Calendula arvensis (Vaill.) L. (field marigold, Asteraceae) is an alimurgic plant, whose flowers and leaves are a common part of local food dishes. The diversity in polar specialized metabolites is herein unraveled, with the aim to further promote and valorize the food use of the plant. To this purpose, following the plant dissection of its organs (florets, fruits, leaves, bracts, stems, and roots), ultrasound assisted maceration has been employed in order to recover phenols and polyphenols. Through an untargeted UHPLC-HR MS (Ultra-High-Performance Liquid Chromatography-High-Resolution Mass Spectrometry) approach, and deeper investigation of the fragmentation patterns of each compound by tandem mass spectrometry, the florets’ constitution in triterpene saponins and flavonol glycosides has been highlighted, whereas hydroxycinnamoyl compounds are mainly in bracts and fruits. The antiradical and reducing capabilities of the organs’ extracts have been assessed, and data acquired have been analyzed by cluster analysis, which allowed bracts and fruits to be observed, despite their negligible food use, as the most active extracts. Chemical and antioxidant data on the diverse organs of field marigold suggest new investigative food and nutraceutical scenarios of this plant, also revalorizing and preserving its traditional uses.

Lavandula austroapennina N.G. Passal., Tundis and Upon has recently been described as a new species endemic to the southern Apennines (Italy). Locally, this species has a long ethnobotanical tradition of use for curative and decoration purposes and has been the protagonist of a flourishing essential oil production chain. Currently, while this tradition has long since ended, attention to the species is necessary, with a view to enhancing marginal and rural areas, as a recovery of a precious resource to (i) get insights into its (poly)phenolic fraction and (ii) address new and innovative uses of all its organs in various application fields (e.g., cosmeceutical sector). Therefore, after field sampling and dissection of its organs (i.e., corolla, calyx, leaf, stem and root), the latter, previously deterpenated and defatted, were subjected to accelerated ultrasound extraction and the related alcoholic extracts were obtained. Chemical composition, explored by UHPLC-QqTOF-MS/MS, and the following multivariate data analysis showed that the hydroxycinnamoyl derivatives are abundant in the leaf, stem and root, while flavonoids are more present in corolla and calyx. In particular, coumaroyl flavonoids with glyconic portion containing also hexuronyl moieties differentiated corolla organ, while yunnaneic acid D isomers and esculin distinguished root. When antiradical and reducing properties were evaluated (by means of ABTS, DPPH and PFRAP tests), a similar clustering of organs was achieved and the marked antioxidant efficacy of leaf, stem and root extracts was found. Thus, following cytotoxicity screening by MTT test on HaCaT keratinocytes, the protective effects of the organ extracts were assessed by wound closure observed after the scratch test. In addition, the extracts from corolla, leaf and stem were particularly active at low doses inducing rapid wound closure on HaCaT cells at a concentration of 1 μg/mL. The diversity in (poly)phenols of each organ and the promising bioactivity preliminarily assessed suggest further investigation to be carried out to fully recover and valorize this precious endemic vascular plant.

Edible, plant-derived foodstuffs are recognized as precious sources of polyphenol compounds, whose consumption has proven to have multiple beneficial effects on human health. However, the awareness that cooking processes are able to induce quali-quantitatively changes in their native occurrence and that their bioavailability after food ingestion is poor led the research to move toward the preparation of nutraceutical supplements aimed at maximizing their content by effective extractive techniques and protecting them from degradation. The present work fits into this context, proposing a green, ready-to-use formulation of capitula, stems, and leaves of Algerian artichokes, in which natural deep eutectic solvents were exploited as extracting solvents but not removed at the end of the process. MTT test on the Caco-2 cell line highlighted that mitochondrial redox activity inhibition was absent below the 50 µg/mL tested dose. Simulated in vitro digestion was used as a predictive model for formulation bioaccessibility, where the joint approach with UHPLC-HRMS techniques allowed to define the release of each polyphenol from the investigated matrices. The capitula-based sample was the richest one in flavonoids, especially luteolin and apigenin glycosides, which survived in the intestinal digesta. On the contrary, simple phenols characterized the stem sample, whose release was mainly in the gastric chyme.

Wild edible plants, once consumed in times of famine or for health purposes, today represent an interesting dietary supplement, aimed at enriching local dishes and/or formulating healthy nutraceutical products. In fact, the broad content of different, and diversely bioactive, specialized metabolites therein suggests new scenarios of use which, in order to be as functional as possible, must maximize the bioactivity of these compounds while preserving their chemistry. In this context, based on a recent investigation on the metabolic profile of the organs of Calendula arvensis that highlighted that florets are abundant in flavonol glycosides and triterpene saponins, the freeze-drying encapsulation of their alcoholic extract (FE) into maltodextrin (MD) was investigated. FE-MD chemical composition was evaluated using Fourier Transform InfraRed spectroscopy (FTIR), while ultra-high performance liquid chromatography coupled with high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) techniques were employed to unravel FE compound preservation also during in vitro simulated digestion. The establishment of H-bonds between FE compounds and MD hydroxyl groups was in line with FE-MD biocompatibility in Caco-2 cells, while in vitro digestion mostly affected structural integrity and/or diversity. Flavonol compounds underwent deglycosylation and demethylation, while deacylation, beyond oxidation, involved triterpene saponins, which massively preserve their aglycone core.

As part of a project aimed at promoting the use of Calendula arvensis (Vaill.) L. (field marigold, Asteraceae) phytocomplexes in cosmeceutical formulations, the chemical composition in apolar specialized metabolites is herein elucidated. Furthermore, the screening of the cytotoxicity of the apolar extracts was evaluated in order to underline their safety as functional ingredients for cosmetics. After dissection of Calendula organs (florets, fruits, leaves, bracts, stems, and roots), ultrasound-assisted maceration in n-hexane as an extracting solvent allowed us to obtain oil-like mixtures, whose chemical composition has been highlighted through a UHPLC-ESI-QqTOF-MS/MS approach. Twenty-nine metabolites were tentatively identified; different compounds, among which the well-known poly-unsaturated fatty acids, and oxylipins and phosphatides were detected for the first time in Calendula genus. The screening of the dose-response cytotoxicity of the apolar extracts of C. arvensis highlighted the concentration of 10 μg/mL as the most suitable for the formulation of cosmeceutical preparations. Sera enriched with leaf and fruit apolar extracts turned out to have the best activity, suggesting it can be used as a new source in skin care thanks to their higher content in fatty acids.

Selenosugars are gaining growing interest due to their antioxidant efficacy, and their ability to inhibit glycosidases, repair skin tissue or reduce endothelial dysfunction. Among selenosugars, those in which selenium replaces heterocyclic oxygen in a 5-membered sugar were our focus, and their coupling with phenolic compounds appears to be a strategy aimed at producing new compounds with enhanced antioxidant efficacy. In this context, the Mitsunobu reaction has been advantageously explored to obtain trans-p-coumaroyl-1,4-deoxy-2,3-O-isopropylidene-4-seleno-d-ribose, trans-caffeoyl-1,4-deoxy-2,3-O-isopropylidene-4-seleno-d-ribose, and trans-feruloyl-1,4-deoxy-2,3-O-isopropylidene-4-seleno-d-ribose. These compounds underwent removal of the iso-propylidene group, to provide the corresponding hydroxycinnamoyl-1,4-deoxy-4-seleno-d-ribose. All compounds were characterized by Nuclear Magnetic Resonance (NMR) spectroscopy and High-Resolution Mass Spectrometry (HRMS). This latter technique was pivotal for ensuing cellular metabolomics analyses. In fact, after evaluating the anti-radical efficacy through 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) methods, which underline the massive role of the phenolic moiety in establishing efficacy, the compounds, whose cytotoxicity was first screened in two highly oxidative-stress-sensitive cells, were tested for their wound healing properties towards human HaCaT keratinocytes cells. Caffeoyl- and feruloyl selenosugars exerted a dose-dependent repair activity, while, as highlighted by the metabolomic approach, they were poorly taken up within the cells.