Enterolignans: from natural origins to cardiometabolic significance, including chemistry, dietary sources, bioavailability, and activity.

The enterolignans, enterolactone and enterodiol, the main metabolites produced from plant lignans by the gut microbiota, have enhanced bioavailability and activity compared to their precursors, with beneficial effects on metabolic and cardiovascular health. Although extensively studied, the biosynthesis, cardiometabolic effects, and other therapeutic implications of mammalian lignans are still incompletely understood. The aim of this review is to provide a comprehensive overview of these phytoestrogen metabolites based on up-to-date information reported in studies from a wide range of disciplines. Established and novel synthetic strategies are described, as are the various lignan precursors, their dietary sources, and a proposed metabolic pathway for their conversion to enterolignans. The methodologies used for enterolignan analysis and the available data on pharmacokinetics and bioavailability are summarized and their cardiometabolic bioactivity is explored in detail. The special focus given to research on the health benefits of microbial-derived lignan metabolites underscores the critical role of lignan-rich diets in promoting cardiovascular health.

Unlocking the potential of olive residues for functional purposes: update on human intervention trials with health and cosmetic products.

Olive mill waste (OMW) is a promising source of valuable compounds such as polyphenols, terpenes, sterols, and other bioactive compounds, which are of interest to the pharmaceuticals and cosmeceutical industries. This review examines the potential of OMW extracts for health and beauty applications based on evidence reports from human clinical trials. The results achieved to date indicate health-enhancing properties, but little is known about the underlying mechanisms of action, dose-response relationships, and long-term impacts. Therefore, while olive by-products, extracted using eco-friendly methods, present opportunities for the development of high-value health and cosmetic products, further studies are necessary to determine the full range of their effects and establish specific therapeutic strategies. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Recent advances in bio-based extraction processes for the recovery of bound phenolics from agro-industrial by-products and their biological activity.

Usually found bound to other complex molecules (e.g., lignin, hemicellulose), phenolic compounds (PC) are widely present in agro-industrial by-products, and their extraction is challenging. In recent times, research is starting to highlight the bioactive roles played by bound phenolics (BPC) in human health. This review aims at providing a critical update on recent advances in green techniques for the recovery of BPC, focusing on enzymatic-assisted (EAE) and fermentation-assisted extraction (FAE) as well as in the combination of technologies, showing variable yield and features. The present review also summarizes the most recent biological activities attributed to BPC extracts until now. The higher antioxidant activity of BPC-compared to FPC-coupled with their affordable by-product source make them medicinally potent and economically viable, promoting their integral upcycling and generating new revenue streams, business, and employment opportunities. In addition, EAE and FAE can have a biotransformative effect on the PC itself or its moiety, leading to improved extraction outcomes. Moreover, recent research on BPC extracts has reported promising anti-cancer and anti-diabetic activity. Yet further research is needed to elucidate their biological mechanisms and exploit the true potential of their applications in terms of new food products or ingredient development for human consumption.

Tomato wastes and by-products: upcoming sources of polyphenols and carotenoids for food, nutraceutical, and pharma applications.

Tomato pomace, a waste product consisting of peels, seeds, rich on fibrous matter, represents an underutilized source of bioactive compounds, such as polyphenols and carotenoids. Here we present a three-pronged review of the circular utilization of tomato waste in line with the United Nations Sustainable Development Goals. First, we explain why tomato waste is important, highlighting the processing techniques that generate it. The bioactive compounds in these by-products are then comprehensively reviewed, focusing especially on phenolic compounds and carotenoids and the methods used for their extraction. Finally, we examine the potential of these bioactive ingredients for application in food systems and pharmaceutical products.

Current strategies to guarantee the authenticity of coffee.

As they become more health conscious, consumers are paying increasing attention to food quality and safety. In coffee production, fraudulent strategies to reduce costs and maximize profits include mixing beans from two species of different economic value, the addition of other substances and/or foods, and mislabeling. Therefore, testing for coffee authenticity and detecting adulterants is required for value assessment and consumer protection. Here we provide an overview of the chromatography, spectroscopy, and single-nucleotide polymorphism-based methods used to distinguish between the major coffee species Arabica and Robusta. This review also describes the techniques applied to trace the geographical origin of coffee, based mainly on the chemical composition of the beans, an approach that can discriminate between coffee-growing regions on a continental or more local level. Finally, the analytical techniques used to detect coffee adulteration with other foods and/or coffee by-products are discussed, with a look at the practice of adding pharmacologically active compounds to coffee, and their harmful effects on health.

Traceability, authenticity and sustainability of cocoa and chocolate products: a challenge for the chocolate industry.

Cocoa beans, the seeds of the tree Theobroma cacao L., are the key raw material for chocolate production that implies an extensive post-harvest process. Chocolate properties can vary depending on cocoa origin, composition and manufacturing procedure, which will give unique sensory properties to the final product. On the other hand, the high global consumption of cocoa products, long recognized as a major source of dietary polyphenols with important health benefits, has increased interest in tracking the geographical origin of cocoa and authenticating chocolate to guarantee product quality and reveal possible commercial fraud. However, the sustainable production of high-quality cocoa is still far from reality, and the cocoa sector continues to face many challenges in this field. This review provides an update on the progress toward the authenticity, traceability and sustainability of cocoa products, issues that chocolate producers still need to resolve.

Extra virgin olive oil: A comprehensive review of efforts to ensure its authenticity, traceability, and safety.

The growing demand for extra virgin olive oil (EVOO), appreciated for its unique organoleptic properties and health benefits, has led to various fraudulent practices to maximize profits, including dilution with lower value edible oils. The adulterated oils would be of poor nutritional quality, more readily oxidized, and may contain unhealthy substances formed during processing. Nevertheless, the range of available techniques to detect fraud in EVOO production has been growing. Reliable markers of EVOO adulteration include fatty acids and minor components such as sterols, tocopherols, triterpene alcohols, phenolic compounds, phospholipids, volatile compounds, and pigments. Additionally, increasing consumer interest in high-quality EVOO has led to the development of robust scientific methods for its traceability. This review focuses on (i) the usefulness of certain compounds as markers of EVOO adulteration; (ii) the potential health risks of consuming adulterated EVOO; and (iii) reliable methods for the geographical traceability of olive oil. In conclusion, fraudulent production practices need to be detected to preserve the beneficial health effects of EVOO and to avoid the potential risks associated with ingesting substandard oil. In this work, as EVOO certification and regulatory framework limitations have already been extensively reviewed, we focus our attention on biomarkers that guarantee both the authenticity and traceability of oil, and consequently its health properties. When it is unavailable to obtain a high-resolution mass spectrometry full fingerprint, stigmastadienes and the sterolic profile are proposed as reliable markers.

High-resolution mass spectrometry (HRMS): Focus on the m/z values estimated by the Savitzky-Golay first derivative.

RATIONALE: The calculation of centroids from profile mass spectra is one of the very first steps in the processing of mass spectra. The output is a signal and a m/z value. We focus on the accuracy of the prediction of the centroids' m/z values. METHODS: A calculation based on the Savizky-Golay algorithm was evaluated on an Orbitrap mass spectrum. Reference m/z values were identified manually. Experimental centroids were extracted (1) automatically using our algorithm or the MSconvert algorithm and (2) manually using the Xcalibur software from Thermo. The three series of experimental m/z values were compared with the reference m/z values. RESULTS: Our algorithm improved the determination of the m/z values compared with MSconvert. However, no improvement was observed over Xcalibur. CONCLUSIONS: Our algorithm improved the automatic estimation of m/z values in the profile-to-centroid calculation. This is of importance when the goal is to determine raw compositions from the experimental m/z values. Nevertheless, the algorithms led to almost the same m/z values on a higher resolution mass spectrum.

Health-promoting properties of oleocanthal and oleacein: Two secoiridoids from extra-virgin olive oil.

Extra virgin olive oil (EVOO) polyphenols, including the secoiridoids oleocanthal (OLC) and oleacein (OLE), are attracting attention because of their beneficial effects on health. Data on OLC and OLE bioavailability are scarce, as most research on EVOO polyphenols has concentrated on hydroxytyrosol, tyrosol, and oleuropein. Consequently, relevant goals for future research are the elucidation of OLC and OLE bioavailability and finding evidence for their beneficial effects through pre-clinical and clinical studies. The aim of this review is to shed light on OLC and OLE, focusing on their precursors in the olive fruit and the impact of agronomic and processing factors on their presence in EVOO. Also discussed are their bioavailability and absorption, and finally, their bioactivity and health-promoting properties.

A Targeted Approach by High Resolution Mass Spectrometry to Reveal New Compounds in Raisins.

Raisins are dried grapes mostly obtained from cultivars of Vitis vinifera L. and are extensively consumed worldwide. They are rich in bioactive compounds such as polyphenols, which are associated with a broad range of health benefits. The aim of the present study was to compare the phenolic profiles of three different raisin varieties (Thompson seedless, Muscat, and sultanas). Total polyphenols (TPs) were evaluated by the Folin-Ciocalteu (F-C) assay and significant differences were observed among all raisin varieties. Furthermore, liquid chromatography coupled with electrospray ionization hybrid linear ion trap quadrupole-Orbitrap-mass spectrometry (LC/ESI-LTQ-Orbitrap-MS) was employed for the comprehensive identification of phenolic constituents. A total of 45 compounds were identified, including hydroxybenzoic and hydroxycinnamic acids, flavanoids, flavonoids, flavonols, flavones, and stilbenoids. The three varieties of raisins showed a similar phenolic profile, although the highest number of phenolic compounds was identified in Muscat raisins owing to the proanthocyanidins extracted from their seeds, while stilbenoids were not detected in the Thompson variety.

NMR spectroscopy: a powerful tool for the analysis of polyphenols in extra virgin olive oil.

Extra virgin olive oil (EVOO), a key component of the Mediterranean diet, has aroused interest in recent years due to its health properties. Nuclear magnetic resonance (NMR) spectroscopy is an appropriate tool for the accurate quantification of minor compounds in complex food matrices, such as polyphenols in olive oil. Flavonoids, lignans, secoiridoids and phenolic acids and alcohols in EVOO have been identified and quantified by NMR. This review provides an overview of the major developments in the structural elucidation of polyphenol compounds in EVOO. © 2019 Society of Chemical Industry.

Organic food and the impact on human health.

In the last decade, the production and consumption of organic food have increased steadily worldwide, despite the lower productivity of organic crops. Indeed, the population attributes healthier properties to organic food. Although scientific evidence is still scarce, organic agriculture seems to contribute to maintaining an optimal health status and decreases the risk of developing chronic diseases. This may be due to the higher content of bioactive compounds and lower content of unhealthy substances such as cadmium and synthetic fertilizers and pesticides in organic foods of plant origin compared to conventional agricultural products. Thus, large long-term intervention studies are needed to determine whether an organic diet is healthier than a diet including conventionally grown food products. This review provides an update of the present knowledge of the impact of an organic versus a conventional food diet on health.

Phenolic Profile of Grape Canes: Novel Compounds Identified by LC-ESI-LTQ-Orbitrap-MS.

Grape canes (Vitis vinifera L.) are a viticulture industry by-product with an important content of secondary metabolites, mainly polyphenols with a broad spectrum of demonstrated health benefits. Grape canes, therefore, have considerable economic potential as a source of high-value phytochemicals. In this work, liquid chromatography coupled with electrospray ionization hybrid linear trap quadrupole-Orbitrap mass spectrometry (LC-LTQ-Orbitrap) was used for the comprehensive identification of polyphenolic compounds in grape canes. Identification of polyphenols was performed by comparing their retention times, accurate mass measured, and mass fragmentation patterns with those of reference substances or available data in the literature. A total of 75 compounds were identified, including phenolic acids, flavanols, flavonols, flavanonols, flavanones, and stilbenoids. The most abundant polyphenols were proanthocyanidins and stilbenoids and their oligomers. Moreover, the high-resolution mass spectrometry analysis revealed the occurrence of 17 polyphenols never described before in grape canes, thereby providing a more complete polyphenolic profile of this potentially valuable by-product.

Effects of Organic and Conventional Growing Systems on the Phenolic Profile of Extra-Virgin Olive Oil.

Extra-virgin olive oil (EVOO) is largely appreciated for its proven nutritional properties. Additionally, organic foods are perceived as healthier by consumers. In this context, the aim of the present study was to compare the phenolic profiles of EVOO from olives of the Hojiblanca variety, cultivated under organic and conventional systems. The quantification and identification of individual polyphenols was carried out by liquid chromatography coupled to mass spectrometry in tandem mode (LC-MS/MS). Significantly higher levels (p < 0.05) of phenolic compounds were found in organic EVOOs. The methodology used was able to detect previously unreported differences in bioactive components between organic and conventional EVOOs.

Quantification of hydroxycinnamic derivatives in wines by UHPLC-MRM-MS.

A UHPLC-MS/MS method was developed for the quantification of the main compounds involved in oxidation reactions occurring in white musts and wines such as hydroxycinnamic acids, their glutathione and cysteinylglycine adducts (GRP, GRP2, 5-(S-glutathionyl)-trans-caftaric acid, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid), and reduced and oxidized glutathione (GSH, GSSG) in wine. Since oxidation is the main concern in white wine-making, directly affecting its quality, the developed method was then applied in a series of white wines made with different pre-fermentation treatments to limit oxidation at must stage. The glucose esters and/or glucosides of hydroxycinnamic acids were quantified as glucogallin equivalent. The developed method led to an overall improvement in the limits of detection (LODs) and quantification (LOQs) for all the compounds studied in comparison to other methods such as high-performance liquid chromatography with fluorescence detection (HPLC-FLD) or diode array UV detection (HPLC-DAD). LOD values ranged from 0.0002 to 0.0140 mg/L and LOQs from 0.0005 to 0.0470 mg/L. The recoveries ranged between 80 and 110% in wines, and the relative standard deviation (RSD) for precision intra- and inter-day was below 15%. The accuracy and intra- and inter-day precision met the acceptance criteria of the AOAC international norms. As far as we know, this study is the first report of quantification of GRP, 2-(S-cysteinylglycyl)-trans-caftaric acid, and 2-(S-glutathionyl)-trans-caffeic acid using these non-commercially available compounds as external standards. Those compounds represent a significant proportion of hydroxycinnamic acid derivatives in wines. The methodology described is suitable for the analysis of hydroxycinnamic derivatives in wines.

Italian and Spanish commercial tomato sauces for pasta dressing: study of sensory and head-space profiles by Flash Profiling and solid-phase microextraction-gas chomatography-mass spectrometry.

BACKGROUND: The sensory and head-space profiles of Italian and Spanish commercial tomato sauces were investigated. The Flash Profiling method was used to evaluate sensory characteristics. Samples within each set were ranked according to selected descriptors. One hundred volatile compounds were identified by solid-phase microextraction-gas chomatography-mass spectrometry. RESULTS: For Italian samples, the sensory notes of basil/aromatic herbs, acid and cooked tomato were among those perceived most by the assessors, whereas, in Spanish samples, the sensory attributes of garlic/onion and onion/sweet pepper and, in Italian samples, cooked tomato were among those found most frequently. Data were elaborated using multivariate statistical approaches and interesting correlations were observed among the different sensory attributes and related volatile compounds. CONCLUSION: Spanish samples were characterized by the highest content of volatiles linked to the thermal treatment of tomatoes and to raw and sautéed garlic and onion, whereas the Italian samples were characterized by terpenic compounds typical of basil and volatile molecules derived from fresh tomato. These results confirm the influence of both formulation and production processes on the aromatic profile (sensory attributes and volatile compounds) of tomato products, which is probably related to the different eating habits and culinary traditions in Italy and Spain. © 2016 Society of Chemical Industry.

Foodomics: A new tool to differentiate between organic and conventional foods.

The demand for organic food is increasing annually due to the growing consumer trend for more natural products that have simpler ingredient lists, involve less processing and are grown free of pesticides. However, there is still not enough nutritional evidence in favor of organic food consumption. Classical chemical analysis of macro- and micronutrients has demonstrated that organic crops are poorer in nitrogen, but clear evidence for other nutrients is lacking. Omics technologies forming part of the new discipline of foodomics have allowed the detection of possible nutritional differences between organic and conventional production, although many results remain controversial and contradictory. The main focus of this review is to provide an overview of the studies that use foodomics techniques as a tool to differentiate between organic and conventional production.

Synthesis, Identification, and Structure Elucidation of Adducts Formed by Reactions of Hydroxycinnamic Acids with Glutathione or Cysteinylglycine.

Grape polyphenols, especially hydroxycinnamic acids such as caftaric and caffeic acid, are prone to enzymatic oxidation reactions during the winemaking process, forming o-quinones and leading to color darkening. Glutathione is capable of trapping these o-quinones and thus limiting juice browning. In this study, the addition of glutathione or cysteinylglycine onto caftaric or caffeic acid o-quinones formed by polyphenoloxidase-catalyzed reactions was investigated by UPLC-DAD-ESIMS and NMR data analyses. Complete identification of adducts has been achieved via NMR data. The results confirmed that the favored reaction is the substitution of the sulfanyl group of cysteine at C-2 of the aromatic ring. Several minor isomers, namely, the cis-isomer of the 2-S adduct and trans-isomers of the 5-S and 6-S adducts, and the 2,5-di-S-glutathionyl adducts were also identified and quantified by qNMR. With the exception of 2-(S-glutathionyl)- and 2,5-di(S-glutathionyl)-trans-caftaric acid, these products had never been formally identified. In particular, the 5-S and 6-S derivatives are reported here for the first time. The first formal identification of 2-S cis-derivatives is also provided. Moreover, NMR and UPLC-DAD-ESIMS analysis showed that signature UV and MS spectra can serve as markers of the conformation and substitution position in the aromatic ring for each of the isomers.

p-Hydroxyphenyl-pyranoanthocyanins: An Experimental and Theoretical Investigation of Their Acid-Base Properties and Molecular Interactions.

The physicochemical properties of the wine pigments catechyl-pyranomalvidin-3-O-glucoside (PA1) and guaiacyl-pyranomalvidin-3-O-glucoside (PA2) are extensively revisited using ultraviolet (UV)-visible spectroscopy, dynamic light scattering (DLS) and quantum chemistry density functional theory (DFT) calculations. In mildly acidic aqueous solution, each cationic pigment undergoes regioselective deprotonation to form a single neutral quinonoid base and water addition appears negligible. Above pH = 4, both PA1 and PA2 become prone to aggregation, which is manifested by the slow build-up of broad absorption bands at longer wavelengths (λ ≥ 600 nm), followed in the case of PA2 by precipitation. Some phenolic copigments are able to inhibit aggregation of pyranoanthocyanins (PAs), although at large copigment/PA molar ratios. Thus, chlorogenic acid can dissociate PA1 aggregates while catechin is inactive. With PA2, both chlorogenic acid and catechin are able to prevent precipitation but not self-association. Calculations confirmed that the noncovalent dimerization of PAs is stronger with the neutral base than with the cation and also stronger than π-π stacking of PAs to chlorogenic acid (copigmentation). For each type of complex, the most stable conformation could be obtained. Finally, PA1 can also bind hard metal ions such as Al3+ and Fe3+ and the corresponding chelates are less prone to self-association.

A Fast and Robust UHPLC-MRM-MS Method to Characterize and Quantify Grape Skin Tannins after Chemical Depolymerization.

A rapid, sensitive, and selective analysis method using ultra high performance liquid chromatography coupled with triple-quadrupole mass spectrometry (UHPLC-QqQ-MS) has been developed for the characterization and quantification of grape skin flavan-3-ols after acid-catalysed depolymerization in the presence of phloroglucinol (phloroglucinolysis). The compound detection being based on specific MS transitions in Multiple Reaction Monitoring (MRM) mode, this fast gradient robust method allows analysis of constitutive units of grape skin proanthocyanidins, including some present in trace amounts, in a single injection, with a throughput of 6 samples per hour. This method was applied to a set of 214 grape skin samples from 107 different red and white grape cultivars grown under two conditions in the vineyard, irrigated or non-irrigated. The results of triplicate analyses confirmed the robustness of the method, which was thus proven to be suitable for high-throughput and large-scale metabolomics studies. Moreover, these preliminary results suggest that analysis of tannin composition is relevant to investigate the genetic bases of grape response to drought.