Assessment of baby disposable diapers application for urine collection and determination of phthalate metabolites.

The baby disposable diapers were investigated as a sampling material for urine collection and validated for the evaluation of the exposure of children to xenobiotics. Phthalate metabolites detected in urine samples were chosen as proof-of-concept analytes. For the determination of phthalate metabolites in children's urine samples, high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) was used. Two sampling approaches were compared, namely sterile containers and baby disposable diapers. Thirty urine samples from infants and toddlers were analyzed by both methods in parallel and the results were compared. It was found that for diaper sampling, lower concentrations of the metabolites were observed, however, the general distribution for particular metabolites remains the same for both methods. For most of the metabolites high determination coefficients were obtained, namely 0.9929 for MEHHP, 0.9836 for MMP, 0.9796 for MECPP, and 0.9784 for 2-cx-MMHP. For MEOHP the determination correlation coefficient was 0.9154, while for MBP was - 0.7771 and MEHP was - 0.5228. In general, for diaper sampling an underestimation for 2-cx-MMHP and MEOHP was observed, while for MMP diaper-based approach provides overestimation. However, the proposed procedure confirms the possibility of using baby disposable diapers as a material for the collection of urine samples for biomonitoring purposes and fast screening of phthalates exposure.

Bisphenol A analogues and metabolic syndrome in women with polycystic ovary syndrome.

Bisphenols (BPs) have become a chemical group of special interest due to their ability to interfere with the endocrine system and their ubiquitous presence in the environment. As some of them possess mild estrogenic and anti-androgenic effects, they might be associated with the diagnosis of polycystic ovary syndrome (PCOS). Acting on multiple tissues, BPs exposure may lead to metabolic derangements characteristic for metabolic syndrome (MetS). Therefore, the aim of this study was to determine the potential relationship between exposure to some BPA analogues and features of the MetS in women with PCOS. Serum BPE, BPC, BPG, BPM, BPP, BPZ, BPFL, and BPBP concentrations did not differ significantly between the PCOS (n = 135) and the control subjects (n = 104). However, women whose serum BPM and BPP concentrations were in the highest tertile were more likely to be diagnosed with PCOS (adjusted OR; [95%CI] 0.43; [0.20; 0.89], P < 0.001 and 0.56; [0.27; 0.96], P = 0.049, consequently). Serum concentrations of BPs were not associated with the MetS diagnosis in the PCOS group. There was a negative correlation between the concentrations of serum BPBP and total serum cholesterol (r = - 0.153; P = 0.019), BPE and serum testosterone (r = - 0.160; P = 0.014) as well as BPC and HDL-cholesterol (r = - 0.138; P = 0.036). There was a positive correlation between the concentrations of BPP and serum triglycerides (r = 0.138; P = 0.036). Our results point to the potential association between exposure to BPM, BPP, and the diagnosis of PCOS, along with the impact of BPBP, BPE, BPC, and BPP on the metabolic features of the MetS.

Antibacterial Porous Systems Based on Polylactide Loaded with Amikacin.

Three porous matrices based on poly(lactic acid) are proposed herein for the controlled release of amikacin. The materials were fabricated by the method of spraying a surface liquid. Description is given as to the possibility of employing a modifier, such as a silica nanocarrier, for prolonging the release of amikacin, in addition to using chitosan to improve the properties of the materials, e.g., stability and sorption capacity. Depending on their actual composition, the materials exhibited varied efficacy for drug loading, as follows: 25.4 ± 2.2 µg/mg (matrices with 0.05% w/v of chitosan), 93 ± 13 µg/mg (with 0.08% w/v SiO2 amikacin modified nanoparticles), and 96 ± 34 µg/mg (matrices without functional additives). An in vitro study confirmed extended release of the drug (amikacin, over 60 days), carried out in accordance with the mathematical Kosmyer-Pepas model for all the materials tested. The matrices were also evaluated for their effectiveness in inhibiting the growth of bacteria such as Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, and Pseudomonas aeruginosa. Concurrent research was conducted on the transdermal absorption, morphology, elemental composition, and thermogravimetric properties of the released drug.

Understanding the early-stage release of volatile organic compounds from rapeseed oil during deep-frying of tubers by targeted and omics-inspired approaches using PTR-MS and gas chromatography.

During deep-frying, a plethora of volatile products is emitted with the fumes. These compounds could act as oil quality indicators and change the indoor air composition leading to health risks for occupants. The presented experiments focus on deep-frying of different tubers in rapeseed oil at different frying temperatures. Here, two scenarios for real-time monitoring of volatile organic compounds (VOCs) using proton transfer reaction mass spectrometry (PTR-MS) were proposed. The first, targeted, involved the application of gas chromatography with a flame ionization detector (GC-FID). The second, omics-inspired, involved the use of solid-phase microextraction (SPME) along with gas chromatography-mass spectrometry (GC-MS) and molecular networking algorithm as a complementary tool to the PTR-MS analysis. In a targeted approach, it was shown that the emission profile of pentanal and hexanal depends on the frying temperature and as the temperature increases, a sudden release of these compounds can be observed in the first minutes of frying. Meanwhile, using an omics-inspired protocol enables finding the relation between 1,4-heptadienal and 2-heptanone, octanal and limonene emissions. Using both approaches it was possible to record real-time changes in emission profiles of various oils' degradation products. It was also observed that the emission profiles of VOCs are strictly related to the frying temperature and the type of fried tuber.

Relative quantification of pork and beef in meat products using global and species-specific peptide markers for the authentication of meat composition.

We used global and species-specific peptide markers for a relative quantitative determination of pork and beef in raw and processed meat products made of the two meat species. Four groups of products were prepared (i.e., minced raw meats, sausages, raw and fried burgers) in order to represent products with different extents of food processing. In each group, the products varied in the pork/beef proportions. All products were analysed by multiple reaction monitoring mass spectrometry (MRM-MS) for the presence/concentration of pork- and beef-specific peptide markers, as well as global markers - peptides widely distributed in muscle tissue. The combined MRM-MS analysis of pork-specific peptide HPGDFGADAQGAMSK, beef-specific peptide VLGFHG and global marker LFDLR offered the most reliable validation of declared pork/beef compositions across the whole range of meat products. Our work suggests that a simultaneous analysis of global and species-specific peptide markers can be used for composition authentication in commercial pork/beef products.

Occurrence and Levels of Biogenic Amines in Beers Produced by Different Methods.

The concentration of biogenic amines (BAs) in beer depends, among other factors, on the activity of microorganisms, in particular lactic acid bacteria. In this work an analytical method based on derivatization with tosyl chloride and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was used to determine 17 BAs in samples of commercially available beers, and to monitor the changes in concentration of several BAs throughout the fermentation process. In some of the analysed samples the concentration of BAs exceeded the safety threshold for consumers. During the fermentation stage of home-brewing of ale the concentration of spermine in the wort increased until the end of the stormy fermentation, to then drop below the initial concentration at the end of fermentation, and below the LOQ after refermentation. The results of the study indicate that monitoring the total content of BAs is required due to the potential risk to human health.

Encapsulation of Amikacin into Microparticles Based on Low-Molecular-Weight Poly(lactic acid) and Poly(lactic acid-co-polyethylene glycol).

The aim of this study was to fabricate novel microparticles (MPs) for efficient and long-term delivery of amikacin (AMI). The emulsification method proposed for encapsulating AMI employed low-molecular-weight poly(lactic acid) (PLA) and poly(lactic acid-co-polyethylene glycol) (PLA-PEG), both supplemented with poly(vinyl alcohol) (PVA). The diameters of the particles obtained were determined as less than 30 µm. Based on an in-vitro release study, it was proven that the MPs (both PLA/PVA- and PLA-PEG/PVA-based) demonstrated long-term AMI release (2 months), the kinetics of which adhered to the Korsmeyer-Peppas model. The loading efficiencies of AMI in the study were determined at the followings levels: 36.5 ± 1.5 µg/mg for the PLA-based MPs and 106 ± 32 µg/mg for the PLA-PEG-based MPs. These values were relatively high and draw parallels with studies published on the encapsulation of aminoglycosides. The MPs provided antimicrobial action against the Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Klebsiella pneumoniae bacterial strains. The materials were also comprehensively characterized by the following methods: differential scanning calorimetry; gel permeation chromatography; scanning electron microscopy; Fourier transform infrared spectroscopy-attenuated total reflectance; energy-dispersive X-ray fluorescence; and Brunauer-Emmett-Teller surface area analysis. The findings of this study contribute toward discerning new means for conducting targeted therapy with polar, broad spectrum antibiotics.

Revealing dynamic changes of the volatile profile of food samples using PTR-MS.

Volatile compounds carry valuable information regarding the properties of foodstuffs. Volatiles emitted from food can be used as, for example, indicators of quality, shelf-life, or authenticity. A better understanding of the multitude of transformations which occur during food processing could facilitate the optimisation of production, increase the desirability of food products, and also their wholesomeness. However, as some of these transformations are fast-paced, it is necessary to monitor them using techniques which enable real-time determination of volatiles, such as proton transfer reaction-mass spectrometry (PTR-MS). Recent years have seen a marked increase in its use in food analysis, since it can be used to obtain insight into the dynamics of the monitored processes and can be the basis for precise quality control methods for food processing. This review highlights recent works in which PTR-MS was used in monitoring during foodstuffs production, preparation and storage.

The bile salt content of human bile impacts on simulated intestinal proteolysis of ß-lactoglobulin.

The gastrointestinal hydrolysis of food proteins has been portrayed in scientific literature to predominantly depend on the activity and specificity of proteolytic enzymes. Human bile has not been considered to facilitate proteolysis in the small intestine, but rather to assist in intestinal lipolysis. However, human bile can potentially influence proteins that are largely resistant to gastric digestion, and which are mainly hydrolysed after they have been transferred to the small intestine. We used purified and food-grade bovine milk ß-lactoglobulin (ßLg) to assess the impact of bile salts (BS) on the in vitro gastrointestinal digestion of this protein. Quantitative analysis showed that the proteolysis rate increased significantly with increasing BS concentration. The effect was consistent regardless of whether individual BS or real human bile samples, varying in BS concentrations, were used. The total BS content of bile was more important than its BS composition in facilitating the proteolysis of ßlg. We also show that the impact of human bile observed during the digestion of purified ßLg and ßLg-rich whey protein isolate can be closely replicated by the use of individual BS mixed with phosphatidylcholine. This could validate simple BS/phosphatidylcholine mixtures as human-relevant substitutes of difficult-to-obtain human bile for in vitro proteolysis studies.

Release Kinetics Studies of Early-Stage Volatile Secondary Oxidation Products of Rapeseed Oil Emitted during the Deep-Frying Process.

The research concerns the use of proton transfer reaction mass spectrometer to track real-time emissions of volatile secondary oxidation products released from rapeseed oil as a result of deep-frying of potato cubes. Therefore, it was possible to observe a sudden increase of volatile organic compound (VOC) emissions caused by immersion of the food, accompanied by a sudden release of steam from a potato cube and a decrease of the oil temperature by more than 20 °C. It was possible to identify and monitor the emission of major secondary oxidation products such as saturated and unsaturated aldehydes, namely acrolein, pentanal, 2-hexenal, hexanal, 2-nonenal and 2-decenal. Each of them has an individual release characteristic. Moreover, the impact of different initial frying temperatures on release kinetics was investigated. Subsequently, it was possible to approximate the cumulative emission by a second-degree polynomial (R2 ≥ 0.994). Using the proposed solution made it possible for the first time to observe the impact of the immersion of food in vegetable oil on the early emission of thermal degradation products oil.

Proteolysis of whey protein isolates in nanoemulsion systems: Impact of nanoemulsification and additional synthetic emulsifiers.

Nanoemulsions are currently of interest in the functional food sector because their small droplet size (100-500 nm) provides a number of potential advantages over conventional emulsions. This study concerned the behavior of nanoemulsions stabilized with whey proteins and two synthetic emulsifiers (Tween 80 and Croduret), and exposed to conditions simulating the human upper gastrointestinal tract. In particular, the effect of synthetic emulsifiers (food additives) on the interfacial composition and digestion rate of milk proteins at the interface of nanoemulsions was determined. The results indicate that the protein was partially co-absorbed with only one synthetic emulsifier (Croduret) at the interface, which made protein more resistant to digestion in the nanoemulsion system. This suggests that the degree of protein digestion can be controlled by appropriate selection of synthetic emulsifiers and presenting the protein in nanoemulsion system.

Serum bisphenol A analogues in women diagnosed with the polycystic ovary syndrome - is there an association?

Due to the endocrine disrupting effects of bisphenol A (BPA) several governmental authorities have banned its use and the manufacturers had to find alternative substances with similar chemical properties. This led to the increase in the use of so-called BPA analogues, which however also turn out to possess mild estrogenic and ani-androgenic properties and thus, may cause fertility problems and sex-hormone dependent endocrinopathies. The aim of this study was to evaluate the potential association between the exposure to BPA and its two analogues: BPS and BPF, with the diagnosis of the polycystic ovary syndrome (PCOS), which remains the most common female endocrinopathy. Serum concentrations of BPA, BPS and BPF were measured using high performance liquid chromatography method with tandem mass spectrometry (HPLC-MS/MS) among 199 women with PCOS and 158 control subjects. In women with PCOS serum BPS concentrations were significantly higher compared to the control subjects (geometric mean [95% CI]: 0.14 ng/mL [0.10; 1.17] vs. 0.08 ng/mL [0.06; 0.09], P = 0.023). Serum BPA and BPF concentrations did not differ between the studied groups. There was however a negative correlation between serum BPA and HOMA-IR (r = - 0.233, P = 0.001) and TST (r = - 0.203, P = 0.006) in women with PCOS. No correlations were found between the serum BPs and other metabolic parameters such as serum lipids, insulin, DHEA-S, androstenedione and FAI. When studying the association between serum BPA analogues and PCOS it turned out that women whose serum BPS concentrations were in the first tertile were more likely to be diagnosed with this endocrinopathy (OR [95% CI]: 1.21 [1.04; 3.46], P = 0.017). This association was also statistically significant when adjusted for age, education, BMI, smoking, income, and alcohol consumption (adjusted OR [95% CI]: 1.12 [1.03; 3.71], P = 0.029). These results point to the potential association between the exposure to BPS and the diagnosis of PCOS. The role of BPA is not clear and warrants further studies.

A nontargeted approach to determine the authenticity of Ginkgo biloba L. plant materials and dried leaf extracts by liquid chromatography-high-resolution mass spectrometry (LC-HRMS) and chemometrics.

The lack of stringent regulations regarding raw materials for herbal supplements used for medicinal purposes has been a constant challenge in the industry. Ginkgo biloba L. leaf extracts attract consumers because of the supposed positive effect on mental performance and memory. Supplements are produced using dried leaf materials and standardized leaf extracts such as EGb 761. Adulteration of Ginkgo biloba L. plants and extracts are becoming more and more common practice due to economically driven motivation from increasing demand in the market and the high cost of raw materials and production. Reinforcement in quality control (QC) to avoid adulterations is necessary to ensure the efficacy of the supplements. In this study, liquid chromatography-high-resolution mass spectrometry (LC-HRMS) was used with principal component analysis (PCA) as an unsupervised exploratory method to analyze, identify, and evaluate the adulterated Ginkgo biloba L. plant materials and dried leaf extracts using the PCA scores and loadings obtained and compound identification.

Real-Time Volatilomics: A Novel Approach for Analyzing Biological Samples.

The use of the 'omics techniques in environmental research has become common-place. The most widely implemented of these include metabolomics, proteomics, genomics, and transcriptomics. In recent years, a similar approach has also been taken with the analysis of volatiles from biological samples, giving rise to the so-called 'volatilomics' in plant analysis. Developments in direct infusion mass spectrometry (DI-MS) techniques have made it possible to monitor the changes in the composition of volatile flux from parts of plants, single specimens, and entire ecosystems in real-time. The application of these techniques enables a unique insight into the dynamic metabolic processes that occur in plants. Here, we provide an overview of the use of DI-MS in real-time volatilomics research involving plants.

Exposure to Bisphenol A Analogs and the Thyroid Function and Volume in Women of Reproductive Age-Cross-Sectional Study.

Bisphenols (BPs) are commonly known plastifiers that are widely used in industry. The knowledge about the impact of BPs on thyroid function is scarce. Proper thyroid functioning is especially important for women of reproductive age, as hypothyroidism affects fertility, pregnancy outcomes and the offspring. There are no studies analyzing the influence of BPs on thyroid function and volume in non-pregnant young women. The aim of this cross-sectional study was to evaluate the relationship between bisphenol A and its 10 analogs (BPS, BPC, BPE, BPF, BPG, BPM, BPP, BPZ, BPFL, and BPBP) on thyroid function and volume in women of reproductive age. Inclusion criteria were: female sex, age 18-40 years. Exclusion criteria were history of any thyroid disease, pharmacotherapy influencing thyroid function, pregnancy or puerperium, and diagnosis of autoimmune thyroid disease during this study. Venous blood was drawn for measurement of thyrotropin (TSH), free thyroxine, thyroid peroxidase antibodies, thyroglobulin antibodies, BPs. Urine samples were analyzed for: ioduria and BPs. Ultrasound examination of thyroid gland was performed. One hundred eighty participants were included into the study. A negative correlation was found between urine BPC and the thyroid volume (R = -0.258; p = 0.0005). Patients with detected urine BPC presented smaller thyroid glands than those with not-detected urine BPC (p = 0.0008). A positive correlation was found between TSH and urine BPC (R = 0.228; p = 0.002). Patients with detected urine BPC presented higher concentrations of TSH versus those with not-detected urine BPC (p = 0.003). There were no relationships between any of serum BPs as well as the other urine BPs and thyroid function and its volume. The only BP that demonstrated the relationship between thyroid function and its volume was BPC, probably because of its chemical structure that most resembles thyroxine. Exposure to this BP may result in the development of hypothyroidism that could have a negative impact on pregnancy and the offspring.

Stabilities of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and their derivatives under controlled conditions analyzed using liquid chromatography coupled with tandem mass spectrometry.

Bisphenol A diglycidyl ether (BADGE), bisphenol F diglycydyl ether (BFDGE), and their related compounds are widely used as precursors in production of epoxy resins. The high reactivity of these compounds makes the development of analytical methodologies that ensure appropriate metrological accuracy crucial. Consequently, we aimed to determine whether and to what extent the composition of the solution and storage conditions affect the stability of selected BADGE and BFDGE derivatives. The stabilities of these compounds were studied using liquid chromatography-tandem mass spectrometry with electrospray ionization (HPLC-ESI-MS/MS). The chromatographic method elaborated here has allowed for separation of the analytes in time shorter than 6 min, for both methanol and acetonitrile-based mobile phases. The obtained calibration curves for all analytes were linear in the range tested. The values of limit of detection (LODs) were in the range of 0.91-2.7 ng/mL, while values of limit of quantitation (LOQs) were in the range of 2.7-5.7 ng/mL. The chosen experimental conditions were compared in terms of the content of organic solvent in solution, storage temperature, and time. Our results show that the content of BADGE, BADGE·HCl, BFDGE, three-ring NOGE decreased with increasing water content (> 40% v/v). For BADGE and three-ring NOGE, significant changes in concentration were noted as early as 24 h after the test solutions had been prepared. In addition, a reduction in the storage temperature (4 to - 20 °C) reduced the rate of transformation of the monitored analytes. Our study will increase quality control in future research and may increase the reliability of the obtained results. Graphical abstract.

MRM-MS of marker peptides and their abundance as a tool for authentication of meat species and meat cuts in single-cut meat products.

The abundance of protein markers in different types of meat cuts was explored in the context of authentication of raw meat (pork, beef and chicken) and processed meat products. Peptides originating from myoglobin (Mb) and myosin (My) were analyzed using multiple reaction monitoring mass spectrometry (MRM-MS). Analytical protocol was optimized for good repeatability (CV < 10%) and high sensitivity. The MS signal intensity of Mb marker peptides in raw pork depended significantly on the cut type (e.g. ham vs knuckle). Importantly, a similar pattern in the abundance of the marker peptides was found for processed meat products made of different types of pork cuts, despite the food processing applied. This suggests the protocol can be used for authentication of raw pork cuts and processed products made of different cuts of pork. More uniform contents of Mb markers were found in raw beef cuts, and for My markers in raw chicken cuts.

New approach for e-cigarette aerosol collection by an original automatic aerosol generator utilizing melt-blown non-woven fabric.

Currently, there is lack of standardized conditions for the collection and analysis of e-cigarette (EC) aerosol. Considering the urgent need for the development of these guidelines, a procedure for EC aerosol analysis was developed. A novel automatic e-cigarette aerosol generator was designed. For the first time, melt-blown non-woven fabric was applied for the effective uptake of compounds released from vaporized e-liquid. The extraction procedure was optimized in terms of type of extraction solvent, amount of sorbent and solvent volume. For optimization, a model e-liquid containing flavour additives belonging to various chemicals group with various chemical properties was investigated. The aerosol trapping efficiency was satisfactory and was equal to 92 ±â€¯7%. Final determination was performed by GC-MS/MS. Quantitation was based on the mass change tracking approach (MCT), which assumes the monitoring of e-liquid mass changes before and after vaping. The combination of non-woven fabric and sampling approach (MCT) was proven to be effective in acquisition of reliable data. Thus, the concentrations in aerosol and emission factors were calculated for aerosols collected during the vaping of both model e-liquids and real samples. Validation was performed by evaluating key analytical parameters, such as linearity, accuracy, precision, limit of detection (LOD) and quantitation (LOQ). For all investigated compounds, recoveries from 70% to 118% together with precision and reproducibility below 12% were achieved. The applicability of the described approach was examined by analysing EC refill solutions commercially available on the Polish market.

Serum bisphenol A concentrations correlate with serum testosterone levels in women with polycystic ovary syndrome.

The aim of this study was to determine serum bisphenol A (BPA) concentrations using high performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) in women with polycystic ovary syndrome (PCOS) (n = 106, age range 18-40 yrs) and to evaluate its potential impact on their hormonal and metabolic profile. The control group consisted of age- and BMI-matched 80 eumenorrheic women with no clinical or biochemical hyperandrogenism. Our results showed that women with PCOS had significantly higher serum BPA concentrations than healthy controls (geometric mean and [95% CI]: 0.202 ng/mL [0.150; 0.255] vs. 0.154 ng/mL [0.106; 0.201], P = 0.035), which correlated positively with serum total testosterone (TST) (R=0.285, P = 0.004) and the free androgen index (FAI) (R = 0.196, P = 0.049). There were no significant correlations between serum BPA and BMI, waist circumference, serum glucose, insulin and lipids. These results point to the potential role of BPA in the pathogenesis of the ovarian hyperandrogenism in women with PCOS.