Comparative Volatilomic Profile of Three Finger Lime (Citrus australasica) Cultivars Based on Chemometrics Analysis of HS-SPME/GC-MS Data.

Finger lime is receiving growing attention as an ingredient of gastronomic preparations of haute cuisine for its delicious flavor and fragrance and for its appealing aspect. Volatile compounds play a crucial role in determining the organoleptic characteristics of the fruit and its pleasantness for consumers. The aim of the present study was to investigate the volatile profiles by headspace solid phase micro-extraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) in the peel and, for the first time, in the pulp of three Australian finger lime cultivars grown in Sicily (southern Italy): Pink Pearl, Sanguinea, and Faustrime, allowing to overall identify 84 volatile organic compounds (VOCs). The analytical data showed that the three cultivars were characterized by distinct volatile chemotypes: limonene/sabinene/bicyclogermacrene in the Pink Pearl, limonene/γ-terpinene/bicyclogermacrene in the Sanguinea, and limonene/ß-phellandrene/γ-terpinene in the Faustrime. Moreover, some volatiles, found exclusively in one cultivar, could be considered potential markers of the individual cultivar. PCA allowed us to clearly discriminate the samples into three clusters: the first related to the Sanguinea peel, the second to the Faustrime peel, and a third group associated with the Pink Pearl peel along with the pulp of the three cultivars. Accordingly, the VOCs that mostly contributed to the differentiation of the three finger lime cultivars were also identified. Among them, D-limonene, sabinene γ-terpinene, α-pinene, α-phellandrene, ß-myrcene, p-cymene, linalool, δ-elemene, ledene, bicyclogermacrene ß-citronellol, α-bergamotene, α-caryophillene, and ß-bisabolene, have been previously reported to exhibit important biological activities, suggesting that these cultivars, in addition to possessing unique volatile profiles, can show promise for several applications in pharmaceutical and food industry, namely for development of functional foods.

Valorisation, Green Extraction Development, and Metabolomic Analysis of Wild Artichoke By-Product Using Pressurised Liquid Extraction UPLC-HRMS and Multivariate Data Analysis.

Valorisation of food by-products has recently attracted considerable attention due to the opportunities to improve the economic and environmental sustainability of the food production chain. Large quantities of non-edible parts of the artichoke plant (Cynara cardunculus L.) comprising leaves, stems, roots, bracts, and seeds are discarded annually during industrial processing. These by-products contain many phytochemicals such as dietary fibres, phenolic acids, and flavonoids, whereby the most challenging issue concerns about the recovery of high-added value components from these by-products. The aim of this work is to develop a novel valorisation strategy for the sustainable utilisation of artichoke leaves' waste, combining green pressurised-liquid extraction (PLE), spectrophotometric assays and UPLC-HRMS phytochemical characterization, to obtain bioactive-rich extract with high antioxidant capacity. Multivariate analysis of the major selected metabolites was used to compare different solvent extraction used in PLE.

A comparative metabolomic investigation of different sections of Sicilian Citrus x limon (L.) Osbeck, characterization of bioactive metabolites, and evaluation of in vivo toxicity on zebrafish embryo.

Citrus fruits are a diverse and economically important group of fruit crops known for their distinctive flavors and high nutritional value. Their cultivation and consumption contribute significantly to the global agricultural economy and offer a wide range of health benefits. Among the genetic diversity of citrus species, Citrus x limon (L.) Osbeck is particularly relevant due to its chemical composition and potential health benefits. Two cultivars from the Sicily region (southern Italy) were compared for their phenolic content and preliminary antioxidant activity to select the distinctive extract with potential biological activity. A detailed characterization revealed the occurrence of phenolics, coumarins, and flavonoids. The quantification of metabolites contained in the selected extract was performed by an ultrahigh-performance liquid chromatographic method coupled with an ultraviolet detector. Different concentrations were tested in vivo through the fish embryo acute toxicity test, and the 50% lethal dose of 107,833 µg mL-1 was calculated. Finally, the effect of the extract on hatching was evaluated, and a dose-dependent relationship with the accelerated hatching rate was reported, suggesting a Femminello Zagara Bianca green peel upregulating effect on the hatching enzymes. PRACTICAL APPLICATION: Citrus fruits and their products continue to be one of the natural food sources with the highest waste output. In this study, we demonstrate how food industry waste, particularly lemon peel, is rich in bioactive compounds with anti-inflammatory and antioxidant properties that may be used in the nutraceuticals industry.

Convergent technologies to tackle challenges of modern food authentication.

The authentication process involves all the supply chain stakeholders, and it is also adopted to verify food quality and safety. Food authentication tools are an essential part of traceability systems as they provide information on the credibility of origin, species/variety identity, geographical provenance, production entity. Moreover, these systems are useful to evaluate the effect of transformation processes, conservation strategies and the reliability of packaging and distribution flows on food quality and safety. In this manuscript, we identified the innovative characteristics of food authentication systems to respond to market challenges, such as the simplification, the high sensitivity, and the non-destructive ability during authentication procedures. We also discussed the potential of the current identification systems based on molecular markers (chemical, biochemical, genetic) and the effectiveness of new technologies with reference to the miniaturized systems offered by nanotechnologies, and computer vision systems linked to artificial intelligence processes. This overview emphasizes the importance of convergent technologies in food authentication, to support molecular markers with the technological innovation offered by emerging technologies derived from biotechnologies and informatics. The potential of these strategies was evaluated on real examples of high-value food products. Technological innovation can therefore strengthen the system of molecular markers to meet the current market needs; however, food production processes are in profound evolution. The food 3D-printing and the introduction of new raw materials open new challenges for food authentication and this will require both an update of the current regulatory framework, as well as the development and adoption of new analytical systems.

LC-MS- and 1H NMR-Based Metabolomics to Highlight the Impact of Extraction Solvents on Chemical Profile and Antioxidant Activity of Daikon Sprouts (Raphanus sativus L.).

Currently, the interest of consumers towards functional foods as source of bioactive compounds is increasing. The sprouts of Raphanus sativus var longipinnatus (Brassicaceae) are "microgreens" popular, especially in gourmet cuisine, for their appealing aspect and piquant flavour. They represent a functional food due to their high nutritional value and health-promoting effects. Herein, the sprouts of daikon were extracted by different solvent mixtures to highlight how this process can affect the chemical profile and the antioxidant activity. An in-depth investigation based on a preliminary LC-ESI/LTQOrbitrap/MS profiling was carried out, leading to the identification of nineteen compounds, including glucosinolates and hydroxycinnamic acid derivatives. An undescribed compound, 1-O-feruloyl-2-O-sinapoyl-ß-D-glucopyranoside, was isolated, and its structure was elucidated by NMR spectroscopy. The phenolic content and radical scavenging activity (DPPH and TEAC assays), along with the ability to activate Nrf2 (Nrf2-mediated luciferase reporter gene assay) of polar extracts, were evaluated. The results showed the highest antioxidant activity for the 70% EtOH/H2O extract with a TEAC value of 1.95 mM and IC50 = 93.97 µg/mL in the DPPH assay. Some 50% and 70% EtOH/H2O extracts showed a pronounced concentration-dependent induction of Nrf2 activity. The extracts of daikon sprouts were submitted to 1H NMR experiments and then analyzed by untargeted and targeted approaches of multivariate data analysis to highlight differences related to extraction solvents.

LC-MS and GC-MS Data Fusion Metabolomics Profiling Coupled with Multivariate Analysis for the Discrimination of Different Parts of Faustrime Fruit and Evaluation of Their Antioxidant Activity.

The comparative chemical composition of different part of Faustrime fruits (peels, pulp, albedo, and seeds) extracted with different solvents was determined by GC-MS and UHPLC-HRMS QTof. The obtained data were also combined for their in vitro antioxidant activity by multivariate analysis to define a complex fingerprint of the fruit. The principal component analysis model showed the significative occurrence of volatile organic compounds as α-bisabolol and α-trans-bergamotol in the pulp and albedo, hexanoic acid in the seeds, and several coumarins and phenolics in the peels. The higher radical scavenging activity of the pulp was related to the incidence of citric acid in partial least square regression.

Garcinia mangostana L. fruits and derived food supplements: Identification and quantitative determination of bioactive xanthones by NMR analysis.

Mangosteen (Garcinia mangostana L.), known as "the queen of fruits", is one of the most praised tropical fruit due to its delicious taste. In the last years, the use of mangosteen in functional products has been increasing, mainly in food beverages and nutraceutical formulations due to its biological activities related to the content of xanthones. The quantitative Nuclear Magnetic Resonance (qNMR) analysis, a rapid and accurate method used for simultaneous quantification of plant metabolites, was here employed to determine the amount of bioactive xanthones in the extracts of G. mangostana arils and shells obtained by using solvent of increasing polarity along with ''eco-friendly'' solvents like ethanol and ethanol-water. Furthermore, the content of xanthones was compared with that occurring in four selected commercial food supplements, among which tablets and capsules, and two fruit juices, based on mangosteen. Quantitative results highlighted a significant variability: the extracts of the shells displayed a higher amount of bioactive xanthones than those of the arils, in particular, of γ-mangostin and α-mangostin, while ß-mangostin, demethylcalabaxanthone, mangostanin, 8-deoxygartanin occurred in higher amounts in arils. A certain variability in the amount of biologically active xanthones (i.e. α-mangostin and γ-mangostin) could be observed in commercial food supplements.

Portulaca oleracea, a rich source of polar lipids: Chemical profile by LC-ESI/LTQOrbitrap/MS/MSn and in vitro preliminary anti-inflammatory activity.

Considering the ongoing interest in foods rich in nutrients like polyunsaturated fatty acids and bioactive polar lipids, the chemical and biological investigation of Portulaca oleracea (purslane), a herbaceous plant typically appreciated in Mediterranean and Asiatic diet, was carried out. The LC-ESI/HRMS/MSn analysis of extracts and lipid enriched fractions of purslane edible parts provided a comprehensive polar lipid profile, ranging from linear and cyclic oxylipins to high molecular weight lipids including glycolipids, phospholipids and sphingolipids. The evaluation of the anti-inflammatory potential by in vitro reporter gene assays highlighted the ability of purslane lipid enriched fractions, at a concentration of 20 µg/ml, to inhibit the TNF-α-stimulated NF-kB pathway by 30-40% and to activate PPAR-É£ and Nrf2 transcription factors to the same extent or more than the positive control, respectively. Altogether, these results encourage to revalue purslane in human nutrition as a source of bioactive polar lipids.

Natural Deep Eutectic Solvents (NADESs) Combined with Sustainable Extraction Techniques: A Review of the Green Chemistry Approach in Food Analysis.

Usual extraction processes for analyzing foods, supplements, and nutraceutical products involve massive amounts of organic solvents contributing to a negative impact on the environment and human health. In recent years, a new class of green solvents called natural deep eutectic solvents (NADES) have been considered a valid alternative to conventional solvents. Compared with conventional organic solvents, NADES have attracted considerable attention since they are sustainable, biodegradable, and non-toxic but also are easy to prepare, and have low production costs. Here we summarize the major aspects of NADEs such as the classification, preparation method physicochemical properties, and toxicity. Moreover, we provide an overview of novel extraction techniques using NADES as potential extractants of bioactive compounds from foods and food by-products, and application of NADEs in food analysis. This review aims to be useful for the further development of NAES and for broadening the knowledge of these new green solvents in order to increase their use for the extraction of bioactive compounds and in food analysis.

Okra fruit: LC-ESI/LTQOrbitrap/MS/MSn based deep insight on polar lipids and specialized metabolites with evaluation of anti-oxidant and anti-hyperglycemic activity.

Okra is a vegetable crop very popular in tropical, subtropical, and warm temperate regions of the world for its edible fruit. Nowadays, this species can be easily found in European local markets, as a basic ingredient in many local and traditional dishes. Considering the extensive and spread use of okra fruits, to achieve deep insight on its chemical composition the analysis of the polar extract by high-performance liquid chromatography coupled to multiple-stage linear ion-trap and orbitrap high-resolution mass spectrometry in negative electrospray ionization mode was carried out. By this approach, 39 metabolites belonging to different polar lipid classes, such as oxylipins, phospholipids, glycolipids, and sphingolipids, were putatively identified for the first time in A. esculentus. Moreover, LC-HRMS/MS analyses guided the isolation and characterization by NMR experiments of 19 specialized metabolites belonging to phenolic acid and flavonoid classes, 8 of them never reported before in A. esculentus. Finally, antioxidant activity and inhibition of α-glucosidase activity were assayed, suggesting a good anti-oxidant anti-hyperglycemic activity for okra fruit.