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This review provides the current laboratory criteria for the detection and evaluation of the possible causes of alteration of non-concentrated industrial derivatives of tomatoes (peeled tomatoes, pulps, purees, sauces, and fillets), packaged in coated or uncoated tinplate cans. We discuss how the product alterations are typically the consequence of technological errors either in the can production, or in the storage process, or in the product sterilization. The described procedures include the quantitative determination of the distribution of gases (H 2 , CO 2 , N 2 , and O 2 ) present in the headspace of the container. The gas composition and ratios can be used as markers to allow easy diagnosis of the causes of microbiologic and/or physical-chemical alterations of the tomatoes, which are usually made evident by swelling of the containers. These tests should be integrated by microbiological analyses aimed at a restricted group of microorganisms, with the chemical analysis of the container and the chemical analysis of the altered product. By way of example, we report the assessment of the causes of alteration in four different case-studies., (© 2022 Institute of Food Technologists®.)

A recently optimized rapid, cheap, and accurate coulometric method has been exploited to determine the antioxidant capacity of bergamot (Citrus bergamia Risso) by-products, including first (FPJ) and second press juices (SPJ), in comparison to analogous products from several citrus species. Extracts from the entire edible part (i.e., juice and pulp) and de-oiled peel of bergamot were also assayed. The Coulometrically Determined Antioxidant Capacity (CDAC) data, expressed as moles of electrons per mass of sample, were evaluated with other parameters such as total phenolic compounds, ascorbic acid, total carotenoids, and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical inhibition. The CDAC of bergamot FPJ (39 mmol e - kg -1 ) was comparable with other citrus juices (20-65 mmol e - kg -1 range), whereas the CDAC of bergamot SPJ (816 mmol e - kg -1 ) was strikingly higher than the counterparts from other citrus fruits. This value approached that of bergamot peel extracts (822 mmol e - kg -1 ). Bergamot peel and SPJ also exhibited the highest DPPH inhibition. The CDAC values were associated with the HPLC-determined content of flavonoids, namely neoeriocitrin, naringin, and neohesperidin, which were 4-10-fold more concentrated in bergamot SPJ and peel than in SPJ from other citrus species. These findings contribute to point at bergamot by-products as rich sources of antioxidant compounds on a quantitative basis, highlighting their enormous potential for pharmaceutical, nutraceutical and food applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Ergothioneine (Egt) is a dietary amino acid which acts as an antioxidant to protect against ageing-related diseases. We investigated the anti-cancer properties of Egt in colorectal cancer cells (CRC). Egt treatment exerted cytotoxicity in a dose-dependent manner, induced reactive oxygen species accumulation, loss of mitochondrial membrane potential and upregulation of the histone deacetylase SIRT3. Immunoblotting analysis indicated that the cell death occurred via necroptosis through activation of the RIP1/RIP3/MLKL pathway. An immunoprecipitation assay unveiled that the interaction between the terminal effector in necroptotic signalling MLKL and SIRT3 increased during the Egt treatment. SIRT3 gene silencing blocked the upregulation of MLKL and abolished the ability of Egt to induce necroptosis. The SIRT3-MLKL interaction may mediate the necroptotic effects of Egt in CRC, suggesting the potential of this dietary amino thione in the prevention of CRC., (© 2022 The Authors. FEBS Letters published by John Wiley & Sons Ltd on behalf of Federation of European Biochemical Societies.)

In this work, we present the fabrication and characterization of bulk-heterojunction solar cells on monolayer graphene (MLG) with nickel-grids (Ni-grid) as semitransparent conductive electrode. The electrodes showed a maximum transmittance of 90% (calculated in 300-800 nm range) and a sheet resistance down to 35 Ω/□. On these new anodes, we fabricated TCO free BHJ-SCs using PTB7 blended with PC70BM fullerene derivative as active layer. The best device exhibited a power conversion efficiency (PCE) of 4.2% in direct configuration and 3.6% in inverted configuration. The reference solar cell, realized on the ITO glass substrate, achieved a PCE of 6.1% and 6.7% in direct and inverted configuration respectively; for comparison we also tested OSCs only with simple Ni-grid as semitransparent and conductive electrode, obtaining a low PCE of 0.7%. The proposed approach to realize graphene-based electrodes could be a possible route to reduce the overall impact of the sheet resistance of this type of electrodes allowing their use in several optoelectronic devices.

Understanding the mechanisms of colorectal cancer progression is crucial in the setting of strategies for its prevention. δ-Valerobetaine (δVB) is an emerging dietary metabolite showing cytotoxic activity in colon cancer cells via autophagy and apoptosis. Here, we aimed to deepen current knowledge on the mechanism of δVB-induced colon cancer cell death by investigating the apoptotic cascade in colorectal adenocarcinoma SW480 and SW620 cells and evaluating the molecular players of mitochondrial dysfunction. Results indicated that δVB reduced cell viability in a time-dependent manner, reaching IC50 after 72 h of incubation with δVB 1.5 mM, and caused a G2/M cell cycle arrest with upregulation of cyclin A and cyclin B protein levels. The increased apoptotic cell rate occurred via caspase-3 activation with a concomitant loss in mitochondrial membrane potential and SIRT3 downregulation. Functional studies indicated that δVB activated mitochondrial apoptosis through PINK1/Parkin pathways, as upregulation of PINK1, Parkin, and LC3B protein levels was observed ( p < 0.0001). Together, these findings support a critical role of PINK1/Parkin-mediated mitophagy in mitochondrial dysfunction and apoptosis induced by δVB in SW480 and SW620 colon cancer cells.

Background: The so-called 'Neapolitan limmo' or 'lemoncetta Locrese' is an old and now rare Mediterranean sweet lime, similar to lemon but smaller. It is a fruit distinguished from orange, lemon, mandarin, and lime for its sweeter, watery, and non-acidic taste, with a pH between 5.6 and 5.9. No compositional studies are currently available for this citrus fruit. Here we report, for the first time, the distribution in the limmo juice of free amino acids and their main derivatives such as betaines and related ammonium compounds., Results: Seven proteinogenic amino acids (proline, asparagine, serine, aspartic acid, glutamine, alanine, and threonine) and a non-protein amino acid (γ-aminobutyric acid) characterize Neapolitan limmo juice. Proline betaine is the predominant betaine. The data were compared with those of other important citrus juices., Conclusion: The specific 'taste quality' of Neapolitan limmo juice can be attributed to its peculiar composition in amino acids. The species-specific presence of the ammonium compound derivatives of the amino acid proline, with proline betaine as the predominant betaine, characterize the non-acidic varieties of Mediterranean sweet lime. Our study constitutes an important step towards the repopulation of this ancient plant and its exploitation in food industry. © 2020 Society of Chemical Industry., (© 2020 Society of Chemical Industry.)

We provide a dataset of 3D coordinate time series of 37 continuous GNSS stations installed for stability monitoring purposes on onshore and offshore industrial settlements along a NW-SE-oriented and ~100-km-wide belt encompassing the eastern Italian coast and the Adriatic Sea. The dataset results from the analysis performed by using different geodetic software (Bernese, GAMIT/GLOBK and GIPSY) and consists of six raw position time series solutions, referred to IGb08 and IGS14 reference frames. Time series analyses and comparisons evidence that the different solutions are consistent between them, despite the use of different software, models, strategy processing and frame realizations. We observe that the offshore stations are subject to significant seasonal oscillations probably due to seasonal environmental loads, seasonal temperature-induced platform deformation and hydrostatic pressure variations. Many stations are characterized by non-linear time series, suggesting a complex interplay between regional (long-term tectonic stress) and local sources of deformation (e.g. reservoirs depletion, sediment compaction). Computed raw time series, logs files, phasor diagrams and time series comparison plots are distributed via PANGAEA ( https://www.pangaea.de ).

Bergamot essential oil (BEO) is well-known for its food preservation activity, as well as anticancer efficacy. However, the poor BEO water solubility and deriving low bioaccessibility have limited its wider applications. The incorporation in nanoemulsions of BEO and its refined fractions was investigated to enhance its dispersibility in water to promote its antimicrobial activity, tested against Escherichia coli, Lactobacillus delbrueckii, and Saccharomyces cerevisiae, and its cytotoxicity already at low concentrations. Different nanoemulsion formulations were tested based on food-grade ingredients, which were characterized in terms of hydrodynamic diameter and polydispersity index, and physical stability. The antimicrobial activity against all the tested micro-organisms was observed to be higher for BEO in its initial composition, than the light fraction, richer in d-limonene, ß-pinene, and γ-terpinene, or the heavy fraction, richer in linalyl acetate and linalool. Remarkably, the use of BEO nanoemulsions notably enhanced the antimicrobial activity for all the tested oils. BEO exhibited also a measurable cytotoxic activity against Caco-2 cells, which was also enhanced by the use of the different nanoemulsions tested, in comparison with free oil, which discourages the direct use of BEO nanoemulsions as a food preservative. Conversely, BEO nanoemulsions might find use in therapeutic applications as anticarcinogenic agents.

"Neapolitan limmo" is an ancient and rare sweet Mediterranean lime, now almost extinct but used until a few decades ago for the production of a fragrant liqueur called the "four citrus fruits". The objective of this work was to compare, through the use of chemical (flavonoids, volatile organic compounds, and chiral compounds) and molecular (DNA fingerprint based on RAPD-PCR) markers, the residual population of Neapolitan limmo with other populations of sweet limes, identified in Calabria and known as "lemoncetta Locrese". We report for the first time specific botanical characteristics of the two fruits and unequivocally show that the ancient sweet Mediterranean limes Neapolitan limmo and lemoncetta Locrese are synonyms of the same Citrus species. Owing to the biodiversity conserved in their places of origin, it will now be possible to recover, enhance and implement the use of this ancient sweet lime for agro-industrial purposes.

Fennel crop has been traditionally used as spice in cooking and fragrances, and in folk medicine for its spectrum of useful properties. Mediterranean is the elective natural cultivation area for this plant with Italy being a leader producer. A limit of this production is due to the high amount of wastes derived still rich of phytochemicals, which are usually underused. Hence, the extraction and characterization of essential oil from residues of fennel horticultural market was investigated to understand the potential profit of their recycling. Forty-eight compounds resulted for fennel oil waste, analysed by GC-FID-MS, with the most abundant among components was anethole. Other constituents contributing to fennel flavour were the monoterpenes limonene and nerol. The exploitation of this oil as a good source of bioactive compounds was assessed by means of its antioxidant power measured with DPPH test.

Quaternary ammonium compounds containing N-trimethylamino moiety, such as choline derivatives and carnitine, abundant in meat and dairy products, are metabolic precursors of trimethylamine (TMA). A similar fate is reported for N ε -trimethyllysine and γ-butyrobetaine. With the aim at investigating the metabolic profile of such metabolites in most employed animal dietary sources, HPLC-ESI-MS/MS analyses on ruminant and non-ruminant milk and meat were performed. Results demonstrate, for the first time, the presence of δ-valerobetaine, occurring at levels higher than γ-butyrobetaine in all ruminant samples compared to non-ruminants. Demonstration of δ-valerobetaine metabolic origin, surprisingly, showed that it originates from rumen through the transformation of dietary N ε -trimethyllysine. These results highlight our previous findings showing the ubiquity of free N ε -trimethyllysine in vegetable kingdom. Furthermore, δ-valerobetaine, similarly to γ-butyrobetaine, can be degraded by host gut microbiota producing TMA, precursor of the proatherogenic trimethylamine N-oxide (TMAO), unveiling its possible role in the biosynthetic route of TMAO., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Ophthalmic acid (OPH), γ-glutamyl-L-2-aminobutyryl-glycine, a tripeptide analogue of glutathione (GSH), has recently captured considerable attention as a biomarker of oxidative stress in animals. The OPH and GSH biosynthesis, as well as some biochemical behaviors, are very similar. Here, we sought to investigate the presence of OPH in plants and its possible relationship with GSH, known to possess multiple functions in the plant development, growth and response to environmental changes., Methods: HPLC-ESI-MS/MS analysis was used to examine the occurrence of OPH in leaves from various plant species, and flours from several plant seeds. Different types of oxidative stress, i.e., water, dark, paraquat, and cadmium stress, were induced in rye, barley, oat, and winter wheat leaves to evaluate the effects on the levels of OPH and its metabolic precursors., Results: OPH and its dipeptide precursor, γ-glutamyl-2-aminobutyric acid, were found to occur in phylogenetically distant plants. Interestingly, the levels of OPH were tightly associated with the oxidative stress tested. Levels of OPH precursors, γ-glutamyl-2-aminobutyric acid and 2-aminobutyric acid, the latter efficiently formed in plants via biosynthetic pathways absent in the animal kingdom, were also found to increase during oxidative stress., Conclusions: OPH occurs in plants and its levels are tightly associated with oxidative stress., General Significance: OPH behaves as an oxidative stress marker and its biogenesis might occur through a biochemical pathway common to many living organisms., (Copyright © 2018 Elsevier B.V. All rights reserved.)

We report the LC-ESI-MS/MS determination of betaines in commercial flours of cereals and pseudocereals most utilized in human nutrition. Results showed that glycine betaine, trigonelline, proline betaine, N ε -trimethyllysine were metabolites common to all examined flours, whereas an uncommon betaine, valine betaine, and glutamine betaine were present only in flours of barley, rye, oat, durum wheat, winter wheat, Triticum dicoccum and Triticum monococcum. Valine betaine and glutamine betaine, the latter never reported before in plants and animals, are not evenly distributed in the Poaceae family, but their presence or absence in flours depends on the subfamily to which the plant belongs. Interestingly, we also report for the first time the occurrence of pipecolic acid betaine (homostachydrine) and its precursor 1,2-N-methylpipecolic acid in rye flour. These two metabolites were not detected in any other cereal or pseudocereal flour, suggesting their potential role as markers of rye flour occurrence in cereal-based foods., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Ergothioneine (Egt), 2-mercapto-L-histidine betaine (ESH), is a dietary component acting as antioxidant and cytoprotectant. In vitro studies demonstrated that Egt, a powerful scavenger of hydroxyl radicals, superoxide anion, hypochlorous acid and peroxynitrite, protects vascular function against oxidative damages, thus preventing endothelial dysfunction. In order to delve the peculiar oxidative behavior of Egt, firstly identified in cell free-systems, experiments were designed to identify the Egt oxidation products when endothelial cells (EC) benefit of its protection against high-glucose (hGluc). HPLC-ESI-MS/MS analyses revealed a decrease in the intracellular GSH levels and an increase in the ophthalmic acid (OPH) levels during hGluc treatment. Interestingly, in the presence of Egt, the decrease of the GSH levels was lower than in cells treated with hGluc alone, and this effect was paralleled by lower OPH levels. Egt was also effective in reducing the cytotoxicity of H 2 O 2 and paraquat (PQT), an inducer of superoxide anion production, showing a similar time-dependent pattern of GSH and OPH levels, although with peaks occurring at different times. Importantly, Egt oxidation generated not only hercynine (EH) but also the sulfonic acid derivative (ESO 3 H) whose amounts were dependent on the oxidative stress employed. Furthermore, cell-free experiments confirmed the formation of both EH and ESO 3 H when Egt was reacted with superoxide anion. In summary, these data, by identifying the EH and ESO 3 H formation in EC exposed to hGluc, highlight the cellular antioxidant properties of Egt, whose peculiar redox behavior makes it an attractive candidate for the prevention of oxidative stress-associated endothelial dysfunction during hyperglycemia., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Plant tryptophan decarboxylase (TDC) converts tryptophan into tryptamine, precursor of indolealkylamine alkaloids. The recent finding of tryptamine metabolites in Citrus plants leads to hypothesize the existence of TDC activity in this genus. Here, we report for the first time that, in Citrus x limon seedlings, deuterium labeled tryptophan is decarboxylated into tryptamine, from which successively deuterated N , N , N -trimethyltryptamine is formed. These results give an evidence of the occurrence of the TDC activity and the successive methylation pathway of the tryptamine produced from the tryptophan decarboxylation. In addition, with the aim to identify the genetic basis for the presence of TDC, we carried out a sequence similarity search for TDC in the Citrus genomes using as a probe the TDC sequence reported for the plant Catharanthus roseus . We analyzed the genomes of both Citrus clementina and Citrus sinensis , available in public database, and identified putative protein sequences of aromatic l-amino acid decarboxylase. Similarly, 42 aromatic l-amino acid decarboxylase sequences from 23 plant species were extracted from public databases. Potential sequence signatures for functional TDC were then identified. With this research, we propose for the first time a putative protein sequence for TDC in the genus Citrus .

Glucosylated forms of tyramine and some of its N-methylated derivatives are here reported for the first time to occur in Citrus genus plants. The compounds tyramine-O-β-d-glucoside, N-methyltyramine-O-β-d-glucoside, and N,N-dimethyltyramine-O-β-d-glucoside were detected in juice and leaves of sweet orange, bitter orange, bergamot, citron, lemon, mandarin, and pomelo. The compounds were identified by mass spectrometric analysis, enzymatic synthesis, and comparison with extracts of Stapelia hirsuta L., a plant belonging to the Apocynaceae family in which N,N-dimethyltyramine-O-β-d-glucoside was identified by others. Interestingly, in Stapelia hirsuta we discovered also tyramine-O-β-d-glucoside, N-methyltyramine-O-β-d-glucoside, and the tyramine metabolite, N,N,N-trimethyltyramine-O-β-glucoside. However, the latter tyramine metabolite, never described before, was not detected in any of the Citrus plants included in this study. The presence of N-methylated tyramine derivatives and their glucosylated forms in Citrus plants, together with octopamine and synephrine, also deriving from tyramine, supports the hypothesis of specific biosynthetic pathways of adrenergic compounds aimed to defend against biotic stress.

The development of efficient charge transport layers is a key requirement for the fabrication of efficient and stable organic solar cells. A graphene-based derivative with planar resistivity exceeding 10(5) Ω/□ and work function of 4.9 eV is here produced by finely tuning the parameters of the chemical vapor deposition process on copper. After the growth, the film is transferred to glass/indium tin oxide and used as hole transport layer in organic solar cells based on a PBDTTT-C-T:[70]PCBM blend. The cells attained a maximum power conversion efficiency of 5%, matching reference cells made with state-of-the-art, Pedot: PSS as the hole transport layer. Our results indicate that functionalized graphene could represent an effective alternative to, Pedot: PSS as hole transport/electron blocking layer in solution-processed organic photovoltaics.

The occurrence of pipecolic acid betaine (homostachydrine) and its biosynthetic precursor N-methylpipecolic acid was detected for the first time in green coffee beans of Robusta and Arabica species. The analyses were conducted by HPLC-ESI tandem mass spectrometry and the metabolites identified by product ion spectra and comparison with authentic standards. N-methylpipecolic acid was found at similar levels in green coffee beans of Robusta and Arabica, whereas a noticeable difference of homostachydrine content was observed between the two green coffee bean species. Interestingly, homostachydrine content was found to be unaffected by coffee bean roasting treatment because of a noticeable heat stability, a feature that makes this compound a candidate marker to determine the content of Robusta and Arabica species in roasted coffee blends. To this end, a number of certified pure Arabica and Robusta green beans were analyzed for their homostachydrine content. Results showed that homostachydrine content was 1.5±0.5mg/kg in Arabica beans and 31.0±10.0mg/kg in Robusta beans. Finally, to further support the suitability of homostachydrine as quality marker of roasted blends of Arabica and Robusta coffee beans, commercial samples of roasted ground coffee blends were analyzed and the correspondence between the derived percentages of Arabica and Robusta beans with those declared on packages by manufacturers was verified., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Chestnut fruits, being poor of simple sugars and consisting mainly of fibers and starch, are among the constituents of Mediterranean diet. While numerous studies report on content of proteins and amino acids in chestnut, no one has appeared so far on betaines, an important class of nitrogen compounds ubiquitous in plants for their protective action in response to abiotic stress. In this study, we analyzed by HPLC-ESI-tandem mass spectrometry, in fruits and flours of varieties of chestnut cultivated in Italy, the composition of betaines and ammonium compounds intermediates of their biosynthesis. Besides the parent amino acids, the compounds quantified were choline, glycerophosphocholine, phosphocholine, glycine betaine, N-methylproline, proline betaine (stachydrine), β-alanine betaine, 4-guanidinobutyric acid, trigonelline, N,N,N-trimethyllysine. Interestingly, some uncommon derivatives of pipecolic acid, such as N-methylpipecolic acid, 4-hydroxypipecolic acid and 4-hydroxy-N-methylpipecolic acid were identified for the first time in chestnut samples and characterized by MS(n) tandem mass spectrometry., (Copyright © 2015 Elsevier Ltd. All rights reserved.)