. The limits of detection (LOD) in canned beverages were 5.0 and 2.0?ng?l^–1 for BPA and BPB, respectively, whereas LOD in powdered infant formula were 60.0 and 30.0?ng?l^–1, respectively. The limits of quantification (LOQ) in canned beverages were 10.0 and 7.0?ng?l–1 for BPA and BPB, respectively, whereas LOQ in powdered infant formula were 200.0 and 100.0?ng?l^–1, respectively. BPA was detected in 21 of 30 canned beverages (ranging from 0.03 to 4.70?µg?l^–1) and in two of seven powdered infant formula samples (0.23 and 0.40?µg?l^–1) collected in Portugal. BPB was only detected in canned beverages being positive in 15 of 30 samples analysed (ranging from 0.06 to 0.17?µg?l^–1). This is the first report about the presence of BPA and BPB in canned beverages and powdered infant formula in the Portuguese market.     

Elimination of matrix effects in the determination of bisphenol A in milk by solid-phase microextraction–high-performance liquid chromatography

Solid-phase microextraction coupled to high-performance liquid chromatography (SPME–HPLC) with fluorescence detection was employed to determine bisphenol A (BPA) in milk samples. The potential influence of the milk matrix on the determination of BPA by SPME–HPLC were investigated. Optimal conditions to eliminate any matrix effects were as follows: milk samples were deproteinized with trichloroacetic acid, diluted 20-fold with BPA-free Ultrapure water, dissolved in methanol, the precipitated protein was filtered out, rinsed with methanol and evaporated to remove the methanol. Then, a 40.0-ml solution was used for SPME extraction and HPLC analysis. Satisfactory recoveries (milk: 93.1–101%; soybean milk: 93.9–102%) were achieved. The proposed method was successfully applied to real samples, BPA being detected within the range 1.6–2.6 ng ml^?1 in four brands of commercial milk but not in soybean milk.     

Determination of polycyclic aromatic hydrocarbons in edible oils and barbecued food by HPLC/UV–Vis detection

Determination of nine polycyclic aromatic hydrocarbons in corn, sunflower, olive oils and barbecued meat and fish by HPLC/UV–Vis method is described. The extraction procedure included a saponification, liquid–liquid extraction and finally purification of PAHs through a house-made silica–alumina column. Chromatographic determination was based on separation of PAHs on ODS column and measurement at 254 nm. All polycyclic aromatic hydrocarbons were separated and analyzed in 12 min on reversed phase ODS column with acetonitrile/water mobile phase at 1.5 mL min⁻¹ flow rate. The detection limits of nine polycyclic aromatic hydrocarbons ranged from 0.26 to 1.15 μg L⁻¹ at a signal/noise ratio of 3. The linearity of the method was between 0.9951 and 0.9996. Oil samples contain different PAHs ranging from 0.44 to 98.92 μg L⁻¹. Barbecuing process increased the concentration (in the range of 2- to 8-fold) and caused the formation of PAHs in food samples.     

Monitoring the Oxidative Stability of Monovarietal Extra Virgin Olive Oils by UV–Vis Spectroscopy and MCR–ALS

The extra virgin olive oil (EVOO) has a certain oxidation resistance when compared to other vegetable oils without refining process, due to their large composition of monounsaturated fatty acids, antioxidants, and bio-compounds. The main of this research was to evaluate and monitor the behavior of autoxidative processes through the storage time in two packaging systems of different EVOO monovarietals produced in Minas Gerais, Brazil by using ultraviolet and visible spectroscopy (UV–Vis) with multivariate curve resolution with alternating least squares (MCR–ALS). We analyzed six EVOOs produced from different monovarietals (Arbequina, Empeltre, Coratina, Grappolo, Koroneiki, and Maria da Fé), over the course of 1 year, performed the analysis in times 0, 30, 90, 180, and 365 days, and storage in glass bottles and tinplate cans. The UV–Vis spectroscopy coupled with MCR–ALS was a feasible tool to monitor autoxidation processes in EVOO through storage time and in the monitoring of the EVOO quality in different package systems. The glass bottles were a package system that provides more protection for the autoxidation processes with the time for the EVOO from monovarietals Empeltre, Arbequina, and Coratina. In addition, it was possible to make a differentiation between the monovarietal olive oils produced in Brazil by observing the amount of phenolic compounds present in the chemical composition of each oil. Allowing gather information about the formation of oxidative products may correlate with the shelf life of the EVOO.     

Microencapsulation and controlled release of α-tocopherol by complex coacervation between pea protein and tragacanth gum: A comparative study with arabic and tara gums

The ability of pea protein isolates (PPI) to form complex coacervates with tragacanth gum (TRAG) was used for the microencapsulation of α-tocopherol mixture with pH-dependent release properties. The microcapsules were compared to three other models: PPI alone, PPI and gum arabic (PPI-GAC, known to form microcapsules of complex coacervates), and PPI and tara gum (PPI-TARA, non-ionic polysaccharides). The behaviors of the complex coacervates and microcapsules were studied according to the protein/polysaccharide mixture and protein/polysaccharide ratio. The formation of complex coacervates from the PPI-TRAG and PPI-GAC mixtures impacted the particle size of the liquid suspensions and microcapsules, the efficiency of encapsulation and the active release profile. An interesting gastroprotective behavior was identified for the PPI-TRAG mixture at the 1:1 ratio in simulated digestion media. Overall, the results showed the ability of PPI associated with polysaccharides to form microcapsules with a pH-dependent release behavior, that is promising in the field of gastroprotective microencapsulation.     

Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC–ICP–MS and HPLC–ESI–MS/MS

Analytical methods for selenium (Se) speciation were developed using high-performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP?CMS) or electrospray ionization tandem mass spectrometry (ESI?CMS/MS). Separations of selenomethionine (Se-Met) and selenocysteine (Se-(Cys)₂) with favorable peak shape and resolution were obtained by both HPLC-ICP-MS and HPLC?CESI?CMS/MS. Both methods achieved low limits of detection, high sensitivity and favorable stability. With HPLC?CESI?CMS/MS, signal suppression was observed when complex matrix was co-eluted, but excellent structural characterization was still achieved. Thus, HPLC-ICP-MS is better for the detection of Se species, and HPLC?CESI?CMS/MS is essential for molecular identification and confirmation. A water-soluble selenoprotein from purified M. anguillicaudatus muscle tissue was analyzed by the two complementary systems (HPLC-ICP-MS and HPLC?CESI?CMS/MS) with high sensitivity and accuracy. The results demonstrated that Se-Met was the predominant selenoamino acid in the purified selenoprotein from M. anguillicaudatus muscle tissue, and the concentration of Se-Met in the selenoprotein was 6.280?mg/kg (dry mass). In addition, in HPLC-ICP-MS, an unknown Se-containing compound with similar polarity to Se-(Cys)₂ was discovered. Using complementary data from HPLC?CESI?CMS/MS, it was determined that this unknown Se-containing compound was not Se(Cys)_2.     

The relationship between disgust sensitivity and BMI: Is the food disgusting or am I?

Core disgust is a negative emotion, comprised of disgust in response to food, animals, and from the body itself (and its products). Individual differences exist in the level to which people experience the emotion of core disgust. Sensitivity to disgust has been associated negatively with Body Mass Index (BMI) in overweight and obese people, and to eating disorders independently from BMI. This study investigates the relationship between disgust sensitivity and BMI by examining data from the Italian Taste Project (n = 2317). We hypothesized that the relationship between disgust sensitivity and BMI, after accounting for age and gender, may be mediated by other factors, such as 6-n-propylthiouracil (PROP) sensitivity or eating restraint, and that this relationship might differ in non-obese and obese individuals. Results showed that the relationship between sensitivity to disgust and food behaviors is complex and differs between obese and non-obese people. Two mediation models were considered. In the first case restrained eating acted as a mediator of disgust sensitivity in the prediction of BMI, while in the second one BMI acted only as a partial mediator of disgust sensitivity in the prediction of restrained eating. This suggests that heightened sensitivity to core disgust may be associated with a heightened sensitivity to self-disgust, motivating restrained eating behaviors when BMI is higher, but only in non-obese individuals.     

Evaluation of cheese authenticity and proteolysis by HPLC and urea–polyacrylamide gel electrophoresis

Chromatographic and electrophoretic methods have been established as useful tools in characterising cheese ripening and in the detection of milk adulteration. The purpose of this work was to evaluate casein proteolysis of cheeses made from bovine, ovine or mixtures of bovine and ovine milks, as well as ovine cheese authenticity, for 30 days of ripening by HPLC and urea–polyacrylamide gel electrophoresis.Complementary information was obtained by both techniques when applied to the study of casein proteolysis during 30 days of ripening of ovine milk cheeses, ovine milk cheeses with 10% and 20% of bovine milk and bovine milk cheeses, manufactured according to the traditional Terrincho technology. For ovine cheeses, α-casein was the fraction that showed the higher degradation during cheese ripening. A similar behaviour was observed for ovine milk cheese with 10% of bovine milk. The profile for ovine milk cheese with 20% of bovine milk was more similar to that obtained for bovine cheese. Concerning bovine milk cheeses, electrophoresis was the most sensitive technique for the evaluation of proteolysis in these cheeses.Ten and 20% of bovine milk could be detected in ovine milk cheeses by urea–polyacrylamide gel electrophoresis and HPLC, respectively, even after 30 days of ripening.     

Determination of ochratoxin A in traditional Chinese medicinal plants by HPLC–FLD

Traditional Chinese medicinal plants (TCMPs), commonly used as spices, additives or foods, are also widely used in China to prevent and cure human disease. Due to their provenance, TCMPs may be contaminated by various fungal species, including ochratoxigenic fungi, during growth, collection, transportation and, especially, storage. A reliable method for the determination of ochratoxin A (OTA) in TCMPs of different origins was developed to monitor OTA levels in China. Analyses involved the extraction of OTA by methanol/water, immunoaffinity column (IAC) clean-up and HPLC quantification with fluorescence detection (FLD). Positive results were further confirmed by LC–ESI–MS/MS. The limit of detection (LOD) was 0.3 µg kg^?1, based on a signal-to-noise ratio of 3 : 1. Among the total of 57 TCMPs samples collected from six different areas, 31 were visibly moldy due to inappropriate storage; 26 sample, purchased from local TCMPs markets, were not visibly moldy. The results showed that 23 of the visibly moldy samples and two of the not visibly moldy were contaminated with OTA at levels ranging 1.2–158.7 and 2.5–5.6 µg kg^?1, respectively. This is the first report of the natural occurrence of OTA in TCMPs.     

The relationship between children’s and mothers’ vegetable liking in Chile,China and the United States

This study analyzed children’s (n = 384), 5 to 12 years old, and their mothers’ (n = 321) vegetable liking in three countries (Chile, China and the USA). Liking measures were collected using tasting sessions in which fourteen different vegetables were tasted. Three factors were tested: country (Chile, China, USA), status (mother/child) and products (vegetables). The results showed that mothers gave higher liking vegetable scores than their children when all the participants were analyzed together (p < 0.05). However, some differences were found between countries when they were analyzed individually. Specifically, American mothers like vegetables more than their children, while Chinese and Chilean mothers like vegetable the same amount as their children. Moreover, it was observed that Chilean mothers liked a smaller variety of vegetables than their children. The use of the 7-point hedonic scale to rate the vegetables was also analyzed. Children in the three countries and Chilean mothers showed a polarized use of the scale (with mostly extreme like and extreme dislike ratings), while mothers in China and the USA showed a pattern of use of the upper part of the scale. Three preference segments were uncovered for children in Chile and China, and two for US children. The variety of the children’s diets, the amount of vegetables eaten at lunch/dinner, and the level of the mothers’ satisfaction with their children’s vegetable intake were factors used to characterize the different child preference segments according to their level of liking (p < 0.05).     

The analysis of saturated and aromatic mineral oil hydrocarbons in dry foods and from recycled paperboard packages by online HPLC–GC–FID

ABSTRACT

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography–gas chromatography–flame ionisation detection (online HPLC–GC–FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7–45% in dry foodstuffs and 4–48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (?C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (?C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a ‘crispy’ product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C₂₀–C₃₅.     

The antibacterial activity and antibacterial mechanism of the tea polyphenol liposomes/lysozyme–chitosan gradual sustained release composite coating

To obtain long-lasting preservation materials, the tea polyphenol liposomes (TP-Lips)/lysozyme (LZM)–chitosan (CS) composite coating with the gradual sustained property was prepared by tape casting method. These coatings were characterised, and their physicochemical properties were measured. Meanwhile, the antibacterial mechanisms of coatings were studied using the spoilage bacteria of aquatic products (Shewanella putrefaciens and Pseudomonas fluorescens) as target strains. Compared with CS coating, the incorporation of TP-Lips makes the cracks and granular matter of the coatings increase. Except for the oxygen permeabilities (OP) and carbon dioxide permeabilities (CDP), the rest of the physicochemical properties are decreased, including tensile strength (Ts), elongation at break (EB) and light transmittance (T). Antibacterial mechanisms indicate that TP and LZM have a synergistic antibacterial effect. The slow-release system composed of liposomes and coating prolongs the action time of TP and LZM. Hence, the TP-Lips/LZM-CS coating could be a hopeful material in food preservation field with excellent antibacterial properties.     

Simultaneous determination of bisphenol A,octylphenol, and nonylphenol by pressurised liquid extraction and liquid chromatography–tandem mass spectrometry in powdered milk and infant formulas

A new analytical method, using pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry (LC–MS/MS), was developed for the simultaneous determination of bisphenol A (BPA), octylphenol (OP) and nonylphenol (NP) in powdered infant formulas (IF) and powdered skimmed milk (PM). The analytes were extracted by PLE, using this optimised conditions: ethyl acetate as solvent, 70 °C of temperature, reversed-phase silica C₁₈ as dispersing agent and three cycles of extraction. The extracts were then injected in LC–MS/MS using a Gemini C₁₈ column and a mixture of 5% water and 95% methanol/acetonitrile, both with 0.1% ammonia, as a mobile phase. Recoveries at different fortification levels (0.5 and 0.05 mg kg⁻¹), were between 89% and 92% for BPA, 84 and 98% for OP, and 93% and 101% for NP. The method was applied to the analysis of samples of PM and IF, bought in Italian and Spanish markets. In positive samples, phenols concentration ranged from 0.07 to 1.29 mg kg⁻¹ for BPA, from 0.028 to 1.55 mg kg⁻¹ for OP and from 0.026 to 1.47 mg kg⁻¹ for NP.     

Development of an HPLC–UV method for the simultaneous determination of tetracyclines in muscle and liver of porcine,chicken and bovine with accelerated solvent extraction

A simple and especially rapid method-using accelerated solvent extraction (ASE) and HPLC has been developed for the quantitative determination of oxytetracycline, tetracycline, chlortetracycline, minocycline, methacycline, demeclocycline and doxycycline in muscle and liver of porcine, chicken and bovine. Samples of muscle and liver were extracted with trichloracetic acid/acetonitrile using ASE instrument, parameters such as extraction temperature (40–80 °C) and pressure (45–85 bar) were investigated and the selected extraction (60 °C, 65 bar) was most effective. The limits of detection were lower than 10 μg/kg and limits of quantification no more than 15 μg/kg for all compounds in muscle and liver. The recoveries of tetracyclines spiked at levels of muscle 50–150 μg/kg, liver 150–450 μg/kg, averaged from 75.0% to 104.9% with the relative standard deviation values less than 10%. The method was applied to determine 30 real porcine livers. It is demonstrated that the new method is robust for detection and quantification of seven tetracycline residues in muscle and liver of porcine, chicken and bovine.     

Effects of selenate supplemented fertilisation on the selenium level of cereals — identification and quantification of selenium compounds by HPLC–ICP–MS

Laboratory experiments were carried out to investigate whether the selenium content of different kinds of cereals grown on Austrian soil could be raised by the application of compound fertilisers containing selenium as selenate. An anion exchange chromatographic system coupled to an HP 4500 inductively coupled plasma mass spectrometer (ICP–MS) was used for the identification and quantification of selenium compounds in cereal samples. The HPLC–ICP–MS system was optimized for the separation of selenite, selenate, selenocystine, and selenomethionine using a Hamilton PRP-X100 column. Separation was obtained, with a 10 mM citrate buffer (pH 5), 2% methanol as mobile phase and a flow rate of 1.5 ml min⁻¹. Four baseline separated chromatographic peaks were obtained within 6 min. The retention behavior of a further five selenium [selenohomocystine (Sehcys), selenocystathionine (Secysta), selenoethionine (Seet), trimethylselenonium iodide (TmSe), and dimethyl(3-amino-3-carboxy-1-propyl)selenonium iodide (DmpSe)] compounds was investigated. Aqueous extraction and enzymatic hydrolysis of the biological materials were also compared with respect to the amount of selenium extracted. In the aqueous extracts only 3–9% of the total concentration of selenium was found. When the cereal samples were exposed to an enzymatic hydrolysis, recovery rates ranging from 80 to 95% were obtained. A major part of the selenate, which had been taken up by the cereals was converted to selenomethionine.