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In the last years, due to the increasing interest of consumers in natural products, market and industry choices were more directed towards the use of fragrances and flavors obtained from natural sources. Fermentation is a biological approach helpful to produce diverse aromatic compounds modifying precursors present in raw material, due to a wide array of extracellular enzymes which could be produced by microorganisms. Following this direction Lacticaseibacillus rhamnosus was employed as a starter for melon and orange by-products fermentation. Simple and vacuum distillation were applied for the recovery of the aromatic fraction and compared to identify the more promising in terms of aromatic profile composition. Detection and characterization of aromatic compounds were achieved using Head SpaceSolid Phase MicroExtraction Gas Chromatography–Mass Spectrometry (HS-SPME/GC–MS) approach. Fermentation led to interesting changes, increasing floral, herbal green and fruity notes. Overall, simple distillation allowed the greater recovery of aromatic compounds in terms of concentration for both substrates. This study highlights a possible strategy to produce complex distillates, composed of a mixture of aroma compounds, to be employed as additives in food, feed or perfumery industries as ingredients of natural origin.

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.

In the present study, we have characterized for the first time the volatile fraction of 20 pomegranate juices from fruits harvested in Northern Italy and southern Montenegro, by means of headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry technique (GC-MS). The volatile profile accounted for 57 compounds belonging mainly to three chemical classes: alcohols, aldehydes and terpenes. Thanks to advance chemometric analysis, the samples were clusterized according to the geographical origin, and the volatiles responsible for differentiation were identified, indicating that the use of volatile profile for discriminating between pomegranate ecotypes grown in different geographical areas is a promising approach. Overall, the chemical information acquired represents a very relevant tool for the retrieval and exploitation of minor varieties and in support of biodiversity of these promising geographical areas for pomegranate cultivation.

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.

Research is more and more focused on studying and selecting food preservatives of natural origin. In this scenario, algae are an excellent source of bioactive compounds, among which are antimicrobials, whose presence is variable depending on the algal species and environmental conditions. The aim of the present study was to obtain, by a food grade approach, antimicrobial extracts from five species already approved as foods and to test their efficacy in vitro (agar well diffusion assay) and in situ (microbial challenge test) towards foodborne pathogenic bacteria. Moreover, the total phenolic compounds of the extracts were determined in order to evaluate possible correlations with the antimicrobial activity. Strains belonging to Salmonella spp., Listeria monocytogenes, Escherichia coli, Staphylococcus aureus, and Bacillus cereus were considered. Overall, the extracts showed a good antimicrobial activity in vitro towards all the tested microorganisms, especially L. monocytogenes (15 mm of inhibition diameter). The effect of inhibition was monitored during 24, 48 and 120 h showing a good persistence in time. Arthrospira platensis exerted the highest efficacy, further revealed towards L. monocytogenes on salmon tartare as bacteriostatic using 0.45% of the extract and bactericidal using 0.90%. The presence of phenolic compounds could be related to the antimicrobial activity but was not revealed as the main component of this activity. The extract with the highest phenolic content (18.79 &plusmn, 1.90 mg GAE/g) was obtained from Himanthalia elongata. The efficacy, confirmed also in a food matrix, might open perspectives for their application as food preservative.

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.

The aim of this study examined the characterization of extra virgin olive oil samples from the main cultivar Chemlali, grown in five olive orchards with different soil type (Sandy, Clay, Stony, Brown, Limestone and Gypsum). Volatile compounds were studied using headspace-solid phase micro-extraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) technics. Moreover, the sterol profile was established using gas chromatography-mass spectrometry. 35 different volatile compounds were identified: alcohols, esters, aldehydes, ketones and hydrocarbons. The chemical composition of the volatile fraction was characterized by the preeminence of 2-hexenal (32.75%) and 1-hexanol (31.88%). Three sterols were identified and characterized. For all olive oil samples, s-sitosterol (302.25 mg/kg) was the most abundant sterol. Interestingly, our results showed significant qualitative and quantitative differences in the levels of the volatile compounds and sterols from oils obtained from olive trees grown in different soil type.

Background: One of the main objectives of the food industry is the shelf life extension of food products, taking into account the safety requirements and the preference of consumers attracted by a simple and clear label. Following this direction, many researchers look to find out antimicrobials from natural sources. Methods: Tomato, carrot, and melon by-products were used as substrates for lactic acid fermentation using seven strains belonging to the Lactobacillus genus, L. plantarum, L. casei, L. paracasei, and L. rhamnosus. The obtained fermented by-products were then extracted and the antimicrobial activity toward fourteen pathogenic strains of Listeria monocytogenes, Salmonella spp., Escherichia coli, Staphylococcus Aureus, and Bacillus cereus was tested through agar well diffusion assay. Results: All the extracts obtained after fermentation had highlighted antimicrobial activity against each pathogen tested. In particular, a more effective activity was observed against Salmonella spp., L. monocytogenes, S. aureus, and B. cereus, while a lower activity was observed against E. coli. Conclusion: Lactic acid fermentation of vegetable by-products can be a good strategy to obtain antimicrobials useful in food biopreservation.

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

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.

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

Environmental conditions may significantly affect both the chemical composition and the morphological parameters of chestnuts. The aim of this work was the evaluation of altitude effects on flour chemical composition and on fruit morphological parameters of different chestnut cultivars (Luetta e Leccardina), grown at two different altitude levels (700 and 1000 m.a.s.l.). In particular, crude protein, crude fat, amino acid and essential fatty acid content were determined on flours. The two genotypes were also studied from a morphological standpoint, by a biometric and descriptive evaluation of fruits at the different altitudes. Compositional and morphological data were statistically evaluated by ANOVA. The altitude influence on chestnut fruit and flour was ascertained; besides significant differences between the two cultivars, equally significant were the differences within each cultivar when plants grown at different altitudes were compared.

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.

The presence of the chestnut (Castanea sativa Mill.) in all Italian regions, within altitude limits depending on latitude, and in very different exposure and soil conditions, favored the formation of a rich patrimony of cultivars. In the course of several centuries of cultivation a number of genotypes appeared and were selected, also by virtue of a widespread habit of propagating the tree by seed; these genotypes differ for numerous traits, particularly for those relating to the fruit, but plant resistance to biotic and abiotic factors has been important in the selection process. However, the large existing genetic patrimony is increasingly at risk of genetic erosion and it is extremely important to study and valorize local germplasm in order to preserve the existing biodiversity and to identify potentially useful characters for a revival of the Italian chestnut industry. The purpose of this study was to characterize genetically, with eight nSSR (di- and trinucleotide, CsCAT and EMCs series respectively) markers, 54 ancient chestnut accessions widespread in a small area of Northern Italy. The set of chosen markers resulted as a whole highly polymorphic, and made possible the characterization of all studied accessions. The use of only three markers allowed the identification of 28 distinct genetic profiles. Data were analyzed by cluster analysis, and results demonstrated a vast genetic variability within the population. The nSSR used, moreover, allowed us to identify most unknown accessions and possible homonyms and synonyms, and cases of intravarietal clones within the local germplasm.

Celiac disease (CD) is an immune-mediated enteropathy triggered by ingested gluten in genetically susceptible individuals and sustained by both adaptive and innate immune responses. Recent studies in murine macrophages demonstrated that the activation of arginase (ARG) metabolic pathway by gluten peptides contributes to the modulation of intestinal permeability in vitro. Here we characterize the effects of gluten on arginine metabolism and cell polarization in human monocytes from both healthy and CD subjects; both a simplified enzymatic digestion of gliadin and a physiological digestion of whole wheat have been tested. Results indicate that gluten digests induce the onset of an M2-like phenotype in activated macrophages; more precisely, both isoforms of arginase, ARG1 and ARG2, are induced likely due to the inhibition of mTOR and the consequent induction of C/EBPβ transcription factor. These effects are independent from the origin of gluten as well as from the digestive protocol employed; moreover, no statistical difference can be evidenced between healthy and CD patients, excluding a diverse predisposition of CD monocytes to gluten-triggered polarization with respect to healthy immune cells. Overall, the present findings sustain a role for arginase pathway in the immune response elicited by human monocytes toward ingested gluten that, hence, deserves particular attention when addressing the pathogenesis of CD.

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.

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.

Head-space solid-phase microextraction (HS-SPME) coupled to gas-chromatography–mass spectrometry was developed and applied to obtain the volatile aromatic fingerprints of three typical Italian wines, Valpolicella, Amarone and Recioto, all produced in the restricted geographical area of Valpolicella (Veneto, Italy) with the same grape cultivars within the regulations of a rigid disciplinary of production. Differences between the three typologies are mainly linked to the different withering times to which grapes are subjected before vinification, which strongly influences the concentration and the development of volatile aroma compounds. A total of 22 different wines (7 Valpolicella, 10 Amarone and 5 Recioto) were characterised in terms of aromatic volatile profile with the aim to distinguish the different products and to evaluate the possibility to differentiate the same product from different brands. For the chemometric evaluation of the data one-way analysis of variance (ANOVA), principal component analysis (PCA) and hierarchical cluster analysis (HCA) were tested. All the chemometric tools employed allow to differentiate between the three products. More intriguing is the ability of the chemometric approach to differentiate between the same product (Amarone, Recioto) from different winery, thus showing the potential of this approach to characterize the brand-dependent typicality of wines, which is usually related to subtle technological differences which nevertheless have strong influences on the organoleptic characteristics of the products.

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.

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.

Oxylipins are fatty acid-derived signaling compounds produced by all eukaryotes so far investigated; in mycotoxigenic fungi, they modulate toxin production and interactions with the host plants. Among the many enzymes responsible for oxylipin generation, Linoleate Diol Synthase 1 (LDS1) produces mainly 8-hydroperoxyoctadecenoic acid and subsequently different di-hydroxyoctadecenoic acids. In this study, we inactivated a copy of the putative LDS1 ortholog (acc. N. FVEG_09294.3) of Fusarium verticillioides, with the aim to investigate its influence on the oxylipin profile of the fungus, on its development, secondary metabolism and virulence. LC-MS/MS oxylipin profiling carried out on the selected mutant strain revealed significant quali-quantitative differences for several oxylipins when compared to the WT strain. The Fvlds1-deleted mutant grew better, produced more conidia, synthesized more fumonisins and infected maize cobs faster than the WT strain. We hypothesize that oxylipins may act as regulators of gene expression in the toxigenic plant pathogen F. verticillioides, in turn causing notable changes in its phenotype. These changes could relate to the ability of oxylipins to re-shape the transcriptional profile of F. verticillioides by inducing chromatin modifications and exerting a direct control on the transcription of secondary metabolism in fungi.

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.

The concentrations of 12 congeners of non-ortho and mono-ortho dioxin-like polychlorinated biphenyls (ΣDL-PCB) were measured in 30 fish samples from Parma markets by GC/MS technique. The samples were randomly purchased, choosing the species commonly found in supermarkets. The concentration of DL-PCBs estimated remained under the fixed Italian limit of 4 pg g −1 ww WHO-TEQ (World Health Organization–Toxic Equivalent) in the major part of the samples, so the situation seems to be not at a level sufficient to pose a risk to human health of the Parma population. The medium daily intake for DL-PCBs for Italian consumers (Parma) was also estimated. This value generally resulted minor than 2 pg g −1 ww WHO-TEQ kg −1 body weight, exceeding only in four cases: eel, smooth hound, starry smooth hound and tuna.

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.