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ABSTRACT: Infant milk formulas are designed to substitute human milk when breastfeeding is unavailable. In addition to human milk and milk-derived products, these formulas can be a vehicle of contaminants. In this work, a multiclass method based on the QuEChERS (quick, easy, cheap, effective, rugged, and safe) approach was developed for the simultaneous determination of contaminants (n = 45), including mycotoxins and veterinary drug residues, occurring in infant milk formulas. By using an ultra-high-performance liquid chromatography quadrupole-Orbitrap coupled with high-resolution mass spectrometry analysis (UHPLC-Q-Orbitrap HRMS; Thermo Fisher Scientific), further retrospective analysis of 337 contaminants, including pesticides, was achieved. The method was validated in accordance with European regulations and applied for the analysis of 54 infant milk samples. Risk assessment was also performed. Dexamethasone was detected in 16.6% of samples (range: 0.905–1.131 ng/mL), and procaine benzyl penicillin in 1 sample at a concentration of 0.295 ng/mL. Zearalenone was found in 55.5% of samples (range: 0.133–0.638 ng/mL) and α-zearalenol in 16.6% of samples (range: 1.534–10.408 ng/mL). Up to 49 pesticides, 11 veterinary drug residues, and 5 mycotoxins were tentatively identified via retrospective analysis based on the mass spectral library. These findings highlight the necessity of careful evaluation of contaminants in infant formulas, considering that they are intended for a vulnerable part of the population.

Breakfast cereals have been reported as one of the most susceptible cereal-based products to mycotoxin contamination. These products pose an even more concerning risk to human health since they are marketed as a ready-to-eat product and one of its main population targets is children. Therefore, the main goal of the present study was to conduct a monitoring study of multiple mycotoxins contained in breakfast cereals samples marketed in Italy through ultra-high performance liquid chromatography coupled to high-resolution Q-Orbitrap tandem mass spectrometry. An acetonitrile-based methodology was validated for quantifying 24 mycotoxins in breakfast cereals. The results showed that 93% of the samples contained at least one mycotoxin. Beauvericin was the most prevalent toxin (86% of samples; mean concentration: 30.66 µg/kg), although the main enniatins, zearalenone-derived forms and fumonisins B1 and B2 were also detected. Co-occurrence was observed in 73% of the positive samples with up to five mycotoxins simultaneously occurring, mainly due to the combination of beauvericin and enniatins. These results provided more evidence about the high impact of non-regulated mycotoxins, such as the emerging Fusarium toxins, in breakfast cereals, and encourages the development of analytical methodologies including these and zearalenone-derived forms that could be going unnoticed with current methodologies.

Coffee contains human health-related molecules, namely polyphenols that possess a wide range of pharmacological functions, and their intake is associated with reduced colon cancer risk. This study aimed to assess the changes in the anti-inflammatory and antioxidant activity of coffee after simulated gastrointestinal digestion. The evaluation of intracellular reactive oxygen species (ROS) levels in the HT-29 human colon cancer cell line and three in vitro spectrophotometric assays were performed to determine the antioxidant activity of the samples. Characterization of coffee composition was also assessed through a Q-Orbitrap high-resolution mass spectrometry analysis. The results highlighted that the levels of polyphenols in the digested coffee brews were higher than those of the non-digested ones. All assayed samples decreased the levels of intracellular ROS when compared to untreated cells, while digested coffee samples exhibited higher antioxidant capacity and total phenolic content than not-digested coffee samples. Digested coffee samples showed a higher reduction in interleukin-6 levels than the not-digested samples in lipopolysaccharide-stimulated HT-29 cells treated for 48 h and fewer cytotoxic effects in the MTT assay. Overall, our findings suggest that coffee may exert antioxidant and anti-inflammatory properties, and the digestion process may be able to release compounds with higher bioactivity.

Agro-industrial wastes contain a large number of important active compounds which can justify their use as innovative ingredients in nutraceutical products. This study aimed to provide a complete analysis of active molecules, namely (poly)phenols in pea pods water-based extracts, through a UHPLC-Q-Orbitrap HRMS methodology. Data showed that 5-caffeoylquinic acid, epicatechin, and hesperidin were the most relevant (poly)phenols found in the assayed extracts, with a mean value of 59.87, 29.46, and 19.94 mg/100 g, respectively. Furthermore, changes in antioxidant capacity and bioaccessibility of total phenolic compounds (TPC) after the simulated gastrointestinal (GI) process were performed using spectrophotometric assays (FRAP, DPPH, ABTS, and TPC by Folin-Ciocalteu). The acid-resistant capsules (ARC) and the non-acid resistant capsules (NARC) containing the pea pod extract underwent simulated GI digestion. The results suggested that the ARC formulations were able to preserve the active compounds along the simulated GI process, highlighting a higher TPC value and antioxidant capacity than the NARC formulations and the not-encapsulated extracts. Hence, the pea pods water-based extracts could be utilized as a potential alternative source of active compounds, and the use of ARC could represent a suitable nutraceutical formulation to vehiculate the active compounds, protecting the chemical and bioactive properties of (poly)phenols.

The metabolic profile of T-2 toxin (T-2) and its modified form T-2-3-glucoside (T-2-3-Glc) remain unexplored in human samples. Therefore, the present study aimed to investigate the presence of T-2, T-2-3-Glc and their respective major metabolites in human urine samples (n = 300) collected in South Italy through an ultra-high performance liquid chromatography (UHPLC) coupled to Q-Orbitrap-HRMS methodology. T-2 was quantified in 21% of samples at a mean concentration of 1.34 ng/mg Crea (range: 0.22–6.54 ng/mg Crea). Almost all the major T-2 metabolites previously characterized in vitro were tentatively found, remarking the occurrence of 3′-OH-T-2 (99.7%), T-2 triol (56%) and HT-2 (30%). Regarding T-2-3-Glc, a low prevalence of the parent mycotoxin (1%) and its metabolites were observed, with HT-2-3-Glc (17%) being the most prevalent compound, although hydroxylated products were also detected. Attending to the large number of testing positive for T-2 or its metabolites, this study found a frequent exposure in Italian population.

Spent coffee ground (SCG) is a significant by-product generated by the coffee industry. It is considered a great source of bioactive molecules well-recognized for exerting biological properties. This study aimed to implement SCG in a baked foods, such as cookies (SCGc), to increase their bioactive potential. A comprehensive study of the polyphenolic fraction of the SCG and SCGc using a high-resolution mass spectrometry analysis was performed. Moreover, the polyphenol bioaccessibility and change in antioxidant activity during simulated gastrointestinal digestion (GiD) were assessed. Data showed that SCGc provided 780 mg of melanoidins, 16.2 mg of chlorogenic acid (CGA), 6.5 mg of caffeine, and 0.08 mg of phenolic acids per 100 g of sample. Moreover, the 5-caffeoylquinic acid was the most relevant CGA found in SCG (116.4 mg/100 g) and SCGc (8.2 mg/100 g) samples. The antioxidant activity evaluated through three spectrophotometric tests, and the total phenolic compounds of SCGc samples exhibited significantly higher values than the control samples. Furthermore, during simulated GiD, the highest bioaccessibility of SCGc polyphenols was observed after the colonic stage, suggesting their potential advantages for human health. Therefore, SCG with high content in bioactive molecules could represent an innovative ingredient intended to fortify baked food formulations.

Fennel (Foeniculum vulgare Mill.) waste contains a broad range of bioactive molecules, including polyphenols, which have poor bioaccessibility during gastrointestinal digestion. This work aimed to investigate the bioaccessibility of total phenolic compounds and the antioxidant capacity during simulated gastrointestinal digestion using two nutraceutical formulations based on non-acid-resistant (NAR) and acid-resistant (AR) capsules containing aqueous-based extracts from fennel waste. Moreover, to obtain a comprehensive investigation of the polyphenolic constituents of the fennel waste extract, a high-resolution mass spectrometry (Q-Orbitrap) analysis was performed. Notably, chlorogenic acids, such as 4-caffeoylquinic acid and 3,4-dicaffeoylquinic acid, were the most detected compounds found in assayed samples (1.949 and 0.490 mg/g, respectively). After in vitro gastrointestinal digestion, the extract contained in AR capsules displayed higher bioaccessibility in both the duodenal and colonic stages (1.96 and 5.19 mg GAE/g, respectively) than NAR capsules (1.72 and 3.50 mg GAE/g, respectively), suggesting that the acidic gastric conditions negatively affected the polyphenol compounds released from the NAR capsules. Therefore, the aqueous extract of fennel waste could be proposed as an innovative and easily available source of dietary polyphenols. Furthermore, the use of an AR capsule could improve the polyphenol bioaccessibility and can be proposed as a nutraceutical formulation.

Coffee represents one of the most traditionally consumed beverages worldwide, containing a broad range of human health–related compounds. According to previous studies, regular coffee consumption may display protective effects against colorectal cancer and other chronic diseases. The main goal of this research was to evaluate the bioaccessibility of phenolic content and variation in antioxidant capacity of three different types of coffee brews after simulated gastrointestinal digestion. This would allow to elucidate how antioxidant compounds present in coffee may exert their effect on the human body, especially in the colonic stage. Moreover, the content of bioactive compounds namely chlorogenic acids (CGAs, n = 11) and caffeine was also assessed throughout ultra-high-performance liquid chromatography followed by high-resolution Orbitrap mass spectrometry (UHPLC-Q-Orbitrap HRMS). The three main isomers of caffeoylquinic acid constituted the highest fraction of CGAs present in the samples, accounting for 66.0% to 70.9% of total CGAs. The bioaccessibility of coffee polyphenols significantly increased in digested samples from 45.9% to 62.9% at the end of the colonic passage, compared to the non-digested samples. These results point to the colonic stage as the major biological site of action of the active antioxidant coffee compounds.

Red cabbage is a native vegetable of the Mediterranean region that represents one of the major sources of anthocyanins. The aim of this research is to evaluate the antioxidant capability and total polyphenol content (TPC) of a red cabbage extract and to compare acquired data with those from the same extract encapsulated in an acid-resistant capsule. The extract, which was qualitatively and quantitatively profiled by UHPLC-Q-Orbitrap HRMS analysis, contained a high content of anthocyanins and phenolic acids, whereas non-anthocyanin flavonoids were the less abundant compounds. An in vitro gastrointestinal digestion system was utilized to follow the extract’s metabolism in humans and to evaluate its colon bioaccessibility. Data obtained showed that during gastrointestinal digestion, the total polyphenol content of the extract digested in the acid-resistant capsule in the Pronase E stage resulted in a higher concentration value compared to the extract digested without the capsule. Reasonably, these results could be attributed to the metabolization process by human colonic microflora and to the genesis of metabolites with greater bioactivity and more beneficial effects. The use of red cabbage extract encapsulated in an acid-resistant capsule could improve the polyphenols’ bioaccessibility and be proposed as a red cabbage-based nutraceutical formulation for counteracting stress oxidative diseases.

Although hemp seed (HS) oil is characterized by more than 80% polyunsaturated fatty acids (PUFAs), a very high ω-6-to-ω-3 ratio is not a popular commodity. The aim of this work was to provide useful data about the bioactive components and cannabidiolic acid content in thirteen different commercial hemp seed oils. The investigated HS oils showed a good ω-6/ω-3 ratio, ranging from 1.71 to 2.27, massively differed in their chlorophylls (0.041–2.64 µg/g) and carotenoids contents (0.29–1.73 µg/g), as well as in total phenols (22.1–160.8 mg Gallic Acid Equivalents (GAE)/g) and tocopherols (3.47–13.25 mg/100 g). Since the high content of PUFAs in HS oils, photo-oxidative stability was investigated by determining the Thiobarbituric Acid Reactive Substances (TBARS) assay and extinction coefficient K232 and K270 after the photo-oxidative test. The percentage of increase in K232 and K270 ranged from 1.2 to 8.5% and from 3.7 to 26.0%, respectively, indicating good oxidative stability, but TBARS showed a 1.5- to 2.5-fold increase in oxidative behavior when compared to the initial values. Therefore, the diversity in bioactive compounds in HS oils, and their high nutritional value, suggest the need for a disciplinary booklet that well defines agronomic and post-harvest management conditions for achieving a good food objective.

Tree nuts have become popular snacks due to their attributed benefits in the health state. Nevertheless, their susceptibility to fungal contamination lead to the occurrence of potentially dangerous mycotoxins. Hence, the aim of this work was to evaluate the presence of mycotoxins in ready-to-eat almonds, walnuts, and pistachios from Italian markets. The most relevant mycotoxin found in almonds was α-zearalanol in 18% of samples (n = 17) ranging from 3.70 to 4.54 µg/kg. Walnut samples showed frequent contamination with alternariol, present in 53% of samples (n = 22) at levels from 0.29 to 1.65 µg/kg. Pistachios (n = 15) were the most contaminated commodity, with β-zearalenol as the most prevalent toxin present in 59% of samples ranging from 0.96 to 8.60 µg/kg. In the worst-case scenario, the exposure to zearalenone-derived forms accounted for 15.6% of the tolerable daily intake, whereas it meant 12.4% and 21.2% of the threshold of toxicological concern for alternariol and alternariol monomethyl-ether, respectively. The results highlighted the extensive presence of Alternaria toxins and zearalenone-derived forms, scarcely studied in ready-to-eat tree nut products, highlighting the necessity to include these mycotoxins in analytical methods to perform more realistic risk assessments.

Fruit juices are common products in modern diets due to the supply of vegetal nutrients combined with its tastiness. Nevertheless, potential contaminants, such as mycotoxins and pesticides, can be present in commercial products due to a potential carry-over. Therefore, the aim of this study was to investigate for the first time the presence of 14 Fusarium mycotoxins using a quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based extraction followed by an ultra-high-performance liquid chromatography-quadrupole Orbitrap high-resolution mass spectrometry in 21 pear juice samples from Italian markets. Up to nine different mycotoxins were detected, particularly an extensive presence of zearalenone (67%, n = 21, mean value = 0.88 ng/mL). Emerging Fusarium mycotoxins enniatins B, B1, A, and A1 were also detected. Additionally, 77 pesticide residues were tentatively identified through a retrospective analysis based on a mass spectral library. The prevalent presence of some non-approved pesticides, such as ethoxyquin (64%, n = 21) and triazophos (55%, n = 21), must be highlighted. The results obtained indicate an extensive contamination of marketed pear juice with undesirable compounds, and they should be taken into consideration when performing risk assessment studies.

Enniatins (Enns) are mycotoxins produced by Fusarium spp. which are a fungus widely spread throughout cereals and cereal-based products. Among all the identified enniatins, Enn B1 stands as one of the most prevalent analogues in cereals in Europe. Hence, the aim of this study was to evaluate for the first time the presence of Enn B1 and its phase I metabolites in 300 human urine samples using an ultrahigh-performance liquid chromatography high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) methodology. Enn B1 was detected in 94.3% of samples ranging from 0.007 to 0.429 ng/mL (mean value: 0.065 ng/mL). In accordance with previous in vitro and in vivo analysis, hydroxylated metabolites (78.0% samples) and carbonylated metabolites (66.0% samples) were tentatively identified as the major products. Results from this biomonitoring study point to a frequent intake of Enn B1 in the studied population, suggesting that in-depth toxicological studies are needed in order to understand the potential effects in humans.

Coffee silverskin (CS), the main by-product in the coffee industry, contains a vast number of human health-related compounds, which may justify its exploitation as a functional food ingredient. This study aimed to provide a comprehensive analysis of the polyphenolic and alkaloid profile through UHPLC-Q-Orbitrap HRMS analysis. The bioaccessibility of total phenolic compounds and changes in the antioxidant activity during an in vitro gastrointestinal digestion were also evaluated through spectrophotometric tests (TPC by Folin-Ciocalteu, ABTS, DPPH, and FRAP), to elucidate their efficacy for future applications in the nutraceutical industry. Caffeoylquinic and feruloylquinic acids were the most representative polyphenols, with a mean concentration of 5.93 and 4.25 mg/g, respectively. Results showed a high content of caffeine in the analyzed CS extracts, with a mean value of 31.2 mg/g, meaning a two-fold increase when compared to coffee brews. Our findings highlighted that both the bioaccessibility and antioxidant activity of CS polyphenols significantly increased in each in vitro gastrointestinal digestion stage. In addition, the colon stage might constitute the main biological site of action of these antioxidant compounds. These results suggest that in vivo, the dietary polyphenols from CS might be metabolized by human colonic microflora, generating metabolites with a greater antioxidant activity, increasing their well-known beneficial effects.

Cannabidiol (CBD) food supplements made of Cannabis sativa L. extracts have quickly become popular products due to their health-promoting effects. However, potential contaminants, such as mycotoxins and pesticides, can be coextracted during the manufacturing process and placed into the final product. Accordingly, a novel methodology using ultra-high-performance liquid chromatography coupled with quadrupole Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS) was developed to quantify 16 mycotoxins produced by major C. sativa fungi, followed by a post-target screening of 283 pesticides based on a comprehensive spectral library. The validated procedure was applied to ten CBD-based products. Up to six different Fusarium mycotoxins were found in seven samples, the most prevalent being zearalenone (60%) and enniatin B1 (30%), both found at a maximum level of 11.6 ng/g. Co-occurrence was observed in four samples, including one with enniatin B1, enniatin A and enniatin A1. On the other hand, 46 different pesticides were detected after retrospective analysis. Ethoxyquin (50%), piperonyl butoxide (40%), simazine (30%) and cyanazine (30%) were the major residues found. These results highlight the necessity of monitoring contaminants in food supplements in order to ensure a safe consumption, even more considering the increase trend in their use. Furthermore, the developed procedure is proposed as a powerful analytical tool to evaluate the potential mycotoxin profile of these particular products.

Industrial hemp (Cannabis sativa L. Family Cannabaceae) contains a vast number of bioactive relevant compounds, namely polyphenols including flavonoids, phenolic acids, phenol amides, and lignanamides, well known for their therapeutic properties. Nowadays, many polyphenols-containing products made of herbal extracts are marketed, claiming to exert health-promoting effects. In this context, industrial hemp inflorescence may represent an innovative source of bioactive compounds to be used in nutraceutical formulations. The aim of this work was to provide a comprehensive analysis of the polyphenolic fraction contained in polar extracts of four different commercial cultivars (Kompoti, Tiborszallasi, Antal, and Carmagnola Cs) of hemp inflorescences through spectrophotometric (TPC, DPPH tests) and spectrometry measurement (UHPLC-Q-Orbitrap HRMS). Results highlighted a high content of cannflavin A and B in inflorescence analyzed samples, which appear to be cannabis-specific, with a mean value of 61.8 and 84.5 mg/kg, meaning a ten-to-hundred times increase compared to other parts of the plant. Among flavonols, quercetin-3-glucoside reached up to 285.9 mg/kg in the Carmagnola CS cultivar. Catechin and epicatechin were the most representative flavanols, with a mean concentration of 53.3 and 66.2 mg/kg, respectively, for all cultivars. Total polyphenolic content in inflorescence samples was quantified in the range of 10.51 to 52.58 mg GAE/g and free radical-scavenging included in the range from 27.5 to 77.6 mmol trolox/kg. Therefore, C. sativa inflorescence could be considered as a potential novel source of polyphenols intended for nutraceutical formulations.

Wine is a popular alcoholic beverage that has been consumed for hundreds of years. Benefits from moderate alcohol consumption have been widely supported by the scientific literature and, in this line, red wine intake has been related to a lesser risk for coronary heart disease (CHD). Experimental studies and meta-analyses have mainly attributed this outcome to the presence in red wine of a great variety of polyphenolic compounds such as resveratrol, catechin, epicatechin, quercetin, and anthocyanin. Resveratrol is considered the most effective wine compound with respect to the prevention of CHD because of its antioxidant properties. The mechanisms responsible for its putative cardioprotective effects would include changes in lipid profiles, reduction of insulin resistance, and decrease in oxidative stress of low-density lipoprotein cholesterol (LDL-C). The aim of this review is to summarize the accumulated evidence correlating moderate red wine consumption with prevention of CHD by focusing on the different mechanisms underlying this relationship. Furthermore, the chemistry of wine as well as chemical factors that influence the composition of the bioactive components of red wine are also discussed.

El propósito de este artículo es exponer, describir y analizar una aerofoto histórica en resguardo del Centro Documental de Estudios sobre el Agua (CDEA), con fecha entre 1931 y 1934, que muestra la planicie tabasqueña y los cambios y permanencias en el paisaje. A partir de la identificación de los cuerpos de agua, edificios y usos del espacio, se realizó un análisis comparativo desde la historia ambiental el cual posibilitó comprender cómo tales modificaciones generaron que las inundaciones esperadas todos los años se convirtieran, durante el siglo XX, en desastres. Con esto, se pretende incentivar entre los historiadores el análisis del paisaje, necesario en la planicie costera del Golfo de México, sin perder de vista las experiencias culturales de reconocimiento territorial que han generado una “cultura del agua”.