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Glyphosate and glufosinate are among the most widely used pesticides in agriculture worldwide. Their extensive use leads to the presence of their residues on crops and in the surrounding environment. Beehives, bees, and apiculture products can represent potential sources for the accumulation of these substances and their metabolites, and the consequences for bee health, as well as the level of risk to human health from consuming contaminated food, are still unclear. Furthermore, information on the contamination levels of honey and other beehive products by these compounds remains poorly documented. This study is part of a broader research effort aimed at developing specific analytical methods for monitoring the level of these contaminants in bee products. The methodology employed enabled the acquisition of preliminary information concerning the levels of glyphosate and glufosinate contamination in honey samples obtained from various retailers in Italy to assess compliance with the limits established by Regulation 293/2013. The liquid chromatography tandem mass spectrometry analysis of the 30 honey samples revealed quantifiable levels of glyphosate in eight samples, with contamination ranging from 5.4 to 138.5 ng/g. Notably, one sample of the wildflower type showed residue levels nearly three times the maximum residue limit. Additionally, trace levels of glyphosate contamination were detected in another ten samples. It is noteworthy that glufosinate and its metabolites were not detected in any of the analyzed samples within the established method's detection ranges. [ABSTRACT FROM AUTHOR]

Hive products have numerous beneficial properties; however, the hive's health is affected by the surrounding environment. The widespread use of herbicides in agriculture, such as glyphosate and glufosinate, has raised alarm among consumers, beekeepers, and environmentalists due to their potential to harm bees and humans through the consumption of bee products. This review aims to provide a comprehensive overview of the presence of glyphosate, glufosinate, and their metabolites in hive products, collecting and comparing available data from peer-reviewed research and surveys conducted across several countries. Moreover, it analyzes and discusses the potential impacts of these substances on human and bee health, analytical aspects, and recent regulatory developments. The data has revealed that these substances can be present in the different matrices tested, but the concentrations found are usually lower than the maximum residue limits set. However, the use of different methodologies with non-uniform analytical performances, together with an incomplete search for regulated analytes, leads to heterogeneity and makes comparisons challenging. In addition to the completion of studies on the toxicology of herbicide active ingredients, further monitoring actions are necessary, harmonizing analytical methodologies and data management procedures. [ABSTRACT FROM AUTHOR]

The analysis of natural cobalamins in dairy products still represents an analytical challenge. The matrix's complexity, low concentration level, light sensitivity, and binding to proteins are just some of the aspects that make their quantification a difficult goal to achieve. Vitamin B12 plays a fundamental role in human nutrition, and its intake is closely linked to a diet that includes the consumption of food of animal origin. In the current literature, few studies have been carried out on the quantitation of cobalamin in ripened cheeses. A sensitive, selective, and robust ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) method was developed, validated, and applied on ripened cheeses from different species (cow, sheep, and goat) purchased from local Italian markets, highlighting species-dependent differences in vitamin B12 concentrations. The vitamin B12 extraction procedure was performed by converting all cobalamins to the cyanocobalamin form. Furthermore, solid-phase extraction was used for matrix clean-up and analyte preconcentration. The proposed method showed good performance in terms of linearity, sensitivity, reproducibility, and repeatability. The mean vitamin B12 content ranged from

Perfluoroalkylated substances (PFASs) are a wide cluster of fluorinated molecules largely engaged industrially and commercially for many purposes. Because of the strength of the fluorine-carbon bond, PFASs show a firm tenacity against thermal degradation, hydrolysis, photolysis and biodegradation. On the other hand, such chemical stability gives them persistent environmental pollutant feature. In 2012, EFSA published a scientific report on PFASs in food, mentioning their adverse effects on health. Based on observational studies evidences, EFSA has recommended a tolerable daily intake (TDI) for the two most known PFASs, i.e. PFOS 150 ng/kg b.w./day and PFOA 1500 ng/kg b.w./day. The aim of this study was to monitor, for the first time, the level of contamination of PFASs in chicken eggs laid in Northern Italy. The eggs were collected from different rearing systems, in order to search a correlation between this variable and the contamination of PFASs. In this study four PFASs [perfluoro-nnonanoic acid (PFNA), perfluoro-noctanoic-acid (PFOA), sodium perfluoro-1-hexanesulfonate (PFHxS) and sodium perfluoro-1-octanesulfonate (PFOS)] were analyzed by liquid chromatography-tandem mass spectrometer (LC-MS/MS). 132 eggs were analyzed, split up in 11 groups according to the geographical origin and rearing system. Results accord with literature data available for chicken eggs: almost all the samples show a PFASs contamination level under the limit of quantification (LOQ) of 0.25 ng/mL. No significant difference results from the rearing system, attesting an equal distribution and a concentration of PFASs detectable under the limit of quantification. [ABSTRACT FROM AUTHOR]

Nasal administration has been proposed as a potential approach for the delivery of drugs to the central nervous system. Ribavirin (RBV), an antiviral drug potentially useful to treat viral infections both in humans and animals, has been previously demonstrated to attain several brain compartments after nasal administration. Here, a powder formulation in the form of agglomerates comprising micronized RBV and spray-dried microparticles containing excipients with potential absorption enhancing properties, i.e. mannitol, chitosan, and α-cyclodextrin, was developed for nasal insufflation. The agglomerates were characterized for particle size, agglomeration yield, and ex vivo RBV permeation across rabbit nasal mucosa as well as delivery from an animal dry powder insufflator device. Interestingly, permeation enhancers such as chitosan and mannitol showed a lower amount of RBV permeating across the excised nasal tissue, whereas α-cyclodextrin proved to outperform the other formulations and to match the highly soluble micronized RBV powder taken as a reference. In vivo nasal administration to rats of the agglomerates containing α-cyclodextrin showed an overall higher accumulation of RBV in all the brain compartments analyzed as compared with the micronized RBV administered as such without excipient microparticles. Hence, powder agglomerates are a valuable approach to obtain a nasal formulation potentially attaining nose-to-brain delivery of drugs with minimal processing of the APIs and improvement of the technological and biopharmaceutical properties of micronized API and excipients, as they combine optimal flow properties for handling and dosing, suitable particle size for nasal deposition, high surface area for drug dissolution, and penetration enhancing properties from excipients such as cyclodextrins. [ABSTRACT FROM AUTHOR]

Vitamin B12 (cobalamin) is a metal complex composed of a central cobalt ion bonded to six ligands. It is essential for major biological functions such as protein, fat and carbohydrate metabolism, the maintenance of the central nervous system, and the formation of red blood cells. Since mammals cannot synthesize cobalamin, dietary intake represents the only natural source for humans. Dairy products can provide significant levels of cobalamin; moreover, the European Food Safety Authority (EFSA) panel has set the recommended intake at 4 µg/day for adults. Vitamin B12 content was determined in milk and several matrices related to the process of transformation of the residual whey from Parmigiano Reggiano cheese-making to obtain ricotta cheese. In addition, vitamin B12 degradation during ricotta cheese shelf-life was studied. The analyses were performed using an ultra performance liquid chromatography-tandem mass spectrometry method. Results show that vitamin B12 amount in ricotta from dairy and experimental cheese-making brings respectively 1/8 to 1/4 of the adequate intake in adults established by EFSA. In addition, shelf-life experiment shows that cobalamine is fairly rapidly degraded in ricotta: light effect seems to be significant, even if the light exposure is short. The use of photoprotective packaging material increases B12 shelf-life in the early stage of storage. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are pollutants of anthropic origin with possible side effects on human health. Diet, and in particular fish and seafood, is considered the major intake pathway for humans. The present study investigated the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in twenty-five samples of fresh fillet of five widely consumed fish species purchased from large retailers in Italy, to be used for an estimation of the Italian population exposure to these contaminants. PFOS and PFOA were found in all samples, at concentrations up to 1896 (mean=627 ng/kg) and 487 ng/kg (mean=75 ng/kg), respectively, confirming the role of fish as high contributor to human exposure. However, a remarkable inter-species variability was observed, and multiple factors were suggested as potentially responsible for such differences, suggesting that the preferential consumption of certain species could likely increase the intake, and thus the exposure. The exposure estimates for both average and high fish consumers resulted far below the tolerable daily intakes for PFOS and PFOA in all age groups, confirming the outcomes of EFSA's scientific report. In particular, the calculated total dietary exposure for the 95th percentile consumers belonging to the toddler age class, the most exposed group, resulted equal to 9.72 ng/kg body weight (BW)/day for PFOS and 8.39 ng/kg BW/day for PFOA. [ABSTRACT FROM AUTHOR]

Bisphenol A (BPA) is a man-made compound, mainly used as a monomer to produce polycarbonate (PC), epoxy resins, non-polymer additives to other plastics, which have many food related applications, such as food storage containers, tableware and internal coating of cans, as well as non-food applications such as electronic equipment, construction materials and medical devices. BPA exposure can occur when the residual monomer migrates into packaged food and beverages. Moreover, due to the ubiquitous presence of this compound, the general population can be exposed to environmental sources such as water, air and soil. Many studies have investigated the potential health hazards associated with BPA, which can elicit toxic and cancerogenic effects on humans. According to the European Food Safety Authority opinion, diet is considered to be the main source of exposure, especially canned food; moreover, among non-canned food, meat and fish products have the highest levels of BPA contamination. This review focuses on BPA contamination in seafood, analysing worldwide literature (from January 2010 to October 2015) on BPA contamination of edible parts. The authors try to identify differences between canned and non-canned seafood in literature, and gaps in the state of art. The data evaluated underline that all concentrations for both canned and non-canned seafood were below the specific migration limit set by the European Community Directive for BPA in food. Moreover, the canned seafood is more contaminated than the non-canned one. [ABSTRACT FROM AUTHOR]

Abstract: A liquid chromatography–tandem mass spectrometry method for the quantitative determination of fumonisin FB1, FB2 and their respective hydrolysed metabolites HFB1 and HFB2 in pig liver has been developed and validated. The method was based on an easy extraction procedure followed by SPE purification. Chromatographic separation of the analytes was performed on a C18 column using 0.3% of formic acid in water and acetonitrile as elution solvent. The mass spectrometer operated in the positive electrospray ionisation mode (ESI+) using multiple reaction monitoring (MRM). An intralaboratory validation was carried out with fortified samples for determining precision, trueness, specificity, limit of detection (LOD) and limit of quantification (LOQ). The method showed good performance characteristics and proved to be sensitive, selective and reliable. The LOD was 0.05ngg−1 and the LOQ was 10ngg−1 for all the analytes. The developed method has been applied to seven pig liver samples in order to test its applicability to evaluate exposure of food animals to fumonisins. [ABSTRACT FROM AUTHOR]

Vascular and traumatic injuries of the central nervous system are recognized as global health priorities. A polypharmacology approach that is able to simultaneously target several injury factors by the combination of agents having synergistic effects appears to be promising. Herein, we designed a polymeric delivery system loaded with two drugs, ibuprofen (Ibu) and thyroid hormone triiodothyronine (T3) to in vitro release the suitable amount of the anti-inflammation and the remyelination drug. As a production method, electrospinning technology was used. First, Ibu-loaded micro (diameter circa 0.95–1.20 µm) and nano (diameter circa 0.70 µm) fibers were produced using poly(l-lactide) PLLA and PLGA with different lactide/glycolide ratios (50:50, 75:25, and 85:15) to select the most suitable polymer and fiber diameter. Based on the in vitro release results and in-house knowledge, PLLA nanofibers (mean diameter = 580 ± 120 nm) loaded with both Ibu and T3 were then successfully produced by a co-axial electrospinning technique. The in vitro release studies demonstrated that the final Ibu/T3 PLLA system extended the release of both drugs for 14 days, providing the target sustained release. Finally, studies in cell cultures (RAW macrophages and neural stem cell-derived oligodendrocyte precursor cells—OPCs) demonstrated the anti-inflammatory and promyelinating efficacy of the dual drug-loaded delivery platform. [ABSTRACT FROM AUTHOR]

Vitamin B12 is a water-soluble molecule composed of a tetrapyrrolic complex with a cobalt atom at its centre. It is an essential regulatory element, synthesized only by bacteria; for this reason it is present only in food of animal origin and the daily requirement for humans is about 1 to 2 μg. Since milk and dairy products provide a significant dietary cobalamin intake, an ultra performance liquid chromatographytandem mass spectrometry method was applied to samples collected at different stages along the process of cheese making in order to evaluate the distribution of this molecule. In particular, samples of milk, rennet, whey, ricotta cheese, curd, mozzarella cheese and caciotta cheese were analysed. Results showed a level of vitamin B12 about 10 times higher in whey and ricotta cheese with respect to the milk they are derived from. These data would confirm the tendency of cobalamine to concentrate in the proteic fractions along the cheese production process. [ABSTRACT FROM AUTHOR]

Pink discoloration defect can cause economic losses for cheese producers due to the impossibility to sell the defected cheese, but few knowledge is currently available on the causes of this defect. To gain more insight on the causes that lead to the formation of pink discoloration in Pecorino Toscano cheese with the Protected Designation of Origin (PDO) status, the bacterial community in defected and not defected cheese was characterized by high-throughput sequencing of bacterial 16S rRNA gene. The bacterial community in the defected cheese significantly differed compared to the control. The relative abundance of the genera Acidipropionibacterium , Enterococcus , Escherichia/Shigella , Lactobacillus , Lentilactobacillus and Propionibacterium was higher in the cheese with pink discoloration defect. The concentration of short chain fatty acids and of lactic acid in cheese was measured and a shift towards the production of propionate in the cheese with pink discoloration defect was observed. Furthermore, the possible involvement of microbially produced vitamin B 12 in the formation of pink discoloration was not supported by the data, since a tendency to a lower concentration of vitamin B 12 was measured in the defected cheese compared to the control. • The bacterial community in sheep cheese with pink discoloration was characterized. • The bacterial communities in the defected cheese and the control were different. • The relative abundance of propionic bacteria was higher in the defected cheese. • The role of vitamin B 12 in the formation of pink discoloration was hypothesized. [ABSTRACT FROM AUTHOR]

• Extensive investigation of PFASs in Italian eggs from backyard chickens (EBC). • More contamination in EBC than in eggs from commercial laying hens. • EBC contribute to PFAS intake of up to 29% of tolerable weekly intake in children. Per- and poly-fluoroalkyl substances (PFASs) are persistent and bioaccumulative compounds with adverse impacts on the environment and human health. Diet is one of the main sources of exposure to PFASs. Recently, the EFSA established a tolerable weekly intake (TWI) limit (4.4 ng/kg b.w.) for a mixture of the four major PFASs. Eggs and egg products can contribute to this intake, with their contamination possibly dependent on the husbandry system. Monitoring Italian eggs from backyard chickens revealed a relatively uniform PFAS contamination, with perfluoro-1-octanesulfonate being the most abundant. Contamination was detected to be significantly higher in eggs from backyard chickens than in eggs from commercial laying hens, consistent with a previous Italian study. According to the recently set TWI value, the consumption of eggs from backyard chickens could contribute significantly to dietary intake of PFASs (up to 29% of the TWI in children, considering the lower bound approach). [ABSTRACT FROM AUTHOR]

Plant extracts traditionally used for male impotence (Tribulus terrestris, Ferula hermonis, Epimedium brevicornum, Cinnamomum cassia), and the individual compounds cinnamaldehyde, ferutinin, and icariin, were screened against phosphodiesterase-5A1 (PDE5A1) activity. Human recombinant PDE5A1 was used as the enzyme source. Only E. brevicornum extract (80% inhibition at 50 microg/mL) and its active principle icariin (1) (IC50 5.9 microM) were active. To improve its inhibitory activity, 1 was subjected to various structural modifications. Thus, 3,7-bis(2-hydroxyethyl)icaritin (5), where both sugars in 1 were replaced with hydroxyethyl residues, potently inhibited PDE5A1 with an IC50 very close to that of sildenafil (IC50 75 vs 74 nM). Thus, 5 was 80 times more potent than 1, and its selectivity versus phosphodiesterase-6 (PDE6) and cyclic adenosine monophosphate-phosphodiesterase (cAMP-PDE) was much higher in comparison with sildenafil. The improved pharmacodynamic profile and lack of cytotoxicity on human fibroblasts make compound 5 a promising candidate for further development.

Organophosphorus pesticides (OPPs), widely used in agriculture, can cause toxic effects to humans and animals. The main purpose of the present work was to determine the contamination in raw milk by the main organophosphorus pesticides used in Italy and to evaluate the opportunity to start specific procedures of risk management along the milk production chain. The samples, collected in 4 Italian dairy plants directly from the tank trucks during the delivering, were representative of 920 tonnes of raw milk. The isolation of the OPPs (acephate, chlorpyriphos, chlorpyriphos-methyl, diazinon, methamidophos, methidathion, phorate, pirimiphos-methyl) was performed by liquid partition followed by clean-up with solid phase extraction. The analyses were carried out by dual column gas chromatography using two nitrogen-phosphorus detectors. Among the 135 samples analysed, 37 were positive in traces and 10 showed an OPP contamination ranging from 5 to 18 microg/kg. The higher results were recorded in the samples collected during the autumn-winter period. The main pollutants detected were acephate and chlorpyriphos. In every positive sample found, the OPP contamination was lower than the maximum residue level (MRL) fixed by the European Commission.

High-performance liquid chromatography with fluorescence detection was used for the analysis of polycyclic aromatic hydrocarbons (PAHs), in "Diavoletto" smoked cheese. Such cheese is typically produced in the Sorrento peninsula, and it is smoked commonly with different materials of vegetable origin. The importance of the smoking generation material is proven by the attention that the EU is paying in indicating the list of wood that may be used to produce smoking flavor agents. The PAHs considered are classified as "probable human carcinogens" by the U.S. Environmental Protection Agency for sufficient data from animal bioassays. The smoked samples contained high molecular mass PAHs with different levels ranging from 0.12 to 6.21 microg/kg. The determination was carried out also on liquid smoking flavor agents, smoke-flavored cheese, and nonsmoked cheese to measure the level of contamination before the treatment.