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Sea fennel (Crithmum maritimum L.) contains several bioactive compounds like vitamin C, polyphenols, essential oils, and fatty acids. The present study was aimed at exploring the lactic acid fermentation of sea fennel sprouts by the selection and inoculation of multiple strain starters to produce laboratory-scale prototypes and, subsequently, a pilot-scale prototype. A rapid pH reduction was seen in the laboratory-scale prototypes, mainly due to lactic acid production. Linoleic and α-linolenic acids were the most abundant detected fatty acids, while among volatile compounds monoterpene hydrocarbons prevailed. Fruity, pungent and yogurt notes emerged from the sensory analysis. The analysis of the pilot-scale prototype confirmed the physico-chemical data collected from the laboratory scale prototypes, except for a slower acidification. In addition, a decrease in antioxidant activity and content of vitamin C, fiber and total polyphenols was seen during fermentation, whereas sensory analysis revealed a kerosene-like note, a salty flavor, and a crunchy consistency. No coagulase positive staphylococci and botulinum toxin-producing clostridia were detected. The results overall collected highlighted the great potential of sea fennel and selected lactic acid bacteria starters to produce high value, safe and microbiologically stable preserves.

A sensitive UHPLC-ESI-MS/MS method, coupled with a suitable extraction protocol, was developed and validated for the rapid detection of four tropane alkaloids (anisodamine, atropine, homatropine, scopolamine) in herbal teas and herbal extracts. The method offers good sensitivity, accuracy and precision. The protocol is suitable for routine determination of tropane alkaloids in dried plants and extracts sold as food supplements or phytotherapics, and was applied to 60 commercial samples. Anisodamine, atropine and/or scopolamine were found in 4 herbal teas samples (LOQ–69 μg/kg for atropine and 50 μg/kg for scopolamine) and in a Lepidium meyenii extract sold as food supplement (traces of anisodamine). The level of contamination do not to pose a direct risk for the consumers if compared to the acute reference dose indicated by EFSA, but the detection confirms the need for suitable methods and careful screenings in order to determine a more precise evaluation of dietary intake for tropane alkaloids.

Background The growing area has a substantial effect on plants, affecting secondary metabolism. For hops, different authors have studied the effect of growing area on the chemical composition of cones with the aim of verifying and understanding the changes in hop characters. Despite the scant literature the subject receives increasing attention by brewers and hop growers. The present study aimed to characterize, using gas chromatography-mass spectrometry (GC-MS), and high-performance liquid chromatography with ultraviolet detection (HPLC-UV), cones of hop (Humulus lupulus L.) cultivar Cascade. Plant material was obtained from nine different areas of Italy and compared with Cascade samples grown in the United States, Germany and Slovenia. Results Differences in bitter acids and xanthohumol content were observed. Nevertheless, no correlation between bitter acids and xanthohumol production, on the one hand, and rainfall, temperatures and latitude, on the other hand, were observed in our samples. The Slovenia samples were richer in molecules that confer hoppy, woody and flower notes; USA2 samples were more characterized by woody, earthy, grassy and floral aroma, quite different characters if compared to USA1, which had the lowest presence of grassy aromatic compounds. In the Italian samples, TRENTINO was the genotype most characterized by limonene presence. Conclusion The results of this study are indicative of the importance for hop users to know and characterize hops coming from different growing regions. The study pays special attention to the characterization of the differences in chemical characters of Cascade hop in Italy, where hop cultivation has developed only recently, but is in continuous expansion. © 2019 Society of Chemical Industry.

Okara is the main soybean by-product resulting from the processing of soy milk and tofu. Despite being a product with a lot of potential and rich in many bioactive compounds such as polyphenols, it presents an unpleasant, rancid aroma. For this reason its use in the food industry is limited. In this study, we have reported the integral use of okara in a solid state fermentation process, conducted with wild strains of lactic acid bacteria, to evaluate the effect of bacterial metabolism on the volatile and polyphenolic profiles. Strains belonging to Lactobacillus acidophilus, Lacticaseibacillus rhamnosus and Pediococcus acidilactici species were used in monoculture and, for the first time, in co-culture. The results showed an improvement in the aromatic fraction showing a decrease in hexanal, responsible for off-flavour, and an increase in ketones with fruity and buttery notes in fermented okara. Polyphenols were also affected, and, in particular, a bioconversion of glucoside isoflavones to the aglycone forms was highlighted in all fermented substrates. In addition, the appearance of both phenyllactic and p-hydroxyphenyllactic acids as well as the increase in indole-3-lactic acid was observed for the first time upon okara fermentation. Overall, the co-culture appears to be the most promising for biovalorization of okara, thereby opening the possibility of its use in the development of functional ingredients.

Arthrospira platensis is a cyanobacterium widely used in food formulation and mainly consumed as a food supplement because of its high amount of proteins, vitamins and minerals. Different probiotic food supplements are present in the market, and a lactic acid fermented food product like dried spirulina could be useful not only to introduce lactic acid bacteria (LAB) with beneficial effects to the diet of consumers, but also to improve or change the aromatic profile of the substrate. Therefore, the aim of this study was the evaluation of lactic acid fermentation of A. platensis biomass, focusing on the consequent changes in the aromatic profile. For this purpose, two different stabilization treatments (UV light treatment and sterilization) were applied prior to fermentation with two LAB strains, Lacticaseibacillus casei 2240 and Lacticaseibacillus rhamnosus GG. The biomass proved to be a suitable matrix for solid-state fermentation, showing a LAB growth of more than 2 log CFU/g in 48 h. The fermentation process was also useful for off-flavor reduction. In particular, the fermentation process significantly influenced the concentration of those compounds responsible for aldehydic/ethereal, buttery/waxy (acetoin and diacetyl), alkane and fermented aromatic notes (isoamyl alcohol). The heat treatment of the matrix, in addition to guaranteed safety for consumers, led to an improved aroma after fermentation. In conclusion, a fermented spirulina powder with a different aromatic profile was obtained with the applied heat treatment. Fermentation with lactic acid bacteria can be an interesting tool to obtain cyanobacterial biomasses with more pleasant sensory properties for potential use in food formulations.

Harmful algal bloom and marine toxins are actual and overgrowing problems. Okadaic acid (OA) is the main toxin responsible for diarrheic shellfish poisoning in humans, while Tetrodotoxin (TTX) is a tremendously strong neurotoxin. Given their high toxicity, strategies to obtain a mitigation of these toxins are every day more fundamental, in the optic of preserve consumer health, and in giving supports to shellfisheries in selling their products. In this context, the ability of lactic acid bacteria (LAB) and Paracoccus spp. to reduce OA and TTX in vitro was evaluated using HPLC/MS-MS technique. Different mechanisms of interaction were observed. Some species of LAB were able to reduce significantly the amount of toxin while in viable state (Lacticaseibacillus rhamnosus 1473 = 30% OA reduction), but also a binding effect of the toxins was observed. Contrarily, Paracoccus spp. was able to reduce significantly the amount of toxin while in a cell-free extract form, in particular Paracoccus aerius 5038 could reduce the presence of TTX of about 24%. This study provided a sound line of evidence for the possible future use of either specific bacteria or selected bacterial components to reduce the level of harmful marine toxins in aquaculture and food production.

The mycotoxin zearalenone may contaminate food and feed worldwide upon infections by Fusarium spp. of plants and raw materials intended for human and animal consumption. Currently, contamination by zearalenone and congeners pose concern for health due to xenoestrogenic effects. However, while zearalenone and the main reduced metabolites are well-known xenoestrogens, some plant metabolites that may enter the food chain have been observed aside. Among them, zearalenone-14-glucoside may be abundant in the edible parts of infected plants, thereby entering significantly the human diet and animal feeding. On the basis of previous works, the lack of xenoestrogenicity for this compound per se was taken for granted, while neglecting the direct proof of estrogenic activity and considering the hydrolysis as a possible source of estrogenically active metabolites. The present work investigated the xenoestrogenicity of zearalenone-14-glucoside, in comparison to zearalenone, deepening the underlying molecular mechanisms through an integrated in vitro/in silico approach. On the basis of our results, zearalenone-14-glucoside effectively stimulated a xenoestrogenic response in cells, but such stimulus can be entirely attributable to the hydrolysis phenomenon, as the glycosylated form turned out to be unable to effectively bind and activate the estrogens receptors.

Food processing, especially thermal treatment, may have implications on mycotoxins in products available for consumers. This research work aimed to study how mycotoxin levels may be influenced by modifying the technological parameters of both whole grain and cocoa biscuit-making processes. The study was mainly focused on the following mycotoxins: deoxynivalenol, deoxynivalenol-3-glucoside, and the minor metabolite culmorin. Special emphasis was given to the recipe formulation, and to the baking conditions, using an industrial-scale operation, starting from naturally contaminated raw materials. Exploiting the power of Design of Experiments (DoE) and a dedicated LC-MS/MS method, the complexity of the different processes was investigated. The models obtained within this study showed a high goodness-of-fit suggesting that the pH and the baking time play important roles for minimizing mycotoxins in the final products, while the recipe formulation has an impact on the mycotoxins extractability by affecting the biscuit microstructure.

Acrylamide is formed during baking in some frequently consumed food products. It is proven to be carcinogenic in rodents and a probable human carcinogen. Thus, the food industry is working to find solutions to minimize its formation during processing. To better understand the sources of its formation, the present study is aimed at investigating how acrylamide concentration may be influenced by bakery-making parameters within a parallel strategy of mycotoxin mitigation (focusing specifically on deoxynivalenol&mdash, DON) related to wholegrain and cocoa biscuit production. Among Fusarium toxins, DON is considered the most important contaminant in wheat and related bakery products, such as biscuits, due to its widespread occurrence. Exploiting the power of a Design of Experiments (DoE), several conditions were varied as mycotoxin contamination levels of the raw materials, recipe formulation, pH value of dough, and baking time/temperature, each selected treatment was varied within a defined range according to the technological requirements to obtain an appreciable product for consumers. Experiments were performed in a pilot-plant scale in order to simulate an industrial production and samples were extracted and analysed by HPLC-MS/MS system. Applying a baking temperature of 200 &deg, C at the highest sugar dose, acrylamide increased its concentration, and in particular, levels ranged from 306 &plusmn, 16 &micro, g/Kg d.m. and 400 &plusmn, 27 &micro, g/Kg d.m. in biscuits made without and with the addition of cocoa, respectively. Conversely, using a baking temperature of 180 &deg, C in the same conditions (pH, baking time, and sugar concentrations), acrylamide values remained below 125 &plusmn, 14 &micro, g/Kg d.m. and 156 &plusmn, 15 &micro, g/Kg d.m. in the two final products. The developed predictive model suggested how some parameters can concretely contribute to limit acrylamide formation in the final product, highlighting a significant role of pH value (correlated also to sodium bicarbonate raising agent), followed by baking time/temperature parameters. In particular, the increasing range of baking conditions influenced in a limited way the final acrylamide content within the parallel effective range of DON reduction. The study represents a concrete example of how the control and optimization of selected operative parameters may lead to multiple mitigation of specific natural/process contaminants in the final food products, though still remaining in the sensorial satisfactory range.

Background: Lactic acid bacteria (LAB) exhibit a great biodiversity that can be exploited for different purposes, such as to enhance flavours or metabolize phenolic compounds. In the present study, the use of dairy and plant-derived LAB strains to perform cherry juice fermentation is reported. Methods: The growth ability of Lactobacillus plantarum, Lactobacillus casei, Lactobacillus paracasei and Lactobacillus rhamnosus was studied in cherry juice. Profiling of sugars, organic acids and volatile compounds was performed by GC-MS (Gas Chromatography-Mass Spectrometry), while the phenolic fraction was characterized using UHPLC (Ultra High Performance Liquid Chromatography) equipped with a linear ion trap-mass spectrometer. Results: Sucrose significantly decreased in all fermented samples as well as malic acid, converted to lactic acid by malolactic fermentation. The total amount of volatile compounds increased. Specifically, propyl acetate, an ester with fruit notes, reached the highest concentration in L. rhamnosus and L. paracasei (dairy strains) fermented juices. Phenolics were extensively metabolized: caffeic acid was converted into dihydrocaffeic acid, p-coumaric acid into 4-ethylphenol and phenyllactic acid was produced. Conclusion: Lactic acid fermentation confer fruit notes to the juice and enhance phenyllactic acids, especially employing dairy strains (L. rhamnosus and L. paracasei). The level of dihydrocaffeic acid, a compound with putative biological activity was also increased (in particular with L. plantarum).

Insects are considered a suitable alternative feed for livestock production and their use is nowadays regulated in the European Union by the European Commission Regulation No. 893/2017. Insects have the ability to grow on a different spectrum of substrates, which could be naturally contaminated by mycotoxins. In the present work, the mycotoxin uptake and/or excretion in two different insect species, Alphitobius diaperinus (Lesser Mealworm, LM) and Hermetia illucens (Black Soldier Fly, BSF), grown on naturally contaminated substrates, was evaluated. Among all the substrates of growth tested, the Fusarium toxins deoxynivalenol (DON), fumonisin 1 and 2 (FB1 and FB2) and zearalenone (ZEN) were found in those based on wheat and/or corn. No mycotoxins were detected in BSF larvae, while quantifiable amount of DON and FB1 were found in LM larvae, although in lower concentration than those detected in the growing substrates and in the residual fractions. Mass balance calculations indicated that BSF and LM metabolized mycotoxins in forms not yet known, accumulating them in their body or excreting in the faeces. Further studies are required in this direction due to the future employment of insects as feedstuff.

This study aimed to investigate the possible correlation between 5-n-alkylresorcinols and hydroxycinnamic acids on mycotoxin accumulation in grains under field conditions. At this purpose, ten different grain varieties characterized by different degree of ploidy (hexaploid, tetraploid, diploid) were chosen, among them common and durum wheat, einkorn, emmer, and spelt. The contamination, expressed as the sum of DON and DON3Glc, was found to be significantly lower in common wheat and spelt than in emmer, durum wheat and einkorn, following a trend hexaploid

This study investigated for the first time the intestinal transfer of two modified forms of zearalenone (ZEN), zearalenone-14-glucoside (ZEN14Glc) and zearalenone-16-glucoside (ZEN16Glc), using polarized monolayers of Caco-2 cells. The cells were apically exposed to 40 μM of ZEN14Glc, ZEN16Glc and ZEN, separately. Results showed that, after apical administration, ZEN14Glc and ZEN16Glc can be detected in cellular extracts indicating uptake by intestinal cells. Moreover, the glucosylated forms were cleaved to release ZEN, with a different cleavage ability for the two conjugated isomers. In particular, ZEN16Glc seems to be less prone to deglycosylation compared to ZEN14Glc, probably on account of an increased steric hindrance. We could show that human cytosolic β-glucosidase is able to cleave ZEN14Glc liberating ZEN, but is unable to cleave ZEN16Glc.All metabolites could cross the cell membrane and be detected in the apical compartment, while ZEN was also found in the basolateral compartment together with the modified mycotoxin form.

Two commercial gluten-free mixtures (F1 gf , and F2 gf ) were enriched with 20 g/100 g and 10 g/100 g of chestnut flour, respectively, to produce technologically and nutritionally improved breads (M1C, M2C) to be compared to gluten-free breads (M1 and M2). Physicochemical (proximate composition, colour, texture, crumb grain characteristics) and nutritional (antioxidant capacity, in vitro digestion) indices were monitored during three days storage. The addition of chestnut flour led to colour browning, lower bulk volume with larger crumb holes and faster staling resulting from crumb cohesiveness and resilience decrease. M2C presented harder crumb and smaller holes compared to M1C, probably due to the lupine proteins in M2C. During storage, the crust hardness decreased (M1C) or increased (M2C) depending on mixture components, as consequence of different water migration. Higher antioxidant activity was observed for both the enriched breads while no variations resulted in starch digestibility. Finally, only breads with 20 g/100 g of enrichment showed a significant increase in total as well as soluble and insoluble fibres.

In the present work, the changes in sugar and organic acid profiles of elderberry juice fermented by lactic acid bacteria were reported for the first time. Twelve different LAB strains belonging to Lactobacillus plantarum, Lactobacillus paracasei, Lactobacillus casei and Lactobacillus rhamnosus species were applied for fermentation. All the samples obtained were analysed by GC-MS technique, after fermentation and cold storage. Lactic acid was the main end product: its concentration ranged between 10287 ± 585 mg/kg (juice started with L. casei 2246) and 27261 ± 4089 mg/kg (juice fermented with L. rhamnosus 1019), increasing its amount of about 40 fold compared to the unstarted product. Malic and citric acids were extensively metabolized by LAB, while glucose and fructose (27080 ± 4062 mg/kg and 27338 ± 4101 mg/kg respectively) were almost unaffected suggesting a switch in the microbial metabolism with the use of organic acids instead of sugars, probably due to the hostile environment represented by elderberry juice. To better highlight the differences among the samples, Discriminant Analysis was performed revealing differences between L. casei and all the other species tested especially due to the organic acid concentrations.

In this study, four strains of Lactobacillus casei, as viable cells or cell-free extracts (CFE), were added to elderberry juice in order to evaluate their effect on phenolic and aromatic profile. Two of them were able to grow in juice while the others showed zero-growth. The same strains were lysed and added as extracts in elderberry juice. Multivariate statistical analysis show a separation among samples containing growing cells, non-growing cells, CFE, highlighting the particularities of specific strains. Juices added with CFE presented the highest amount of esters. The strains showing growth phenotype cause an increase of phenyllactic acids. The highest concentration of volatile compounds, particularly of alcohols, terpenes and norisoprenoids (responsible for typical elderberry notes) was observed in samples with strains showing zero-growth. Moreover, a significant increase in anthocyanin content was observed in these samples, suggesting the possible use of Lactobacillus for increasing specific molecules, even for non-multiplying bacterial cell. Considering that this is the first study concerning the use of non-growing cells in fruit juice, the potential of strains is still to be explored and it may have a significant technological application in the development of a microbial collection useful for fruit juice industry.

In this study, ten strains of Lactobacillus were used to assess the in vitro metabolism of elderberry juice polyphenols. Total polyphenolic compounds increased after starter addition, especially with three L. rhamnosus and one L. plantarum strains, of dairy origin: quercetin-3-O-rutinoside was the most abundant compound (from 39.02 ± 5.28 to 127.56 ± 11.34 µg/mL) and hydroxycinnamic acids, flavonols and anthocyanins reached the highest amounts. When L. plantarum were used phenyllactic acids presented a value of 7.05 ± 2.38 µg/mL, while in the other samples it was around 5.56 ± 1.65 µg/mL. Hydroxycinnamic and hydroxybenzoic acids were subjected to lactic acid bacteria metabolism: caffeic and protocatechuic acids were consumed during fermentation while dihydrocaffeic acid and catechol were produced. Anthocyanins increased in a strain-specific way. So, by this study we highlighted that dairy strains can produced (phenyllactic acids), modified (hydroxycinnamic acids) or increased (flavonols glycosides and anthocyanins) phenolic compounds.

Chestnut (Castanea sativa Mill.) is an important fruit crop, representing a fundamental economic resource in rural areas. The consumption of chestnut fruit has increased in recent years, after decades of neglect due to high prices and loss of food traditions. Nevertheless, chestnut is a precious food, since it is a source of starch, essential fatty acids, essential amino acids, antioxidants and vitamins. Moreover, chestnut flour can be used in gluten free formulations. The aim of this work was to evaluate by proximate analysis the fatty acids and amino acids profile and the antioxidant capacity of nine native cultivars from Emilia Romagna region, for two consecutive years. By using 2-way ANOVA analysis considering the factors “C. sativa cultivar” and “harvesting year” it was possible to state the non-dependence of carbohydrates on these two factors. On the contrary, the variability of crude fat, crude proteins, free amino acids profile and total antioxidant capacity depend both on cultivar and harvesting year. Chestnut flours are a good source of oleic and linoleic acids: their levels, together with that of palmitic acid, are affected by the cultivar; stearic and linolenic acid variability is instead due to the harvest year. The nutritional data from this research can provide useful information for the bakery industry, in view of the new trend of functional products able to merge tradition and innovation.

In the scientific field, there is a progressive awareness about the potential implications of food processing on mycotoxins especially concerning thermal treatments. High temperatures may cause, in fact, transformation or degradation of these compounds. This work is aimed to study the fate of mycotoxins during bakery processing, focusing on deoxynivalenol (DON) and deoxynivalenol-3-glucoside (DON3Glc), along the chain of industrial rusk production. Starting from naturally contaminated bran, we studied how concentrations of DON and DON3Glc are influenced by modifying ingredients and operative conditions. The experiments were performed using statistical Design of Experiment (DoE) schemes to synergistically explore the relationship between mycotoxin reduction and the indicated processing transformation parameters. All samples collected during pilot plant experiments were analyzed with an LC-MS/MS multimycotoxin method. The obtained model shows a good fitting, giving back relevant information in terms of optimization of the industrial production process, in particular suggesting that time and temperature in baking and toasting steps are highly relevant for minimizing mycotoxin level in rusks. A reduction up to 30% for DON and DON3Glc content in the finished product was observed within an acceptable technological range.

A new method for the simultaneous quantitative determination in human urine of 3-monochloropropane-1,2-diol (3-MCPD), a toxic food contaminant, and its metabolite, 2,3-dihydroxypropyl mercapturic acid (DHPMA), was developed and validated. After urine dilution, the analytes were separated on an Atlantis®dC18 column and quantified by liquid chromatography-tandem mass spectrometry using isotopically labelled internal standards. The limits of quantification (S/N = 10) were 1.90 and 2.21 μg/L for 3-MCPD and DHPMA, respectively. Intra- and inter-day precision were lower than 6 % for each compound. Matrix effects were evaluated. Due to the high sensitivity and good accuracy of the method, 3-MCPD and DHPMA were found in 67 and 100 % of urine samples of healthy subjects, respectively.

Fumonisin B 1 (FB 1 ) is a Fusarium mycotoxin frequently occurring in maize-based food and feed. Alkaline processing like nixtamalisation of maize generates partially and fully hydrolysed FB 1 (pHFB 1 and HFB 1 ) and thermal treatment in the presence of reducing sugars leads to formation of N- (1-deoxy-D-fructos-1-yl) fumonisin B 1 (NDF). The toxicity of these metabolites, in particular their effect on the sphingolipid metabolism, is either unknown or discussed controversially. We produced high purity FB 1 , pHFB 1 a+b, HFB 1 and NDF and fed them to male Sprague Dawley rats for three weeks. Once a week, urine and faeces samples were collected over 24 h and analysed for fumonisin metabolites as well as for the sphinganine (Sa) to sphingosine (So) ratio by validated LC–MS/MS based methods. While the latter was significantly increased in the FB 1 positive control group, the Sa/So ratios of the partially and fully hydrolysed fumonisins were indifferent from the negative control group. Although NDF was partly cleaved during digestion, the liberated amounts of FB 1 did not raise the Sa/So ratio. These results show that the investigated alkaline and thermal processing products of FB 1 were, at the tested concentrations, non-toxic for rats, and suggest that according food processing can reduce fumonisin toxicity for humans.

The influence of cornmeal industrial production processing on the distribution of fumonisins in thevarious different production chain corn derivatives (corn, corn flour, germ, middlings, broken corn,cornflake and cornmeal flour)was studied.Free and hydrolyzed fumonisin fractions were extracted and their content was determined by HPLC-MS/MS analysis. Results showed that fumonisin amounts decreased significantly after cleaning and corn-flaking processes, achieving a final reduction of about 40% in the cornmeal semolina, while higher levelof contamination in corn flour (fumetto) and middlings were detected. Furthermore, in order to betterunderstand the influence of the different treatments on fumonisin distribution, the occurrence of theirfree and masked forms during this industrial processing was investigated.Results for masked fumonisins showed that they were not detected probably due to different climaticand technological factors.© 2014 Elsevier Ltd. All rights reserved. 1. IntroductionFumonisins are a group of secondary metabolites mainly pro-duced by Fusarium verticilloides and Fusarium proliferatum, that canoccur in corn and corn-base products. These mycotoxins, especiallythose pertaining to B series (FBs), may cause a variety of undesir-able effects in mammals, such as hepatocarcinogenic, hepatotoxic,nephrotoxic, and cytotoxic diseases. In human, the high incidenceof esophageal cancer has been related with FB1 exposure (Creppy,2002). The consumption of fumonisin-contaminated maize hasalso been associated with the occurrence of neural tube defects(Marasas et al, 2004). For these reasons FB1 has been classified as a2B carcinogenic by the International Agency of Research on Cancer(IARC, 2002). The joint FAO/WHO Expert Committee on Food Ad-ditives (JECFA) has determined a maximum tolerable daily intake(PMTDI) of 2

In this study we explored, for the first time, the lactic acid fermentation of elderberry juice (EJ). A total of 15 strains isolated from dairy and plant matrices, belonging to L. plantarum, L. rhamnosus and L. casei, were used for fermentations. The volatile profile of started and unstarted EJ was characterized by HS-SPME/GC-MS technique after 48 h of fermentation and 12 days of storage at 4 °C. All L. plantarum and L. rhamnosus strains exhibited a good capacity of growth while not all L. casei strains showed the same ability. The aromatic profile of fermented juices was characterized by the presence of 82 volatile compounds pertaining to different classes: alcohols, terpenes and norisoprenoids, organic acids, ketones and esters. Elderberry juice fermented with L. plantarum strains showed an increase of total volatile compounds after 48 h while the juices fermented with L. rhamnosus and L. casei exhibited a larger increase after the storage. The highest concentration of total volatile compounds were observed in EJ fermented with L. plantarum 285 isolated from dairy product. Ketones increased in all fermented juices both after fermentation and storage and the most concentrated were acetoin and diacetyl. The organic acids were also affected by lactic acid fermentation and the most abundant acids detected in fermented juices were acetic acid and isovaleric acid. Hexanol, 3-hexen-1-ol (Z) and 2-hexen-1-ol (E) were positively influenced during dairy lactic acid bacteria strains fermentation. The most represented esters were ethyl acetate, methyl isovalerate, isoamyl isovalerate and methyl salicylate, all correlated with fruit notes. Among terpenes and norisoprenoids, β-damascenone resulted the main representative with its typical note of elderberry. Furthermore, coupling obtained data with multivariate statistical analyses, as Principal Component Analysis (PCA) and Classification Trees (CT), it was possible to relate the characteristic volatile profile of samples with the different species and strains applied in this study.

Urinary biomarkers of mycotoxin exposure were evaluated in a group of celiac patients (n = 55) and in a control group of healthy subjects (n = 50) following their habitual diet. Deoxynivalenol (DON), zearalenone (ZEN), and fumonisin B1 (FB1) were monitored in 105 urinary samples collected from the two groups. Dietary habits were also recorded through compilation of a seven-day weighed dietary diary. Biomarkers of mycotoxin exposure were detected in 21 celiac patients and in 15 control subjects, corresponding to about 34% of total participants. In particular, ZEN was the most detected mycotoxin among all the studied subjects with a total of 19 positive cases. Results did not show a statistically significant difference in mycotoxin exposure between the two groups, and the presence of specific mycotoxins was not related to the intake of any particular food category. Our findings suggest little urgency of specific regulation for gluten free products, although the prevalence of exposure observed in free-living diets of both celiac and healthy subjects underlines the need of a constant surveillance on mycotoxins occurrence at large.

Food processing may induce thermal degradation of fumonisins in corn via Maillard-type reactions, or alkaline hydrolysis via loss of the two tricarballylic acid moieties. In the former case, N-(1-deoxy-D-fructos-1-yl)-fumonisin B(1) (NDF) can be formed, while the latter derivative is called hydrolysed fumonisin B(1) (HFB(1)). The aim of this study was to deepen the knowledge about the gastrointestinal stability of HFB(1) and NDF in humans. Due to the lack of standard, NDF was chemically synthesised and cleaned up in high purity to be used for further experiments. While NDF is already partially cleaved (about 41%) during simulated digestion, it remained rather stable towards human colon microflora. In contrast to this, HFB(1) is partially metabolised by the colon microflora to unknown compounds after 24 h of fermentation, as seen by a loss of about 22%. Concluding, the cleavage of NDF during digestion as well as the likely metabolisation of HFB(1) emphasise the need for animal trials to ascertain their toxicity in vivo.

Sous vide treatment is encountering a renewed interest among chefs and catering operators, but an important concern is that they had been joined by those who were not aware resulting in foods held at time/temperature combination that may be not appropriate by a qualitative point of view. In this study, beef semitendinosus muscles were sous vide cooked by applying two different time/temperature treatments, a typical low temperature–long time (LT-LT) condition realized by cooking 36 h at 75 °C (SV75) and an innovative high temperature–short time (HT-ST) one for 2 h at 100 °C (SV100). Data were compared to traditionally boiled meat, and changes in pasteurization values, weight loss, texture, color, vitamins of B group as well as volatile compounds profile were evaluated. HT-ST treatment proved to achieve a pasteurization value sufficient to exclude Clostridium perfringens risk, while on the contrary, LT-LT may be a sous vide cooking approach that could be subjected to this microbiological hazard. Total weight loss of SV100 resulted significantly lower compared to SV75. SV75 samples showed the lowest shear force and hardness, being also less red than the other two samples. In addition, vitamin B3 retention was very similar for both sous vide methods, while LT-LT condition allowed a higher retention of B12. Finally, volatile compounds of beef muscles cooked by means of LT-LT and HT-ST sous vide conditions showed lower accumulation of off-flavor such as hexanal or 3-octanone in comparison to traditional boiling technique and better preserved the volatile profile of raw meat. Sous vide cooking at HT-ST condition used in this study could represent a feasible alternative to low-temperature treatment allowing to obtain comparable or better qualitative standards except for vitamin B12 retention and hardness.

One of the main struggles of the large-scale apple processing industry is pomace disposal. One solution for this problem is to convert this waste into a resource. Apple pomace could be used as a substrate for lactic acid bacteria and could induce the formation of a more complex aroma profile, making this fermented product an innovative aromatizer for alcoholic beverages, such as beer. In this study, for the first time, the effect of lacto-fermented apple pomace addition in beer was evaluated. Three bacterial strains (Lactobacillus rhamnosus 1473 and 1019, and L. casei 2246) were tested for apple pomace fermentation, and L. rhamnosus 1473 was the strain that best modified the aromatic profile. The addition of fermented apple pomace to beer increased the complexity of the aroma profile, demonstrating the potential of this byproduct as an aromatizer in the alcoholic beverage industry.

This paper presents a comprehensive analysis of the phytochemical profile of a proprietary rosemary (Rosmarinus officinalis L.) extract rich in carnosic acid. A characterization of the (poly)phenolic and volatile fractions of the extract was carried out using mass spectrometric techniques. The (poly)phenolic composition was assessed by ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MSn) and a total of 57 compounds were tentatively identified and quantified, 14 of these being detected in rosemary extract for the first time. The rosemary extract contained 24 flavonoids (mainly flavones, although flavonols and flavanones were also detected), 5 phenolic acids, 24 diterpenoids (carnosic acid, carnosol, and rosmanol derivatives), 1 triterpenoid (betulinic acid), and 3 lignans (medioresinol derivatives). Carnosic acid was the predominant phenolic compound. The volatile profile of the rosemary extract was evaluated by head space solid-phase microextraction (HS-SPME) linked to gas chromatography-mass spectrometry (GC-MS). Sixty-three volatile molecules (mainly terpenes, alcohols, esters, aldehydes, and ketones) were identified. This characterization extends the current knowledge on the phytochemistry of Rosmarinus officinalis and is, to our knowledge, the broadest profiling of its secondary metabolites to date. It can assist in the authentication of rosemary extracts or rosemary-containing products or in testing its bioactivity. Moreover, this methodological approach could be applied to the study of other plant-based food ingredients.

The present paper reports a complete mass spectrometric characterization of both the phenolic and volatile fractions of a dried spearmint extract. Phenolic compounds were analysed by ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS(n)) and a total of 66 compounds were tentatively identified, being the widest phenolic characterisation of spearmint to date. The analysis suggests that the extract is composed of rosmarinic acid and its derivatives (230.5 ± 13.5 mg/g) with smaller amounts of salvianolic acids, caffeoylquinic acids, hydroxybenzoic acids, hydroxycinnamic acids, flavones, and flavanones. Head space solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) technique, that was applied to characterize the volatile fraction of spearmint, identified molecules belonging to different chemical classes, such as p-cymene, isopiperitone, and piperitone, dihydroedulan II, menthone, p-cymen-8-ol, and β-linalool. This comprehensive phytochemical analysis can be useful to test the authenticity of this product rich in rosmarinic acid and other phenolics, and when assessing its biological properties. It may also be applied to other plant-derived food extracts and beverages containing a broad range of phytochemical compounds.

Mycotoxins are secondary metabolites produced by fungi that can contaminate a wide range of food and feed commodities and that are harmful to humans for their poisonous and toxic effects. An increasing amount of data have been accumulated in the last years, showing that mycotoxins may also occur in modified forms originating by plant, fungi or animal metabolism or by food processing. In particular, this modified forms may be produced via conjugation with sugars or other biological components (masked mycotoxins) or may occur as non extractable forms on account of strong interaction, association or binding with macromolecules in the food matrix (bound or hidden mycotoxins). Analytical methods have been set up in order to check for the occurrence of these forms and to evaluate their amount, in order to obtain reliable data for toxicity and exposure studies. In this paper hyphenated chromatographic methods for the determination and structural characterization of masked mycotoxins are reviewed, with a particular emphasis on liquid chromatography-(tandem) mass spectrometry as the most effective approach for their determination.

Fumonisins are a family of food-borne mycotoxins with a wide spectrum of toxicological activities, produced by Fusarium verticillioides. Twenty-eight fumonisin analogues have been characterised so far, which can be separated into four main groups, identified as fumonisin A, B, C and P, being fumonisin B the most widely occurring in maize and corn-based food. In this work, major and minor fumonisin analogues produced by F. verticillioides have been determined by the development of a suitable tandem mass spectrometry procedure for target compound identification and quantification. The method has been applied to the determination of the major fumonisins in culture media of F. verticillioides and in mouldy maize. In addition to the main fumonisins produced by F. verticillioides, also secondary compounds such as FB4, FB5, FAs and FCs have been detected in both fungal liquid cultures and contaminated maize samples. The use of this method for quantification of major and minor fumonisins may be useful for an exhaustive evaluation of their occurrence and toxicological relevance in food; moreover, it may be applied for a better definition of the fumonisin biosynthetic pathways in different growing media as well as in maize.

Fumonisins can occur in foodstuffs as free forms (prent, partially hydrolysed, or totally hydrolysed), as covalently bound fumonisins (bound fumonisins) and as non-covalently bound fumonisins (hidden fumonisins). The formation of several covalently bound fumonisin B1 conjugates upon reaction with sugars and/or amino acids has been reported in the literature so far, but occurrence data are still very poor. Since very little is known about the relevance of both hidden and bound fumonisins in processed products, the present study aimed to evaluate the occurrence of both masked forms in maize-based food products and to study their stability under digestive conditions. The behaviour of covalently bound fumonisin B1 conjugates upon in vitro digestion was evaluated, demonstrating their stability under these conditions. In addition, the co-occurrence of hidden and bound fumonisins in maize-based food products was investigated by application of both alkaline hydrolysis and simulated in vitro digestion assay. The experiments clearly showed that bound fumonisins were rather stable under the applied conditions, whereas hidden fumonisins released their parent forms.

This study reports for the first time the metabolic profile of cocoa (Theobroma cacao L.) beans using the (1)H NMR technique applied to polar extracts of fermented cocoa beans. The simultaneous detection and quantification of amino acids, polyalcohols, organic acids, sugars, methylxanthines, catechins, and phenols were obtained by assigning the major signals of the spectra for different varieties of cocoa beans (Forastero, Criollo, and Trinitario) from different countries (Ecuador, Ghana, Grenada, and Trinidad). The data set obtained, representative of all classes of soluble compounds of cocoa, was useful to characterize the fermented cocoa beans as a function of the variety and geographic origin.

1H NMR spectra were recorded of methanolic extracts of seven soybean varieties (Glycine max.), cultivated using traditional and organic farming techniques. It was possible to identify signals belonging to the groups of amino acids, carbohydrates, organic acids and aromatic substances in the spectra. In the aromatic zone, the isoflavone signals were of particular interest: genistein, daidzein, genistin, daidzin, malonylgenistin, acetylgenistin, malonyldaidzin signals were assigned and these compounds were quantified, resulting in accordance with published data, and further demonstrating the potential of the NMR technique in food science.

We report for the first time the detection of glucose acetates in balsamic vinegars. It is well known that during traditional balsamic vinegar (TBV) ageing several modifications occur. In this paper it was experimentally determined that some modifications take also place during the short maturation time of balsamic vinegar of Modena (BVM), with an increase of the esters content due to the reaction between acetic acid and sugars, in particular glucose. The formation of esters was observed both on reference solutions containing glucose and acetic acid, subjected to an accelerated ageing by heating at 50 °C, and on real balsamic vinegar samples. Glucose esters were mainly detected as α- and β-glucopyranose acetates. The formation of fructose acetates in reference solutions, was also studied, recording a more complex pattern of products. The structures of the esters were determined by GC/MS analyses and NMR spectroscopy.

Lipid molecules are increasingly recognized as signals exchanged by organisms interacting in pathogenic and/or symbiotic ways. Some classes of lipids actively determine the fate of the interactions. Host cuticle/cell wall/membrane components such as sphingolipids and oxylipins may contribute to determining the fate of host–pathogen interactions. In the present field study, we considered the relationship between specific sphingolipids and oxylipins of different hybrids of Zea mays and fumonisin by F. verticillioides, sampling ears at different growth stages from early dough to fully ripe. The amount of total and free fumonisin differed significantly between hybrids and increased significantly with maize ripening. Oxylipins and phytoceramides changed significantly within the hybrids and decreased with kernel maturation, starting from physiological maturity. Although the correlation between fumonisin accumulation and plant lipid profile is certain, the data collected so far cannot define a cause-effect relationship but open up new perspectives. Therefore, the question—“Does fumonisin alter plant lipidome or does plant lipidome modulate fumonisin accumulation?”—is still open.

The presence of mycotoxins in food and feed may affect human and animal health on account of a broad spectrum of adverse health effects. Among them, deoxynivalenol is considered the most common contaminant in cereal worldwide. Recently, the co-occurrence of fungal and plant metabolites together with the parent compounds in food has been described. However, these compounds are still not covered by regulations, since data about their toxicological relevance are still poor. The stability of these derivatives upon digestion is a crucial point in risk assessment, because a possible release of the parent compound in the gastrointestinal tract may lead to an underestimation of the actual human exposure. A number of publications have addressed the gut microbiome-driven chemical modification of nutrients in humans, while similar processes involving xenobiotics have not been extensively studied. This chapter is thus focused on the role played by the gut microbiome on the catabolic fate of deoxynivalenol derivatives.

The drying process is commonly applied to maize grain to guarantee a safe storage. Two different conditions were tested (70 °C × 24 h and 95°C × 9 h) on 6 maize hybrids collected in 2010 in Italy. Maize samples were analysed for fungal incidence, kernel chemical composition (proteins, fat, starch) and free and hidden forms of fumonisins (FBs) pre- and post-drying treatments. Drying treatments reduced fungal incidence; in particular, both temperature × time combinations were able to reduce more than 85% Fusarium spp. incidence. In general, both free and total FBs increased after drying, especially at 70 °C for 24 h exposure. Regarding chemical composition, proteins and starch resulted unvaried, while fat content had a mean decrement of 26% and 14% after treatment at 70 °C × 24 h and 95 °C × 9 h, respectively. A possible retrogradation of starch, and in particular amylose, after heating has been proposed in this study; these changes seemed to be strongly related to the modifications in detectable fumonisin. This study confirms the variation in detectable FBs occurring after the drying treatment. Therefore, the quantification of fumonisin after the post-harvest treatments is strongly suggested to avoid maize contaminated above the legal limit to enter the food/feed chain.

The role of lipids in maize – Fusarium verticillioides interaction and fumonisin production in natural field conditions were investigated. In 2010, ten maize hybrids were grown in fields located in 3 districts in Northern Italy and sampled at 4 growing stages, from early dough to full ripe. Chemical composition, fungal incidence and free and hidden fumonisin contamination were determined in all grain samples. All the hybrids considered within this study showed a strong fungal incidence, with Fusarium section Liseola as prevalent, already at the early dough maturity and along the ripening period. Fumonisins accumulated over the growing season and reached the maximum level at the full ripe stage; hidden fumonisins were found significant in all the considered samples (~57% of the free form at harvest). Hybrid H9 showed more than 50% of kernels infected by Aspergillus flavus and no hidden fumonisins were detected. This finding stresses the relevance of monitoring both free and total fumonisins for a comprehensive assessment of consumer exposure to mycotoxins. Previous studies showed a positive correlation between the content of linoleic acid and fumonisin accumulation into maize kernels infected with Fusarium section Liseola. Hence, an untargeted and targeted lipid analysis of maize kernels along the growing season and at harvest was performed. Results suggested a significant involvement of lipid composition of maize kernels in fungal infection and toxin accumulation. Specifically, mass spectrometry data pinpointed that at least 4 lipid entities might differentiate high-contaminated from low-contaminated samples when the cut-off of 2,000 μg/kg of fumonisins was selected. Among them, the oxylipin 9-HODE and three sphingolipids were identified. These results suggest that sphingolipid and oxylipin metabolism in maize kernels interferes with F. verticillioides growth and fumonisin production in plants growing in field.

Alternaria toxins are mycotoxins produced by Alternaria species. These fungi cause serious diseases in many crops such as cereals, oil seeds, and fruits. More than 70 Alternaria toxins have been reported and only some of them have been physicochemically characterized. Among the most common in food commodities, alternariol (AOH), alternariol methyl ether (AME), altenuene (ALT), and tenuazonic acid were mainly studied. Available in vitro data indicate that AOH, AME, and ALT are hydroxylated, mostly to catechol metabolites, and form glucuronide and sulfate conjugates. AOH and AME are genotoxic in bacteria and mammalian cells in vitro . Although there are no in vivo genotoxicity or carcinogenicity data available for Alternaria toxins, some indications of precancerous changes have been reported in esophageal mucosa of mice. In this review, the state of the art about the toxic effects of the major Alternaria toxins will be reported, and new data about their stability under in vitro human simulated gastrointestinal conditions will be described.

Deoxynivalenol (DON) is the most prevalent trichothecene in Europe and its occurrence is associated with infections of Fusarium graminearum and F. culmorum, causal agents of Fusarium head blight (FHB) on wheat. Resistance to FHB is a complex character and high variability occurs in the relationship between DON content and FHB incidence. DON conjugation to glucose (DON-3-glucoside, D3G) is the primary plant mechanism for resistance towards DON accumulation. Although this mechanism has been already described in bread wheat and barley, no data are reported so far about durum wheat, a key cereal in the pasta production chain. To address this issue, the ability of durum wheat to detoxify and convert deoxynivalenol into D3G was studied under greenhouse controlled conditions. Four durum wheat varieties (Svevo, Claudio, Kofa and Neodur) were assessed for DON-D3G conversion; Sumai 3, a bread wheat variety carrying a major QTL for FHB resistance (QFhs.ndsu-3B), was used as a positive control. Data reported hereby clearly demonstrate the ability of durum wheat to convert deoxynivalenol into its conjugated form, D3G.

Fusarium mycotoxins are secondary metabolites produced by Fusarium spp. in cereals. Among them, deoxynivalenol (DON) and zearalenone (ZEN) are widespread worldwide contaminants of cereal commodities and are ranked as the most important chronic dietary risk factors. Their conjugates, known as masked mycotoxins, have been described but are still not accounted for in risk assessment studies. This study demonstrates for the first time that DON and ZEN are effectively deconjugated by the human colonic microbiota, releasing their toxic aglycones and generating yet unidentified catabolites. For this reason, masked mycotoxins should be considered when evaluating population exposure.

Fusarium verticillioides is one of the most important fungal pathogens causing ear and stalk rot in maize. Even if frequently asymptomatic, it can produce a harmful series of compounds named fumonisins. Plant and fungal oxylipins play a crucial role in determining the outcome of the interaction between the pathogen and its host. Moreover, oxylipins are factors able to modulate the secondary metabolism in fungi. To uncover the existence of the relationship between oxylipin production and fumonisin synthesis in F. verticillioides, we analysed some molecular and physiological parameters, such as the expression of genes whose products are related to oxylipin synthesis (i.e. lipoxygenase, diol synthases and fatty acid oxidase), the oxylipin profile of both cracked maize and the pathogen by using a lipidomic approach (i.e. combining LC-TOF and LC-MS/MS approaches with a robust statistical analysis) and the synthesis of fumonisin B1. The results suggested a close relationship between the modification of the pathogen oxylipin profile with the fumonisin synthesis. Notably, a modification of the oxylipin profile of the pathogen during its growth on cracked maize can be demonstrated. The switch in oxylipin synthesis could indicate that the ‘presence’ of maize determinants (e.g. plant cell wall fragments and/or lipids) was able to promote the modification of the pathogen lifestyle, also by adapting the secondary metabolism, notably fumonisin synthesis.

Head space solid-phase microextraction (HS-SPME) coupled with GC–MS analysis has been applied for the determination of the characteristic volatile profile of Balsamic Vinegar of Modena (BVM) with the aim to distinguish the less matured products (matured in wooden barrels for at least 60 days) from the aged ones (aged in wooden barrels for at least 3 years). Coupling the HS-SPME/GC–MS analysis data with multivariate statistical techniques, such as Principal Components Analysis (PCA) and Classification Trees (CT), it has been possible to classify BVMs on the basis of different maturation and ageing. A matured BVM presents an aromatic profile characterised by high contents of 3-methyl-1-butanol, 4-ethyl-phenol, and 3-methyl-1-butanol acetate, while an aged BVM is characterised by a prevalence of ethyl acetate, ethyl acetoacetate, furans, 2,3-butanediol and 2,3-butanediol acetate. This work represents a first attempt to classify Balsamic Vinegars of Modena on the basis of their maturation and ageing.

Fermented cocoa beans (Theobroma cacao L., Sterculiaceae) from different countries of origin (Ecuador, Ghana, Trinidad) and cocoa beans roasted under defined conditions (industrial roasting; 150-220 degrees C for 20 min, dry roasting in conventional oven) were analyzed for their contents of certain chiral hydroxy acids, catechins, and amino acids. Cocoa beans are fermented, dried, and industrially transformed by roasting for the production of chocolate, cocoa powders, and other cocoa-related products. Fermentation and roasting conditions influence the contents of chiral compounds such as hydroxy acids, amino acids, and polyphenols, depending on technological procedures as well as some technical parameters. The aim of this work was to check if the content and nature of the named chiral compounds present both in fermented and roasted cocoa beans could be related to the traditional parameters used to classify the variety of seeds and the degree of fermentation. The extent of racemization of amino acids in fermented cocoa beans was low while it slowly increased during roasting, depending on the temperature applied. L-lactic acid was always higher than the D-form while citric acid was generally the most abundant hydroxy acid detected in beans. A correlation was found between polyphenol content and degree of fermentation, while epimerization of (-)-epicatechin to (+)-catechin was observed during roasting. On the whole, results showed that several chiral compounds could be considered as good quality markers for cocoa seeds and cocoa-related products of different quality and geographic origin.

Celiac disease (CD) is an immune-mediated enteropathy sustained by dietary gluten in susceptible individuals, and characterized by a complex interplay between adaptive and innate responses against gluten peptides (PTG). In a recent contribution we have demonstrated that the treatment with PTG induces the expression and activity of arginase in both murine macrophages and human monocytes from healthy subjects, thus suggesting a role for arginine and its metabolites in gluten-triggered response of these cells. Here we further explore this field, by addressing the effects of PTG on polyamine synthesis and release in murine RAW264.7 macrophages, and how they affect epithelial permeability of Caco-2 monolayers. Results obtained show a massive production and release of putrescine by macrophages upon incubation with gluten peptides; this, in turn, causes a decrease in TEER in epithelial cells, indicating that PTG-driven secretion of polyamines by macrophages has a role in the modulation of intestinal permeability in vitro. At a molecular level, putrescine production appears referable to the activation of C/EBPβ transcription factor, which is known to be responsible for arginase induction in activated macrophages and is a crucial mediator of inflammation. Whether these pathways are stimulated also in vivo deserves to be further investigated, as well as their role in gluten-driven cellular and intestinal defects typical of CD patients.