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2-Furaldehyde (2-FA), also known as furfural or 2-furancarboxaldehyde, is an heterocyclic aldehyde that can be obtained from the thermal dehydration of pentose monosaccharides. This molecule can be considered as an important sustainable intermediate for the preparation of a great variety of chemicals, pharmaceuticals and furan-based polymers. Despite the great importance of this molecule, its gas-phase basicity (GB) has never been measured. In this work, the GB of 2-FA was determined by the extended Cooks's kinetic method from electrospray ionization triple quadrupole tandem mass spectrometric experiments along with theoretical calculations. As expected, computational results identify the aldehydic oxygen atom of 2-FA as the preferred protonation site. The geometries of O-O-cis and O-O-trans 2-FA and of their six different protomers were calculated at the B3LYP/aug-TZV(d,p) level of theory; proton affinity (PA) values were also calculated at the G3(MP2, CCSD(T)) level of theory. The experimental PA was estimated to be 847.9 ± 3.8 kJ mol(-1), the protonation entropy 115.1 ± 5.03 J mol(-1) K(-1) and the GB 813.6 ± 4.08 kJ mol(-1) at 298 K. From the PA value, a ΔH°(f) of 533.0 ± 12.4 kJ mol(-1) for protonated 2-FA was derived.

Organic-inorganic composites can be conveniently obtained by sol-gel recipes. They can find interesting applications in several fields, including drug delivery, scaffolding, bio-sensing, energetics, etc. Herein, we reconsider and reinvestigate our previous work in the field, by considering the sol-gel synthesis and physicochemical characterization of class-I organic-inorganic hybrids, and by trying to highlight some unifying elements that can be of help for the development of more efficient and precise synthesis methods. Systems based on poly(ethylene glycol) with SiO2 and ZrO2 as the ceramic phase will be discussed. Emphasis will be put on the role played by solid-state NMR spectroscopy in unveiling the interactions at the base of hybrid formation.

Taraxacum kok-saghyz (TKS) and T. brevicorniculatum (TB) are broadly investigated as natural rubber-producing plants and possible alternative supply sources for this relevant raw material. To fully exploit Taraxacum as a profitable crop, all the potential co-products should be investigated, through in-depth analysis of metabolites present in different organs of the plant. In the present study, natural rubber (NR), inulin, and resin content was measured by accelerated solvent extraction from the roots of TB and TKS, highlighting a 5-fold more content of NR in TKS compared to TB. Moreover, the chemical composition of both acetone and methanolic extracts from the roots and leaves of TKS and TB has been characterized by ultra-high-pressure liquid chromatography/tandem mass spectrometry (UHPLC-HRMS) technique and the content of target compounds between TKS and TB was also compared. The analysis resulted in the detection of 55 metabolites, whose identification was discussed based on chemical classes and the extraction method. Thus, sesquiterpenoids, fatty acids and their derivatives, phenolic compounds, mainly caftaric and chicoric acid, were identified. Hence, both the leaves and roots of TB, and especially of TKS, are rich in a wide variety of high-value-added compounds exploitable along with NR and inulin to increase the commercial value of these two dandelion species.

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.

The genus Quercus supplies a large amount of residual material (e.g., bark, acorns, leaves, wood), the valorization of which can favor a supply of antioxidant polyphenols to be used in the pharmaceutical, nutraceutical, or cosmeceutical sector. The recovery of specialized metabolites could also benefit livestock feeding, so much so that polyphenols have gained attention as rumen fermentation modifiers and for mitigating the oxidative imbalance to which farm animals are subject. In this context, leaves of Quercus robur L. from Northern Germany were of interest and the alcoholic extract obtained underwent an untargeted profiling by means of ultra-high-performance liquid chromatography/high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) techniques. As triterpenes and fatty acids occurred, the alcoholic extract fractionation pointed out the obtainment of a polyphenol fraction, broadly constituted by coumaroyl flavonol glycosides and condensed tannins. Total phenol, flavonoid and condensed tannins content assays, as well as antiradical (DPPH● and ABTS+●) and reducing activity (PFRAP) were carried out on the alcoholic extract and its fractions. When the effects on rumen liquor was evaluated in vitro in terms of changes in fermentation characteristics, it was observed that oak leaf extract and its fractions promoted an increase in total volatile fatty acids and differently modulated the relative content of each fatty acid.

Glass recycling reduces the amount of waste to be treated or disposed in landfills, allowing both to limit environmental damage and to save on the costs of transportation and disposal of waste. In this paper, an advantageous method for recycling glass containers (bottles, jars, jars for food, glasses and cans for drinks, etc.) is presented. The glass was crushed and without being washed or separated from any foreign bodies it was safely incorporated into a metakaolin-based geopolymeric matrix. Pure metakaolin and mixtures obtained by adding different percentages (30-50 wt%) of glass cullet were consolidated via alkali activation at 50°C. Infrared spectroscopy was able to reveal the formation of bonds in the mixtures between the geopolymeric matrix and the glass. Leaching tests were carried out to evaluate the eventual release of toxic metals, while the antibacterial tests completed the environmental evaluation of the final consolidated products that showed how the mechanical performance were modified by adding different amount of glass [1]. References [1] G. Dal Poggetto, M. Catauro, G. Crescente and C. Leonelli. Efficient addiction of waste glass in MK-based geopolymers: microstructure, antibacterial and cytotoxicity investigation. Polymers, 2021, 13, 1493.

The high amount of organic and inorganic wastes has increased the attention to new strategies aiming to reduce the waste disposals. Organic wastes, such as tomato wastes (TWs), are a good source from which the red color can be obtained. Among the different technologies, the geopolymers had been proposed as a powerful technology able to incorporate various kinds of wastes. In this paper, pure metakaolin and a mixture obtained by adding 10% of red TW-derived (peels) are consolidated by alkali activation at room temperature, 40 and 60 degrees C without the pigment extraction. Fourier-transform infrared (FTIR) spectra confirmed the geopolymerization occurrences. Moreover, the obtained materials are analyzed for their conductivity and pH after the sample extractions at different times. The integrity tests assessed the resistance of the synthesized geopolymers and the presence of red tomato-wastes led to a release of yellow organic hydro-soluble compounds. Finally, the weight loss confirmed the integrity test. Indeed, there are no differences at 16 and 30 d.

Cannabidiolic acid (CBDA) is the main precannabinoid in industrial hemp. It represents a common constituent of hemp seed oil, but mainly abundant in the aerial parts of the plant (including their processing waste). Thus, the optimization of fast and low-cost purification strategies is mandatory, as well as a deep investigation on its nutraceutical and cosmeceutical properties. To this purpose, CBDA content in hemp seed oil is evaluated, and its recovery from wasted leaves is favorably achieved. The cytotoxicity screening towards HaCaT cells, by means of MTT, SRB and LDH release assays, suggested it was not able to decrease cell viability or perturb cell integrity up to 10 μM concentration. Thus, the ability of CBDA to differentially modulate the release of proinflammatory cytokines and chemokines mediators has been evaluated, finding that CBDA decreased IFN-γ, CXCL8, CXCL10, CCL2, CCL4 and CCL5, mostly in a dose-dependent manner, with 10 μM tested concentration exerting the highest activity. These data, together with those from assessing antimicrobial activity against Gram(+) and Gram(−) bacteria and the antibiofilm formation, suggest that CBDA is able to counteract the inflammatory response, also preventing bacteria colonization.

Castanea sativa Mill. (Fagaceae) is a deciduous tree grown for its wood and edible fruits. Chestnut processing produces residues (burs, shells, and leaves) exploitable for their diversity in bioactive compounds in animal nutrition. In fact, plant-specialized metabolites likely act as rumen modifiers. Thus, the recovery of residual plant parts as feed ingredients is an evaluable strategy. In this context, European chestnut leaves from northern Germany have been investigated, proving to be a good source of flavonoids as well as gallo- and ellagitannins. To this purpose, an alcoholic extract was obtained and an untargeted profiling carried out, mainly by means of ultra-high-performance liquid chromatography/high-resolution tandem mass spectrometry (UHPLC-HR MS/MS) techniques. To better unravel the polyphenol constituents, fractionation strategies were employed to obtain a lipophilic fraction and a polar one. This latter was highly responsive to total phenolic and flavonoid content analyses, as well as to antiradical (DPPH● and ABTS+●) and reducing activity (PFRAP) assays. The effect of the alcoholic extract and its fractions on rumen liquor was also evaluated in vitro in terms of fermentative parameter changes and impact on methanogenesis. The data acquired confirm that chestnut leaf extract and the fractions therefrom promote an increase in total volatile fatty acids, while decreasing acetate/propionate ratio and CH4 production.

Dietary supplements based on Teucrium chamaedrys L. subsp. chamaedrys aerial parts were banned, due to the hepatotoxicity of furan-containing neo-clerodane constituents. Indeed, the plant leaf content in phenolic compounds could be further exploited for their antioxidant capability. Accordingly, bio-guided fractionation strategies have been applied, obtaining seven partially purified extracts. These latter were chemically investigated through 1D and 2D NMR techniques and tested for their antiradical, reducing and cytotoxic capability. Data acquired highlighted that, through a simple phytochemical approach, a progressive neo-clerodane depletion occurred, while maximizing phenylethanoid glycosides in alcoholic fractions. Thus, although the plant cannot be used as a botanical remedy as such, it is suggested as a source of healthy compounds, pure or in mixture, to be handled in pharmaceutical, nutraceutical and/or cosmeceutical sectors.

This Special Issue, entitled “Food Bioactives: Chemical Challenges and Bio-Opportunities”, was born with the aim of attracting contributions on analytical challenges in food bioactives’ chemistry and bioactivity, which form the basis of proper bio-opportunities [...]

Chickpea (Cicer arietinum L.) from Valle Agricola is a legume cultivated in Southern Italy whose intake is strictly linked to rural traditions. In order to get new biochemical insight on this landrace and to promote its consumption and marketing, nutritional values (moisture content, total proteins, lipids, total and free amino acids) and metabolic traits are deeply investigated. Valle Agricola chickpea is nutritionally rich in proteins (19.70 g/100 g) and essential amino acids (7.12 g/100 g, ~40% of total). Carbohydrates, whose identity was unraveled by means of UHPLC-HR MS/MS analysis, were almost 60% of chemicals. In particular, a di-galactosylglycerol, a pinitol digalactoside, and a galactosylciceritol were found as constitutive, together with different raffinose-series oligosaccharides. Although lipids were the less constitutive compounds, glycerophospholipids were identified, while among free fatty acids linoleic acid (C18:2) was the most abundant, followed by oleic (C18:1) and palmitic (C16:0) acids. Isoflavones and hydroxybenzoic acid derivatives were also detected. Valle Agricola chickpeas showed very good levels of several mineral nutrients, especially magnesium (164 mg/100 g), potassium (748 mg/100 g), calcium (200 mg/100 g), zinc (4.20 mg/100 g) and manganese (0.45 mg/100 g). The boiling process favorably decreases trypsin and chymotrypsin activities, depleting this precious seed of its intrinsic antinutritional factors.

Currently, radiotherapy is one of the most effective strategies to treat cancer. However, deleterious toxicity against normal cells indicate for the need to selectively protect them. Reactive oxygen and nitrogen species reinforce ionizing radiation cytotoxicity, and compounds able to scavenge these species or enhance antioxidant enzymes (e.g., superoxide dismutase, catalase, and glutathione peroxidase) should be properly investigated. Antioxidant plant-derived compounds, such as phenols and polyphenols, could represent a valuable alternative to synthetic compounds to be used as radio-protective agents. In fact, their dose-dependent antioxidant/pro-oxidant efficacy could provide a high degree of protection to normal tissues, with little or no protection to tumor cells. The present review provides an update of the current scientific knowledge of polyphenols in pure forms or in plant extracts with good evidence concerning their possible radiomodulating action. Indeed, with few exceptions, to date, the fragmentary data available mostly derive from in vitro studies, which do not find comfort in preclinical and/or clinical studies. On the contrary, when preclinical studies are reported, especially regarding the bioactivity of a plant extract, its chemical composition is not taken into account, avoiding any standardization and compromising data reproducibility.

The hydroxycinnamoyl compound caffeic acid (CA), broadly occurring in plants, is receiving special attention in materials science thanks to its antioxidant, anti-inflammatory, and antimicrobial activities that make it promising for application use in various sectors. In this context, CA–based peptide biomaterials are recently developed as eco-friendly and multifunctional free radical scavengers useable in a wide range of consumer manufacture, ranging from cosmetics to household products, as well as clinical applications, including imaging, drug delivery, and disinfection. Furthermore, a water-soluble chitosan-caffeic acid conjugate, effective in delaying lipid oxidation, is also synthetized. Herein, exploiting sol-gel route versatility, CA/silica materials are synthetized. Hybrids, chemically characterized mainly through spectroscopic techniques, varied in their relative CA content, which represented 5%, 10%, 15%, or 20% of materials’ weight. The synthetized materials are able to elicit anti-radical properties. The CA amount appeared to be determinant in anti-radical activity, as well as in biocompatibility assessment. To this latter purpose, mouse embryonic fibroblast cell line NIH-3T3 cells are utilized and directly exposed to hybrid materials. Redox mitochondrial activity is evaluated by means of the MTT test, whose results are in accordance with the materials’ biocompatibility.

European beech (Fagus sylvatica L.) is a deciduous tree, widely distributed in Europe and largely appreciated for its wood and nutritive nuts. Beech leaf also enjoys food use as salad, but an understanding of its nutraceutical value is still far from being achieved. Indeed, and also taking into account beech leaf as a consistent biomass residue available beechwood production and use, it needs to be explored as a valuable renewable specialized source of bioactive molecules. In this context, an untargeted ultra-high-performance liquid chromatography hyphenated with high resolution mass spectrometry (UHPLC-HRMS) approach was favorably applied to a beech leaf alcoholic extract, which also was evaluated for its antiradical capability (by means of assays based on 2,2-diphenyl-1-picrylhydrazyl (DPPH) and [2,2’-azinobis-(3-ethylbenzothiazolin-6-sulfonic acid)] (ABTS) radical cation) and its ferric ion reducing power. Redox mitochondrial activity towards Caco-2 cells paved the way to explore the extract’s capability to inhibit intracellular Reactive Oxygen Species (ROS) using 2’,7’dichlorofluorescin diacetate (DCFH-DA) assay. Hydroxycinnamoyl derivatives, mainly belonging to the chlorogenic acid class, and flavonoids were the main constituents. Uncommon flavanone C-glycosides were also found, together with a plentiful flavonol diversity. Cell-free and cell-based assays highlight its dose-dependent antioxidant efficacy, providing a foundation for further investigation of beech leaf constituents and its valorization and use as a reservoir of bioactive natural products with potential nutraceutical applications.

The high amount of organic and inorganic wastes has increased the attention to new strategies aiming to reduce the waste disposals. Among the different technologies, the geopolymers had been proposed as a powerful technology able to incorporate various kind of wastes [1]. Pure metakaolin and a mixture obtained by adding 10% of tomato waste-derived were consolidated by alkali activation at room temperature, 40 and 60°C. FT-IR spectra confirmed the geopolymerization occurrences. Conductivity and pH were evaluated at different time. The integrity tests assessed the resistance of the synthesized geopolymers and the presence of tomato-wastes led to a release of yellow organic hydro-soluble compound. Weight loss confirmed the integrity test, indeed there were no differences at 16 and 30 days. Finally, the antibacterial properties of the synthesized geopolymers were investigated [2]. References [1] H.K. Tchakouté, C.H. Rüscher, S. Kong, E. Kamseu, C. Leonelli, Constr Build Mater. 2016, 114, 276 – 289 [2] G. Dal Poggetto, M. Catauro, G. Crescente, C. Leonelli, Polymer. 2021, 13, 1493

The epidemic, caused by SARS-CoV-2 at the beginning of 2020, led us to a serious change in our lifestyle that for about three months has confined us to our homes, far from our laboratory routine. In this period, the belief that the work of a researcher should never stop has been the driving force in writing the present paper. It aims at reviewing the recent scientific knowledge about in vitro experimental data that focused on the antiviral role of phenols and polyphenols against different species of coronaviruses (CoVs), pointing up the viral targets potentially involved. In the current literature scenario, the papain-like and the 3-chymotrypsin-like proteases seem to be the most deeply investigated and a number of isolated natural (poly)phenols has been screened for their efficacy.

After a long period defined by prohibition of hemp production, this crop has been recently re-evaluated in various industrial sectors. Until now, inflorescences have been considered a processing by-product, not useful for the food industry, and their disposal also represents an economic problem for farmers. The objects of the present work are coffee blends enriched with shredded inflorescences of different cultivars of industrial hemp that underwent solid/liquid extraction into the Italian &ldquo, moka&rdquo, coffee maker. The obtained coffee drinks were analyzed by Ultra-High-Performance Liquid Chromatography-High Resolution Mass Spectrometry (UHPLC-HRMS) tools for their quali-quantitative phytocannabinoid profiles. The results showed that they are minor constituents compared to chlorogenic acids and caffeine in all samples. In particular, cannabidiolic acid was the most abundant among phytocannabinoids, followed by tetrahydrocannabinolic acid. Neither &Delta, 9-tetrahydrocannabinol (THC) nor cannabinol, its main oxidation product, were detected. The percentage of total THC never exceeded 0.04%, corresponding to 0.4 mg/kg, far below the current maximum limits imposed by the Italian Ministry of Health. This study opens up a new concrete possibility to exploit hemp processing by-products in order to obtain drinks with high added value and paves the way for further in vitro and in vivo investigations aimed at promoting their benefits for human health.

Although hemp seed (HS) oil is characterized by more than 80% polyunsaturated fatty acids (PUFAs), a very high &omega, 6-to-&omega, 3 ratio is not a popular commodity. The aim of this work was to provide useful data about the bioactive components and cannabidiolic acid content in thirteen different commercial hemp seed oils. The investigated HS oils showed a good &omega, 6/&omega, 3 ratio, ranging from 1.71 to 2.27, massively differed in their chlorophylls (0.041&ndash, 2.64 &micro, g/g) and carotenoids contents (0.29&ndash, 1.73 &micro, g/g), as well as in total phenols (22.1&ndash, 160.8 mg Gallic Acid Equivalents (GAE)/g) and tocopherols (3.47&ndash, 13.25 mg/100 g). Since the high content of PUFAs in HS oils, photo-oxidative stability was investigated by determining the Thiobarbituric Acid Reactive Substances (TBARS) assay and extinction coefficient K232 and K270 after the photo-oxidative test. The percentage of increase in K232 and K270 ranged from 1.2 to 8.5% and from 3.7 to 26.0%, respectively, indicating good oxidative stability, but TBARS showed a 1.5- to 2.5-fold increase in oxidative behavior when compared to the initial values. Therefore, the diversity in bioactive compounds in HS oils, and their high nutritional value, suggest the need for a disciplinary booklet that well defines agronomic and post-harvest management conditions for achieving a good food objective.

Cannabidiolic acid (CBDA) is the main phytocannabinoid in fiber and seed-oil hemp (Cannabis sativa L.) plants, but its potential health-related capabilities have been masked for years by a greater scientific interest towards its neutral derivative cannabidiol (CBD). This review aims to collect from the literature and critically discuss all the information about this molecule, starting from its biosynthesis, and focusing on its bioactivity, as an anti-inflammatory, anti-emetic, anti-convulsant, and anti-cancerogenic drug. Furthermore, in the awareness that, despite its multiple bioactive effects, currently poor efforts have been made to achieve its reliable purification, herein, we propose a relatively simple, fast, and inexpensive procedure for its recovery from pollen of industrial hemp cultivars. Spectroscopic and spectrometric techniques allowed us to unequivocally identify pure isolated CBDA and to distinguish it from the constitutional isomer tetrahydrocannabinolic acid (THCA-A).

Silica/polycaprolactone and titania/polycaprolactone hybrid organic/inorganic amorphous composites were prepared via a sol-gel method starting from a multi-element solution containing tetramethyl orthosilicate (TMOS) or titanium butoxide (TBT), polycaprolactone (PCL), water and methylethylketone (MEK). The molecular structure of the crosslinked network was based on the presence of the hydrogen bonds between organic/inorganic elements as confirmed by Fourier Transform Infra-Red (FT-IR) analysis. In particular, the structure of crosslinked network was realized by hydrogen bonds between the X-OH (X = Si or Ti) group (H donator) in the sol-gel intermediate species and ester groups (H-acceptors) in the repeating units of the polymer. The morphology of the hybrid materials, pore size distribution, elemental homogeneity and surface features, was studied by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) and by atomic force microscopy (AFM). The bioactivity of the synthesized hybrid materials was confirmed by observing the formation of a layer of hydroxyapatite (HAP) on the surface of the samples soaked in a simulated body fluid. The antimicrobial behavior of synthetized hybrids was also assessed against Escherichia coli bacteria. In conclusion, the prepared hybrid materials are proposed for use as future bone implants.

The sol&ndash, gel route represents a valuable technique to obtain functional materials, in which organic and inorganic members are closely connected. Herein, four hybrid materials, containing caffeic acid entrapped in a silica matrix at 5, 10, 15, and 20 wt.%, were synthesized and characterized through Fourier-Transform Infrared (FT-IR) and Ultraviolet-Visible (UV&ndash, Vis) spectroscopy. FT-IR analysis was also performed to evaluate the ability to induce the hydroxyapatite nucleation. Despite some structural changes occurring on the phenol molecular skeleton, hybrid materials showed scavenging properties vs. 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and 2,2&prime, azinobis-(3-ethylbenzothiazolin-6-sulfonic acid) radical cation (ABTS&bull, +), which was dependent on the tested dose and on the caffeic acid wt.%. The SiO2/caffeic acid materials are proposed as valuable antibacterial agents against Escherichia coli and Enterococcus faecalis.

Quercetin, whose health-promoting effects are acclaimed, is entrapped in a silica-based and silica/polymer hybrid material via sol–gel route, to develop new antioxidant biomaterials for preventing the onset of ROS-related diseases. The materials’ morphology is detected by SEM analysis, whereas the chemical characterization is achieved by spectroscopic and spectrometric techniques. Despite an oxidation reaction in the quercetin structure, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS [2,2′-azinobis-(3-ethylbenzothiazolin-6-sulfonic acid)] data show that all the materials preserve its antioxidant efficacy. MTT [3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide] test indicates a mild cytotoxicity in NIH-3T3, PC12, and U251 cells. Furthermore, materials with the highest quercetin percentage are able to inhibit the H2O2-induced intracellular ROS production in murine fibroblasts.

Seven previously undescribed sesquiterpene lactones, three known sesquiterpene lactones (ixerin D, 15-p-hydroxyphenylacetyllactucin, and 15-p-hydroxyphenylacetyllactucin-8-sulfate), and two known quinic acid derivatives (3-O-feruloylquinic acid and 3,5-di-O-caffeoylquinic acid) were isolated from Sonchus palustris L. roots. Four formerly undescribed compounds were elucidated to be 3β,14-dihydroxycostunolide-3-O-β-D-glucopyranosyl-(2-O-p-hydroxyphenylacetyl)-14-O-p-hydroxyphenylacetate, 15-p-methoxyphenylacetyllactucin, 15-p-methoxyphenylacetyllactucin-8-sulfate, and 8-p-hydroxyphenylacetyllactucin-15-sulfate. Additionally, three undescribed conjugates of lactucin and a eudesmanolide type sesquiterpenic acid, sonchpalustrin, 4″-O-methylsonchpalustrin, and isosonchpalustrin, were characterized. The structures of the newly discovered natural products were elucidated using 1D and 2D NMR spectroscopy and UHPLC-HRMS. 15-p-Hydroxyphenylacetyllactucin and 15-p-methoxyphenylacetyllactucin showed significant in vitro cytotoxicity against CEM and BJ cells with IC50 values ranging from 3.9 to 9.8 μM. Compounds 3 and 4 showed also strong anti-inflammatory activity in vitro.

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.

The current cancer treatment scenario lacks drugs acting as both radiosensitizer and radioprotector agents. In this context, the radiomodulatory properties exerted by an aqueous extract from the fruits of the Italian Prunus avium cv. Della Recca (PaDRw) were investigated. The extract, obtained through an environmentally-friendly ultrasound-assisted extraction, seemed to act as a radioprotector at lower tested doses (25 and 50 μg mL-1) and a radiosensitizer at 400 and 500 μg mL-1 dose levels towards the neuroblastoma SH-SY5Y cell line, irradiated with four graded X-ray doses (0, 0.5, 2, and 4 Gy). The fractionation of PaDRw by Amberlite XAD-4 non-ionic polymeric resin, coupled to LC-UV-MS/MS techniques, proved to be efficient also in the disclosure of lower constituents. About 63% of the whole PaDRw extract was constituted of hexitol, followed by fructose (∼22.8%) and glucose (∼10.7%). Chlorogenic acids and flavonoids, which accounted only for ∼2.2%, were hypothesized to be the main actors in PaDRw-induced radiomodulation.

The growing need for biomass recovery suggests forest waste leaf material for technological applications in a circular economy scenario. In this context, white poplar (Populus alba L.) foliar material was recovered in a forest site planted on a former agricultural land was identified in Tuscany (Italy), and intercropping eventually occurred was also valuated. In fact, the mixed plantation was characterized by tree different associations consisting of broad-leaf trees, including Populus alba L. intercropped with another valuable species (walnut, Juglans regia L.), and different nurse species (Italian alder, Alnus cordata (Loisel.); hazelnut, Corylus avellana L., Autumn olive, Elaeagnus umbellata (Thunb.)). Thus, Populus albaleaves were investigated for their lignin and phenol content, and for their anti-radical activity by (2,2-diphenyl-1-picrylhydrazyl) DPPH and [2, 2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid)] ABTS assays. Furthermore, Populus alba extracts were profiled by liquid chromatography hyphenated to high-resolution tandem mass spectrometry (LC-HRMS/MS), in order to deepen into the intercropping influence on specialized metabolites’ content. In particular, it was observed that when Populus alba grows in presence of the nurse species Elaeagnus umbellata, a decrease in the aforementioned parameters was observed, as well as a negative impact on the polyphenol profile. Thus, our findings are in line with the observation that white poplar leaf residue has a high potential for achieving bioactive polyphenol compounds, and that an intercropped nurse species such as Alnus cordata could favourably augment flavonoids and chlorogenic acids to be used as multifunctional ingredients.

The interest in industrial hemp-based products and by-products to be utilized in food and nutraceutical sector is strictly linked to the demand for improved analytical methods to rapidly discriminate acid phytocannabinoid isomers. Indeed, the differentiation of acid phytocannabinoids, also named pre-cannabinoids, is not properly exploited and valued until now, and it is challenging. Herein, using high-resolution MS/MS, the most common pre-cannabinoids with the resorcinol core linked to the alkyl five carbons chain were deeply investigated in terms of their reactivity to collision-induced dissociation, gaining key data on the integrated energy framework of their dissociation pathway. In fact, CBD-, THC- and CBC-type pre-cannabinoids could be discriminated based on the base peak identity, and the intensity of common fragment ions, when collision energy fragmented precursor ions by 70-75 %. In particular, energy-resolved CID mass spectra highlighted that fragmentation occurs, unrelatedly to alkyl chain length, at phenolic and monoterpenic moieties levels. Accordingly, this tool is effective for further differentiating pre-cannabinoid homologues, from methyl- up to heptyl-homologues, getting new insight in acid cannabinoids heritage of hemp and its products.

Through an integrated approach, which combines tools and techniques in design and food chemistry disciplines, new sustainable products have been experimented in cosmetic field. The design tools, acting in multiple and diversified fields, aim at valuing and increasing capabilities by creative training for generating sustainable and reproducible goods, whereas the investigation of the chemical composition of foods and their by-products is one of the main goals in food chemistry research. In this context, agri-food sector by-products are an inexhaustible source of bioactive, whose re-use, as alternative sources of low-cost and bio-sus- tainable active ingredients, is desirable in the nutraceutical field. Furthermore, the recycling of waste could reduce its environmental impact and the related disposal costs. The collaborative methodology is prompt to convey a new concept of wellness and body care through a new eco-oriented product production in which food winter-wastes are investigated for their cosmeceutical value for the formulation of green-cosmetic products. The paper reports the ex- perience carried out in the design and food chemistry laboratories. Key Words: green-cosmetic products, food waste, bio-sustainable active ingredients.

Ageritin is the first reported ribotoxin-like protein from basidiomycetes fungi. It can induce ribosomal integrity damage and translation block, and interferes with mitochondrial redox activity of some glioma and neuroblastoma cell lines. Herein, Ageritin has been investigated as a valuable neurotoxin towards either undifferentiated or retinoic acid (RA)-differentiated SH-SY5Y neuroblastoma cells showing a selective cell toxicity against undifferentiated cells. MTT and sulforhodamine B (SRB) assays highlighted that Ageritin markedly decreases the mitochondrial redox activity and viability of undifferentiated cells, meanwhile inducing evident morphological changes eliciting neuronal-like appearance in these cells. Data from lactate dehydrogenase release assay, cytofluorimetric analysis and caspase-3 enzymatic activity measurement suggest that Ageritin promotes cell death through a caspase-dependent apoptotic pathway. The Z-VAD-FMK caspase inhibitor was able to prevent this apoptotic pathway activation. Based on the interesting behaviour of Ageritin vs. SH-SY5Y cells, the development of a scale-up procedure to obtain the purified protein in larger amounts (yield 2.5 mg per 100 g) has been optimized.

The aerial parts of rock hyssop (Hyssopus officinalis subsp. aristatus (Godr.) Nyman), well-known for bearing essential oil-producing glands, are also rich in phenol and polyphenol compounds. These latter, still rarely studied in rock hyssop and other hyssop species, markedly differ based on the plant collection site. In fact, their biosynthesis, maximized in the wild, is finely regulated by multiple abiotic and biotic factors. In this context, to reach an accurate and deep understanding of the polyphenol constitution of a homemade-like preparation (HOEE) from rock hyssop growing wild in Southern Italy, analyses, based on ultra-high pressure liquid chromatography coupled with high-resolution mass spectrometry (UHPLC HRMS), were carried out. HOEE mainly consisted of hydroxycinnamoyl derivatives (57.2%), among which some different and never reported coumarin and lignan compounds. Dicaffeoyl quinic acids were the main chlorogenic compounds, whereas flavonoid glycosides and methoxyflavonoids were the less abundant compounds. The preliminary assessment of HOEE antiradical properties through differen t-test tube assays provided a solid basis for originally exploring its antioxidant activity towards differentiated Caco-2 cells. Experimental evidence on genoprotective activity of hyssop aerial parts, herein testified for the first time, raised the potential of their using as a functional food for oxidative stress-induced diseases prevention.

Five flavonoid glycosides were isolated from the aerial parts of Ornithopus compressus L., yellow serradella (Fabaceae). The structures of the isolated natural products were determined as kaempferol 3-O-(2,6-di-O-β-D-glucopyranosyl)-β-D-galactopyranoside (1), kaempferol 3-O-β-D-glucopyranosyl-(1→6)-[2-O-(2E)-feruloyl-β-glucopyranosyl]-(1→2)-β-D-galactopyranoside (2), quercetin 3-O-(2,6-di-O-β-D-glucopyranosyl)-β-D-galactopyranoside (3), quercetin 3-O-β-D-glucopyranosyl-(1→6)-[2-O-(2E)-feruloyl-β-glucopyranosyl]-(1→2)-β-D-galactopyranoside (4), and isorhamnetin 3-O-(2,6-di-O-β-D-glucopyranosyl)-β-D-galactopyranoside (5). While compounds 1 and 3 have been described previously, compounds 2, 4 and 5 represent formerly undescribed natural products. For structure elucidation UV, HRMS, and NMR (1H NMR, 13C NMR, H,H-COSY, HMBC, and HSQC) were employed. Absolute sugar configurations were confirmed using GLC–MS/MS after hydrolysis, octylation, and acetylation of the isolated compounds. Additionally, DPPH radical and ABTS radical cation scavenging activities as well as cytotoxic activities of the isolated compounds were assessed.

Total phenolic content and antioxidant activity of polar extracts of edible resources from Fedora hemp cultivar (Cannabis sativa L.), namely seed, flour and oil, were evaluated. The main components in the polar extracts were identified using HPLC-DAD and HPLC-ESI-MS/MS. As expected, the molecular profile of components from seeds and flour was strictly similar, dominated by N-trans-caffeoyltyramine. The profile of oil polar extracts contained hydroxycinnamic acid derivatives and cannabinoids at lower extent. While the extracts from hemp seed and flour did not interfere with growth of Caco-2 and HT-29 cell, the one from oil (150µg/mL) significantly reduced cell viability after 24 h of treatment. This effect was associated with the activation of apoptotic cell death and was independent from the antioxidant capacity of the oil polar extract. Notably, HT-29 cells differentiated with sodium butyrate were not sensitive to the cytotoxic effect of the oil extract. Total phenolic content and antioxidant activity of polar extracts of edible resources from Fedora hemp cultivar (Cannabis sativa L.), namely seed, flour and oil, were evaluated. The main components in the polar extracts were identified using HPLC-DAD and HPLC-ESI-MS/MS. As expected, the molecular profile of components from seeds and flour was strictly similar, dominated by N-trans-caffeoyltyramine. The profile of oil polar extracts contained hydroxycinnamic acid derivatives and cannabinoids at lower extent. While the extracts from hemp seed and flour did not interfere with growth of Caco-2 and HT-29 cell, the one from oil (150µg/mL) significantly reduced cell viability after 24 h of treatment. This effect was associated with the activation of apoptotic cell death and was independent from the antioxidant capacity of the oil polar extract. Notably, HT-29 cells differentiated with sodium butyrate were not sensitive to the cytotoxic effect of the oil extract.

The metabolite profiling of plant extracts always represents an exciting challenge, as the chemical diversity of natural products is still far beyond the researchers' imagination, even focusing on a plant that is thought to have already been broadly investigated. Herein UHPLC-HRMS/MS techniques were applied to an alcoholic crude extract from nettle leaves and proved to be a precious tool for the disclosure of secondary metabolites never found before. Hydroxycinnamic acid derivatives were the most representative constituents, with a 2-caffeoilisocitric acid cyclodimer described for the first time, besides four C-glycosylated flavones, bearing a 3-hydroxy-3-methylglutaryl function. This deep investigation paves the way for the isolation and full characterization of these molecules by means of spectroscopic techniques. Moreover, based on preliminary cytotoxicity evaluation, further research on the use of this nettle extract as a valuable nutraceutical product is encouraged.

Marketed green teas (GTs) can highly vary in their chemical composition, due to different origins, processing methods, and a lack of standardization of GT-based products. Consequently, biological activities become difficult to correlate to the presence/content of certain constituents. Herein, ultra-high-performance liquid chromatography (UHPLC) combined with high-resolution tandem mass spectrometry (HR MS/MS) was successfully applied to six commercial GT products, extracted by ethanol sonication, to disclose their polyphenol profile beyond the well-known catechins. The relative abundance of each class of metabolites was correlated to antiradical and antilipoperoxidant data through hierarchical clustering analysis, since it reasonably affects the beneficial properties of the product that reaches the consumer. The thiobarbituric acid reactive substances (TBARS) assay demonstrated that GT extracts effectively counteracted the UV-induced lipoperoxidation of hemp oil, which is highly rich in Polyunsaturated Fatty Acids (PUFAs), and therefore highly unstable. The Relative Antioxidant Capacity Index (RACI) comprehensively emphasized that gunpower and blend in filter GTs appeared to be the less active matrices, and except for a GT-based supplement, the Sencha GT, which was particularly rich in flavonol glycosides, was the most active, followed by Bancha GT.

The weak but noteworthy presence of (poly)phenols in hemp seeds has been long overshadowed by the essential polyunsaturated fatty acids and digestible proteins, considered responsible for their high nutritional benefits. Instead, lignanamides and their biosynthetic precursors, phenylamides, seem to display interesting and diverse biological activities only partially clarified in the last decades. Herein, negative mode HR-MS/MS techniques were applied to the chemical investigation of a (poly)phenol-rich fraction, obtained from hemp seeds after extraction/fractionation steps. This extract contained phenylpropanoid amides and their random oxidative coupling derivatives, lignanamides, which were the most abundant compounds and showed a high chemical diversity, deeply unraveled through high resolution tandem mass spectrometry (HR-MS/MS) tools. The effect of different doses of the lignanamides-rich extract (LnHS) on U-87 glioblastoma cell line and non-tumorigenic human fibroblasts was evaluated. Thus, cell proliferation, genomic DNA damage, colony forming and wound repair capabilities were assessed, as well as LnHS outcome on the expression levels of pro-inflammatory cytokines. LnHS significantly inhibited U-87 cancer cell proliferation, but not that of fibroblasts, and was able to reduce U-87 cell migration, inducing further DNA damage. No modification in cytokines&rsquo, expression level was found. Data acquired suggested that LnHS acted in U-87 cells by inducing the apoptosis machinery and suppressing the autophagic cell death.

Leaves of Vitis vinifera cv. Greco di Tufo, a precious waste made in the Campania Region (Italy), after vintage harvest, underwent reduction, lyophilization, and ultrasound-assisted maceration in ethanol. The alcoholic extract, as evidenced by a preliminary UHPLC-HR-MS analysis, showed a high metabolic complexity. Thus, the extract was fractionated, obtaining, among others, a fraction enriched in flavonol glycosides and glycuronides. Myricetin, quercetin, kaempferol, and isorhamnetin derivatives were tentatively identified based on their relative retention time and TOF-MS2 data. As the localization of saccharidic moiety in glycuronide compounds proved to be difficult due to the lack of well-established fragmentation pattern and/or the absence of characteristic key fragments, to obtain useful MS information and to eliminate matrix effect redundancies, the isolation of the most abundant extract&rsquo, s compound was achieved. HR-MS/MS spectra of the compound, quercetin-3-O-glucuronide, allowed us to thoroughly rationalize its fragmentation pattern, and to unravel the main differences between MS/MS behavior of flavonol glycosides and glycuronides. Furthermore, cytotoxicity assessment on the (poly)phenol rich fraction and the pure isolated compound was carried out using central nervous system cell lines. The chemoprotective effect of both the (poly)phenol fraction and quercetin-3-O-glucuronide was evaluated.

Nowadays, the research for secondary metabolites with health promoting effects in countering or slowing-down chronic and degenerative diseases (e.g. cancer, cardiovascular, and neurodegenerative diseases) identify phenols and polyphenols, widespread and mostly copious in dietary plant sources, as beneficial for human health. These compounds, as intrinsically antioxidant, are claimed as nutraceuticals with preventive efficacy in offsetting oxidant species over-genesis in normal cells, and with the potential ability to halt or reverse oxidative stress-related diseases. In this context, pure (poly)phenols and/or their herbal/food complexes were found to exert both anti- and pro-oxidant activities, suggesting also a promising chemopreventive efficacy. In fact, different evidence further highlights their ability to induce apoptosis, growth arrest, DNA synthesis inhibition and/or modulation of signal transduction pathways. Indeed, a full understanding of the phenolic and polyphenolic composition of plant species, which still now represent their inestimable and worth exploring source, is an important challenge, which today can and must be favourably pursued in the consciousness that the bioactivity of a plant extract is always in its chemistry. To reach this purpose a number of new and advanced techniques are available for extraction, purification and structural identification purposes, but, taking into account how, when and where (poly)phenols are biosynthesized, their use must be highly rationalized. This is particularly true for mass spectrometry techniques which, although representing one of the most powerful tools and in continuous evolution in this era, often suffer from an automatism that does not give justice to the chemical goodness of a plant species and particularly those of nutraceutical interest. This review will deepen into polyphenol research, focusing on biosynthesis, analytical approaches for a conscious exploitability of nutraceutical plant extracts rich in antioxidant and anti-inflammatory polyphenols and/or pure isolated polyphenols.