Time Domain NMR Approach in the Chemical and Physical Characterization of Hazelnuts (Corylus avellana L.).

'Tonda Gentile Romana' and 'Tonda di Giffoni' (Corylus avellana L.) are two Italian hazelnut cultivars, recognized under the quality labels "Protected Designation of Origin" (PDO) and "Protected Geographical Indication" (PGI), respectively. Hazelnut seeds are characterized by a complex microstructure and the presence of different physical compartments. This peculiarity has been studied and evidenced by Time Domain (TD) Nuclear Magnetic Resonance (NMR) experiments. This technique allowed the assessment of the presence of different diffusion compartments, or domains, by evaluating the distribution of the spin-spin relaxation time (T2).The aim of this research was to develop a method based on 1H NMR relaxometry to study the mobility in fresh hazelnut seeds ('Tonda di Giffoni' and 'Tonda Gentile Romana'), in order to determine differences in seed structure and matrix mobility between the two cultivars. TD-NMR measurements were performed from 8 to 55 °C in order to mimic post-harvest processing as well the microscopic textural properties of hazelnut. The Carr-Purcell-Meiboom-Gill (CPMG) experiments showed five components for 'Tonda Gentile Romana' and four components for 'Tonda di Giffoni' relaxation times. The two slowest components of relaxation (T2,a about 30-40% of the NMR signal, and T2,b about 50% of the NMR signal) were attributed to the protons of the lipid molecules organized in the organelles (oleosomes), both for the 'Tonda Gentile Romana' and for the 'Tonda di Giffoni' samples. The component of relaxation T2,c was assigned to cytoplasmic water molecules, and showed a T2 value dominated by diffusive exchange with a reduced value compared to that of pure water at the same temperature. This can be attributed to the water molecules affected by the relaxation effect of the cell walls. The experiments carried out as a function of temperature showed, for 'Tonda Gentile Romana', an unexpected trend between 30 and 45 °C, indicating a phase transition in its oil component. This study provides information that could be used to strengthen the specifications underlying the definitions of "Protected Designation of Origin" (PDO) and "Protected Geographical Indication" (PGI).

Valorization Potentials of Rapeseed Meal in a Biorefinery Perspective: Focus on Nutritional and Bioactive Components.

Rapeseed meal (RSM), a by-product of oilseed extraction connected to the agri-food and biofuel sectors, is currently used as animal feed and for other low-value purposes. With a biorefinery approach, RSM could be valorized as a source of bio-based molecules for high-value applications. This study provides a chemical characterization of RSM in the perspective of its valorization. A qualitative study of main functional groups by fourier transform infrared (FTIR) spectroscopy was integrated with a chemical characterization of macronutrients, minerals by inductively coupled plasma optical emission spectrometry (ICP-OES), phenolic acids and lipid components by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), HPLC-diode-array detector (HPLC-DAD) and gas chromatography-mass spectrometry/flame ionization detector (GC-MS/FID). The study, conducted on different lots of RSM collected over a one-year period from an oil pressing factory serving a biofuel biorefinery, highlighted a constant quality over time of RSM, characterized by high protein (31-34%), fiber (33-40%) and mineral (5.5-6.8%) contents. Polyphenol extracts showed a significant antioxidant activity and a prevalence of sinapic acid, accounting for more than 85% of total phenolic acids (395-437 mg kg-1 RSM). Results highlight the potentialities of RSM for further valorization strategies that may lead to the creation of new cross-sector interconnections and bio-based value chains with improvement of the economics and sustainability of the bioeconomy sectors involved.

Dietary Antioxidants and Metabolic Diseases.

Introduction [...].

Fruit Wastes as a Valuable Source of Value-Added Compounds: A Collaborative Perspective.

The by-products/wastes from agro-food and in particular the fruit industry represents from one side an issue since they cannot be disposed as such for their impact on the environment but they need to be treated as a waste. However, on the other side, they are a source of bioactive healthy useful compounds which can be recovered and be the starting material for other products in the view of sustainability and a circular economy addressing the global goal of "zero waste" in the environment. An updated view of the state of art of the research on fruit wastes is here given under this perspective. The topic is defined as follows: (i) literature quantitative analysis of fruit waste/by-products, with particular regards to linkage with health; (ii) an updated view of conventional and innovative extraction procedures; (iii) high-value added compounds obtained from fruit waste and associated biological properties; (iv) fruit wastes presence and relevance in updated databases. Nowadays, the investigation of the main components and related bioactivities of fruit wastes is being continuously explored throughout integrated and multidisciplinary approaches towards the exploitation of emerging fields of application which may allow to create economic, environmental, and social value in the design of an eco-friendly approach of the fruit wastes.

Sodium Intake and Related Diseases.

Moderation in the use of salt (sodium chloride) in food and food preparations prevents the tendency of blood pressure to increase with age, and this is documented by many studies in current literature [...].

Sodium Intake and Related Diseases 2.0.

Many statements have been reported in literature from various sources warning of the possible risk to health connected to high salt (as sodium chloride) intake in the everyday diet, and it is increasingly pressing [...].

Corn Bioethanol Side Streams: A Potential Sustainable Source of Fat-Soluble Bioactive Molecules for High-Value Applications.

This paper reports data from a characterization study conducted on the unsaponifiable lipid fraction of dry-grind corn bioethanol side streams. Phytosterols, squalene, tocopherols, tocotrienols, and carotenoids were quantified by High Performance Liquid Chromatography with Diode-Array Detector (HPLC-DAD) and Liquid Chromatography-tandem Mass Spectrometry (LC-MS/MS) in different lots of post-fermentation corn oil and thin stillage collected from a bioethanol plant over a time-span of one year. Fat-soluble bioactives were present at high levels in corn oil, with a prevalence of plant sterols over tocols and squalene. Beta-sitosterol and sitostanol accounted altogether for more than 60% of total sterols. The carotenoid profile was that typical of corn, with lutein and zeaxanthin as the prevalent molecules. The unsaponifiable lipid fraction profile of thin stillage was qualitatively similar to that of post-fermentation corn oil but, in quantitative terms, the amounts of valuable biomolecules were much lower because of the very high dilution of this side stream. Results indicate that post-fermentation corn oil is a promising and sustainable source of health-promoting bioactive molecules. The concomitant presence of a variegate complex of bioactive molecules with high antioxidant potentialities and their potential multifaceted market applications as functional ingredients for food, nutraceutical, and cosmeceutical formulations, make the perspective of their recovery a promising strategy to create new bio-based value chains and maximize the sustainability of corn dry-grind bioethanol biorefineries.

Towards a Valorization of Corn Bioethanol Side Streams: Chemical Characterization of Post Fermentation Corn Oil and Thin Stillage.

First-generation biofuel biorefineries may be a starting point for the development of new value chains, as their by-products and side streams retain nutrients and valuable molecules that may be recovered and valorized for high-value applications. This study provides a chemical characterization of post-fermentation corn oil and thin stillage, side streams of dry-grind corn bioethanol production, in view of their valorization. An overall long-term study was conducted on the two co-products collected over 1 year from a bioethanol plant. Water content, acid value, sedimentation, mineral composition, and fatty acid profiles were analyzed on post-fermentation corn oil. Results highlighted that its acid value was high (19.72-24.29 mg KOH/g), indicating high levels of free fatty acids, but stable over the year due to standardized operating conditions. The fatty acid profile was that typical of corn oil, with a prevalence of linoleic (54-59% of total fatty acids) over oleic (23-27%) and palmitic (12-17%) acids. Macronutrients, fatty acid, and mineral profiles were investigated in thin stillage. Results revealed the acidic pH (4.05-4.68) and high dilution (90-93% water) of this side stream. The dry mass was composed of fats (19-30%), proteins (8.8-12.8%), ash (8.7-9.5%), and fiber (7.3-9.8%). The concomitant presence of a variegate complex of molecules of nutritional interest in corn bioethanol co-products, with several potential high-value market applications, make the perspective of their recovery a promising strategy to create new cross-sector interconnections according to circular economy principles.

NMR-Based Metabolomic Comparison of Brassica oleracea (Var. italica): Organic and Conventional Farming.

Brassicaceae family provides several crops which are worldwide known for their interesting phytochemical profiles, especially in terms of content of glucosinolates. These secondary metabolites show several beneficial effects toward consumers' health, and several studies have been conducted to identify cultivation factors affecting their content in crops. One of the agronomic practices which is attracting growing interest is the organic one, which consists in avoiding the use of mineral fertilizers as well as pesticides. The aim of this study is to define the metabolic profile of Brassica oleracea (var. italica) and to compare the samples grown using organic and conventional fertilization methods. The hydroalcoholic and organic extracts of the samples have been analyzed by NMR spectroscopy. Forty-seven metabolites belonging to the categories of organic acids, amino acids, carbohydrates, fatty acids, sterols, and other molecules have been identified. Thirty-seven metabolites have been quantified. Univariate and multivariate PCA analyses allowed to observe that the organic practice influenced the nitrogen transport, the carbohydrate metabolism, the glucosinolate content and the phenylpropanoid pathway in B. oleracea (var. italica).

Stability of the Meat Protein Type I Collagen: Influence of pH, Ionic Strength, and Phenolic Antioxidant.

The water-holding capacity (WHC) is among the key factors in determining the quality of meat and its value, which is strongly influenced by the content and quality of the connective tissue proteins like collagen. Therefore, the factors that influence the proteins' stability, e.g., pH, ionic strength, and the antioxidants which are used to increase the meat shelf-life, also affect the WHC. The interaction of collagen, whose structure is strongly influenced by the interaction with water molecules, can be studied following the behavior of water diffusion by low-resolution 1H NMR experiments. The present study is addressed to study the collagen stability as a function of pH, ionic strength, and phenolic antioxidants like catechin. The experimental study demonstrated how the 1H NMR time domain (TD) experiments are able to evaluate the hydration properties of collagen, not only as a function of ionic strength and pH, but also in determining the ability of catechin to interact both on the surface of the collagen fibrils and inside the fibrillar domain.

Role of catechin on collagen type I stability upon oxidation: a NMR approach.

The study focuses on the understanding, at molecular level, the mechanism of interaction between protein and flavonoids. Collagen and catechin interactions were investigated by NMR in solution and solid state. The effect of catechin on the stability of collagen to oxidation was also explored. Collagen was treated with two concentrations of catechin solutions. Oxidation was carried out by incubation of collagen solution with three oxidation systems: Fe(II)/H2O2, Cu(II)/H2O2, and NaOCl/H2O2. The effects of oxidation systems were evaluated by high resolution 1 D and 2 D proton spectroscopy and solid state NMR (13C CP MAS) experiments. Interactions between collagen and catechin preferentially occur between catechin B ring and the amino acids Pro and Hyp of collagen. Results showed that both iron and copper oxidation systems were able to interact with collagen by site specific attack. Moreover, catechin protects collagen proline from oxidation by metal/H2O2 systems, preventing copper and iron approach to collagene molecule;this behaviour was more evident for the copper/H2O2 system.

Grape Seeds: Chromatographic Profile of Fatty Acids and Phenolic Compounds and Qualitative Analysis by FTIR-ATR Spectroscopy.

The primary product of the oenological sector is wine. Nonetheless, the grape processing produces large amounts of by-products and wastes, e.g., the grape seeds. In the context of a sustainable production, there is a strong push towards reutilizing these by-products and waste for making useful derivatives since they are rich of bioactive substances with high additional value. As it is true for the wine itself, bringing these by-products derivatives to the market calls for quality measures and analytical tools to assess quality itself. One of the main objectives is to collect analytical data regarding bioactive compounds using potentially green techniques. In the present work, the profile of fatty acids and the main phenolic compounds were investigated by conventional methods. The qualitative analysis of the main functional groups was carried out by Fourier Transform Infrared (FTIR) spectroscopy. Moreover, the successful use of FTIR technique in combination with chemometric data analysis is shown to be a suitable analytical tool for discriminating the grape seeds. Grape seeds of different origin have different content of bioactive substances, making this technique useful when planning to recover a certain substance with specific potential application in health area as food supplement or nutraceutical. For example, Cesanese d'Affile seeds were found to have a rather high fat content with a significant fraction of unsaturated fatty acids. On the other hand, the seeds of Nero d'Avola exhibit the highest amount of phenolic compounds.

Carotenoid profiling of five microalgae species from large-scale production.

The carotenoid profiles of biomass from five eukaryotic microalgae, Porphyridium cruentum, Isochrysis galbana, Phaeodactylum tricornutum, Tetraselmis suecica and Nannochloropsis gaditana, produced at an industrial plant in outdoor photobioreactors, were investigated. Pigments were solvent-extracted after an ultrasonic pre-treatment and separated by HPLC-photodiode-array using a reversed-phase C18 column. Microalgae showed species-specific carotenoid profiles. Carotenoids were mostly in their free form, with a prevalence of xanthophylls over carotenes. Beta-carotene was the only carotenoid common to all species. The Rhodophyta P. cruentum exhibited the lowest total carotenoid content (167.2 mg 100 g-1 dw) and the simplest profile, with (all-E)-zeaxanthin (94.2 mg 100 g-1 dw, 56% of total carotenoids) and (all-E)-ß- carotene (53.4 mg 100 g-1 dw, 32% of total carotenoids) as the major carotenoids. The Haptophyta Isochrysis galbana and the Bacillariophyta Phaeodactylum tricornutum were the species with the highest total carotenoid content (1760 mg and 1022 mg 100 g-1 dw, respectively). These species were characterized by similar carotenoid profiles, with (all-E)-fucoxanthin as the chief compound (1346 mg and 776.8 mg 100 g-1 dw for I. galbana and P. tricornutum, respectively), accounting for about 76% of total carotenoids. The Chlorophyta Tetraselmis suecica was the species showing the greatest variety of carotenoids, with both α- carotene and ß- carotene and their derivatives present. (All-E)-lutein (85.4 mg 100 g-1 dw) and (all-E)-violaxanthin (81.8 mg 100 g-1 dw) were the major pigments in this species. In the Ochrophyta Nannochloropsis gaditana, (all-E)-violaxanthin was the prevalent carotenoid (336.7 mg 100 g-1 dw), followed by (all-E)-ß-carotene (100.1 mg 100 g-1 algal dw). The carotenoid content of the microalgal biomass studied compared favourably to that of major vegetable sources. Due to their characteristics, these microalgae, most of them currently finding their main application in aquaculture, may be also regarded as valuable sources of carotenoids to be used in the formulation of functional food and nutraceuticals.

Bio-Based Compounds from Grape Seeds: A Biorefinery Approach.

Food and agricultural waste represents a growing problem with negative effects on the economy, environment, and human health. Winemaking produces byproducts with high added value, which can be used for new productions in several application fields. From the perspective of biorefinery and circular economy, grape seeds could be exploited by extracting bioactive compounds with high added value before using biomass for energy purposes. The markets concerned are, in addition to the food, cosmetics, and pharmaceuticals sectors, which use bioactive compounds, the sector of biopolymeric materials and of energy for the production of biohydrogen and biomethane. Generally, bioactive components should be investigated through an integrated and multidisciplinary study approach based on emerging analytical techniques; in this context, attention is addressed towards green and sustainable procedures; an update of extraction techniques, innovative technologies, and chemometrics are described. Nowadays, processes so far tested on a pilot scale for grape waste are developed to enhance the extraction yields. Here, a picture of the Italian experience applied to the byproducts of the wine industry is given.

A conceptual framework for the collection of food products in a Total Diet Study.

A total diet study (TDS) provides representative and realistic data for assessing the dietary intake of chemicals, such as contaminants and residues, and nutrients, at a population level. Reproducing the diet through collection of customarily consumed foods and their preparation as habitually eaten is crucial to ensure representativeness, i.e., all relevant foods are included and all potential dietary sources of the substances investigated are captured. Having this in mind, a conceptual framework for building a relevant food-shopping list was developed as a research task in the European Union's 7th Framework Program project, 'Total Diet Study Exposure' (TDS-Exposure), aimed at standardising methods for food sampling, analyses, exposure assessment calculations and modelling, priority foods, and selection of chemical contaminants. A stepwise approach following the knowledge translation (KT) model for concept analysis is proposed to set up a general protocol for the collection of food products in a TDS in terms of steps (characterisation of the food list, development of the food-shopping list, food products collection) and pillars (background documentation, procedures, and tools). A simple model for structuring the information in a way to support the implementation of the process, by presenting relevant datasets, forms to store inherent information, and folders to record the results is also proposed. Reproducibility of the process and possibility to exploit the gathered information are two main features of such a system for future applications.

The Potential Health Benefits of Polyphenol-Rich Extracts from Cichorium intybus L. Studied on Caco-2 Cells Model.

Phytochemicals can exert their bioactivity without reaching the systemic circulation; scarcely absorbed antioxidants might reach the large bowel contributing to protection from oxidative damage-induced gastrointestinal diseases. In the present work, we aimed to study the relationship between potential activity of polyphenol-rich extracts from Cichorium intybus L. and changes in morphological characteristics on Caco-2 cells. Phytochemicals content (carotenoids and flavonoids) and total antioxidant activity of Red Chicory of Treviso and Variegated Chicory of Castelfranco were evaluated. The bioactivity of polyphenol-rich extracts from chicories was studied in in vitro Caco-2 cell monolayers model. Morphological characteristics changes to test the antioxidant and/or prooxidant effect were verified by histological analysis and observed by Electronic Scansion Microscopy (SEM). On Caco-2 cell model, the polyphenols fractions from chicories have indicated a moderate antioxidant behavior until 17 µM concentration, while 70 µM and 34 µM exert cytotoxic effects for Treviso's and Castelfranco's Chicory, respectively, highlighted by TEER decreasing, increased permeability, and alteration of epithelium. Our findings support the beneficial effects of these products in counteracting the oxidative stress and cellular damage, induced in vitro on Caco-2 cell model, through interaction with the mucopolysaccharide complexes in the glycocalyx, maintaining in vivo a healthy and effective intestinal barrier.

Red chicory (Cichorium intybus L. cultivar) as a potential source of antioxidant anthocyanins for intestinal health.

Fruit- and vegetable-derived foods have become a very significant source of nutraceutical phytochemicals. Among vegetables, red chicory (Cichorium Intybus L. cultivar) has gained attention for its content of phenolic compounds, such as the anthocyanins. In this study, we evaluated the nutraceutical effects, in terms of antioxidant, cytoprotective, and antiproliferative activities, of extracts of the whole leaf or only the red part of the leaf of Treviso red chicory (a typical Italian red leafy plant) in various intestinal models, such as Caco-2 cells, differentiated in normal intestinal epithelia and undifferentiated Caco-2 cells. The results show that the whole leaf of red chicory can represent a good source of phytochemicals in terms of total phenolics and anthocyanins as well as the ability of these phytochemicals to exert antioxidant and cytoprotective effects in differentiated Caco-2 cells and antiproliferative effects in undifferentiated Caco-2 cells. Interestingly, compared to red chicory whole leaf extracts, the red part of leaf extracts had a significantly higher content of both total phenolics and anthocyanins. The same extracts effectively corresponded to an increase of antioxidant, cytoprotective, and antiproliferative activities. Taken together, these findings suggest that the red part of the leaf of Treviso red chicory with a high content of antioxidant anthocyanins could be interesting for development of new food supplements to improve intestinal health.

Micronutrients in Italian ham: a survey of traditional products.

The study provides original analytical data on the micronutrient profile of some traditional Italian hams, representative of the major ham categories produced in Italy: 4 dry-cured hams (Modena, Nazionale, Parma, San Daniele), 3 cooked hams (Cotto, Scelto, Alta Qualità), 1 smoked ham (Speck). Data on macronutrients (protein, lipid, moisture), energy, trace elements (Fe, Zn, Cu, Mn, Se), B vitamins (B1, B2, PP, B6, B12) and vitamin E level in the 80 Italian hams sampled are reported. Smoked and dry-cured ham were the richest sources of Fe, Zn and Se and, among vitamins, dry-cured ham had the highest level of B2, PP, B6 and B12; cooked ham provided the lowest energy intake. The contribution of ham to micronutrients recommended dietary allowances was estimated: a ham portion (50g) was a good source especially of Zn and Se providing over 12% of RDA of both; among B vitamins, dry-cured ham greatly contributed to B1 and B6 vitamins RDA (both over 30%).

Influence of Heat Treatments on Carotenoid Content of Cherry Tomatoes.

Tomatoes and tomato products are rich sources of carotenoids-principally lycopene, followed by ß-carotene and lutein. The aim of this work was to study the effect of heat treatment on carotenoid content in cherry tomatoes. Raw and canned products were sampled and analysed; furthermore whole, skin and pulp fractions of cherry tomatoes were analysed when raw and home-processed, in order to better understand heat treatment effects. Lycopene content in canned tomatoes was two-fold higher than in raw tomatoes (11.60 mg/100 g versus 5.12 mg/100 g). Lutein and ß-carotene were respectively 0.15 mg/100 g and 0.75 mg/100 g in canned tomatoes versus 0.11 mg/100 g and 1.00 mg/100 g in raw tomatoes. For home-processed tomatoes, ß-carotene and lutein showed a content decrease in all thermally treated products. This decrease was more evident for ß-carotene in the skin fraction (-17%), while for lutein it was greater in the pulp fraction (-25%). Lycopene presented a different pattern: after heat treatment its concentration increased both in the whole and in pulp fractions, while in the skin fraction it decreased dramatically (-36%). The analysis of the isomers formed during the thermal treatment suggests that lycopene is rather stable inside the tomato matrix.

Influence of growing system on nitrate accumulation in two varieties of lettuce and red radicchio of Treviso.

BACKGROUND: Green leafy vegetables contribute greatly to the total intake of nitrates from the daily diet. This study evaluates the influence of different cultivation systems on nitrate accumulation in leafy vegetables. Two varieties of lettuce (Lactuca sativa L.) (Lattuga Romana, Foglia di Quercia) and two varieties of red radicchio of Treviso (Cychorium intibus L.) (Early, Late) were selected. Lettuce varieties were both organically and biodynamically grown; red radicchio varieties were conventionally grown both in the field and in spring water. RESULTS: Both lettuce varieties biodynamically grown accumulated 1.3-2 times less nitrate than the respective organically grown plants. The two lettuce varieties showed differences in nitrate accumulating capacity: Foglia di Quercia was almost three times richer in nitrate than Lattuga Romana. The traditional growing systems applied to the red radicchio of Treviso varieties strongly influenced nitrate accumulation in leaves, the Early variety having up to 15 times higher nitrate than the Late variety. CONCLUSIONS: Our findings on nitrate levels in both lettuce and red radicchio of Treviso varieties suggest that both genetic factors and cultivation systems strongly affect the nitrate accumulation capacity. This study also highlights how the cultivation strategy can reduce nitrate levels in leafy vegetables, suggesting the possibility of modulating the N supply along the harvesting time.