Polyphenol-Rich Extracts from Agroindustrial Waste and Byproducts: Results and Perspectives According to the Green Chemistry and Circular Economy.

Polyphenols are natural secondary metabolites found in plants endowed with multiple biological activities (antioxidant, anti-inflammatory, antimicrobial, cardioprotective, and anticancer). In view of these properties, they find many applications and are used as active ingredients in nutraceutical, food, pharmaceutical, and cosmetic formulations. In accordance with green chemistry and circular economy strategies, they can also be recovered from agroindustrial waste and reused in various sectors, promoting sustainable processes. This review described structural characteristics, methods for extraction, biological properties, and applications of polyphenolic extracts obtained from two selected plant materials of the Mediterranean area as olive (Olea europaea L.) and pomegranate (Punica granatum L.) based on recent literature, highlighting future research perspectives.

Phenolic-Rich Extracts from Circular Economy: Chemical Profile and Activity against Filamentous Fungi and Dermatophytes.

Fungal infections represent a relevant issue in agri-food and biomedical fields because they could compromise quality of food and humans' health. Natural extracts represent a safe alternative to synthetic fungicides and in the green chemistry and circular economy scenario, agro-industrial wastes and by-products offer an eco-friendly source of bioactive natural compounds. In this paper, phenolic-rich extracts from Olea europaea L. de-oiled pomace, Castanea sativa Mill. wood, Punica granatum L. peel, and Vitis vinifera L. pomace and seeds were characterized by HPLC-MS-DAD analysis. Finally, these extracts were tested as antimicrobial agents against pathogenic filamentous fungi and dermatophytes such as Aspergillus brasiliensis, Alternaria sp., Rhizopus stolonifer, and Trichophyton interdigitale. The experimental results evidenced that all extracts exhibited a significant growth inhibition for Trichophyton interdigitale. Punica granatum L., Castanea sativa Mill., and Vitis vinifera L. extracts showed a high activity against Alternaria sp. and Rhizopus stolonifer. These data are promising for the potential applications of some of these extracts as antifungal agents in the food and biomedical fields.

Natural Active Ingredients for Poly (Lactic Acid)-Based Materials: State of the Art and Perspectives.

This review describes the state of the art in the field of poly (lactic acid) (PLA)-based materials activated by natural compounds and extracts (active ingredients, AIs) from plant sources for food and biomedical applications. With a multidisciplinary approach, after a description of the synthesis and properties of PLA, special attention was paid to the chemical properties and unconventional extraction technologies of AIs used for PLA activation. Innovative techniques for the incorporation of AIs into PLA; characterization and the antioxidant and antimicrobial properties of the novel materials were discussed. In view of future perspectives, this study has evidenced that some aspects need to be further investigated from joint research between academia and industry, according to the green chemistry principles and circular economy strategy.

Utility of SIFT-MS to evaluate volatile organic compounds in nephropathic patients' breath.

Several studies highlighted a correlation between exhaled air volatile organic compounds (VOCs) and some pathological conditions, such as chronic kidney disease (CKD), chronic liver disease, etc. In fact, in literature has been reported that CKD is characterized by an increased concentration of ammonia, trimethylamine (TMA) and isoprene compared to healthy subjects. Currently, there is not a validate and standardized method to detect VOCs. For this purpose, we examined the utility of selected ion flow tube-mass spectrometry (SIFT-MS) to measure VOCs in CKD patients and we evaluated the possible correlation between VOCs and the presence of CKD and its stage. We enrolled 68 CKD patients under conservative therapy and 54 healthy subjects. The analysis of the VOCs of the exhaled air of the enrolled subjects was performed by SIFT-MS. Among all the VOCs analyzed, the most relevant results by ROC curves were observed for TMA, acetone, ammonia and dimethyl sulfide. We found that a breath TMA concentration superior to 26 ppbv characterizes a 6.11 times greater risk of CKD, compared to subjects with lower levels. Moreover, we detected an increased concentration of acetone and ammonia in CKD patients compared to healthy subjects. We highlight the potential utility of SIFT-MS in CKD clinical management.Clinical trial registry: R.S. 15.19 of 6 February 2019.

Analysis of aroma and polyphenolic compounds in Saperavi red wine vinified in Qvevri.

The purpose of this study is to analyze and characterize a Georgian red wine from Saperavi grape, obtained in Qvevri (Georgian traditional winemaking method), by using innovative techniques for the determination of the polyphenolic content, aroma, and its correlation to the sensory characteristics. This peculiar red wine, after high-performance liquid chromatography with diode-array detection and mass spectrometry (HPLC-DAD-MS), headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS), and HS-SPME-GCxGC-MS/TOF (two-dimensional gas chromatography) chemical characterization showed a high polyphenol content (19.6 × 102 mg/L, 38.4% anthocyanins) and a wide range of volatile compounds, among which terpenes were associated with the aroma of flowers, lemongrass, and wood. Analyses were also conducted to determine the total polyphenol content correlated to antioxidant activity with the Folin-Ciocalteu spectrophotometric in vitro method (4.650 g GAE/L). In conclusion, for the first time on Saperavi wine, innovative techniques such as HPLC-DAD-MS, GC-MS, and GCxGC-MS/TOF were simultaneously applied in association with the traditional analytic techniques to perform a complete chemical characterization. These activities are part of a project about circular viticulture in the Georgian territory that will lead the production of traced quality wines and the valorization of the Georgian wine sector.

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

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

Effect of Hydrolysable Tannins and Anthocyanins on Recurrent Urinary Tract Infections in Nephropathic Patients: Preliminary Data.

Urinary tract infections (UTIs) are caused by uropathogenic microorganism colonization. UTIs often require an antibiotic therapy that can cause the selection of antibiotic-resistant bacterial strains. A natural bioactive compound may represent a valid therapeutic adjuvant approach, in combination with drug therapy. In this paper, we present a pilot study, based on the administration of an oral food supplement (OFS), containing chestnut tannins and anthocyanins, to nephropathic patients suffering from recurrent UTIs (16 treated patients with 1 cp/day and 10 untreated patients). We performed laboratory tests and quality of life and body composition assessments, at T0 (baseline) and T1 (after 6 weeks OFS assumption). The analysis of OFS was performed by HPLC-DAD-MS for its content in polyphenols and by in vitro tests for its antioxidative and anti-free radical activities. In each capsule, polyphenol content was 6.21 mg (4.57 mg hydrolysable tannins, 0.94 mg anthocyanosides, 0.51 mg proanthocyanidins, 0.18 mg quercetin derivatives). A significant reduction of erythrocyte sedimentation rate was observed only in male patients. Urinalysis showed a significant reduction of leukocytes in both genders, whereas urinary bacterial flora at T1 significantly decreased only in male subjects. Tannins seem to exert an antimicrobial action according to gender, useful to counteract the recurrence of UTIs.

Sweet chestnut standardized fractions from sustainable circular process and green tea extract: In vitro inhibitory activity against phytopathogenic fungi for innovative applications in green agriculture.

In the present study, the antifungal activities of two commercial tannins-rich dry fractions towards different filamentous fungi of agronomical and food interest were evaluated. In particular, a standardized fraction from sweet chestnut (Castanea sativa Mill.) wood by-products and a commercial green tea (Camellia sinensis L.) leaf extract were tested at different concentrations (0.1-5.0% and 0.2% w/v respectively). The Sweet Chestnut Wood fraction was produced in an industrial plant through an environmentally and economically sustainable process, involving hot-water extraction and a sequence of membrane filtration steps with different molecular cut-offs for fractionation and concentration of the active principles. The Sweet Chestnut Wood and Green Tea Leaf extracts were characterised via HPLC/DAD/MS quali-quantitative analysis. The first extract showed a polyphenolic content of 20.5% w/w, 100% hydrolysable tannins; the second one showed a polyphenolic content of 87.5% w/w, of which 96.2% epigallocatechin gallate and 3.8% epicatechin gallate. The antifungal activity of the Sweet Chestnut fraction in aqueous solutions was evaluated towards different filamentous fungi, in particular telluric phytopathogens (Fusarium oxysporum f. sp. radicis-lycopersici; Fusarium solani; Rhizoctonia solani; Sclerotium rolfsii) and post harvest pathogens (Botrytis cinerea, that can also attack field plants; Penicillium digitatum; Penicillium italicum), and compared to the activity of Green Tea Leaf extract solutions. The experimental results evidenced, for almost all tested fungi, inhibition of the mycelial growth rate in presence of tannins. The lowest inhibitions were observed for B. cinerea (7.5%, to 28.9%) and P. italicum (53.8% in 5.0% w/v Sweet Chestnut extract substrate). A proportional inhibitory effect to tannin concentration was observed for F. oxysporum f. sp. radicis-lycopersici and F. solani (from 33.7% to 56.6%), R. solani (from 29.7% to 68.8%) and P. digitatum (64.7% to 87.0%). The highest effect resulted for S. rolfsii, (5.0% to 100%).

An Industrial and Sustainable Platform for the Production of Bioactive Micronized Powders and Extracts Enriched in Polyphenols From Olea europaea L. and Vitis vinifera L. Wastes.

In the last few years, literature data have reported that health status is related to the consumption of foods rich in polyphenols, bioactive compounds found in the plant world, in particular in vegetables and fruit. These pieces of scientific evidence have led to an increase in the demand for functional foods and drinks enriched in polyphenols, so that plant materials are more and more requested. The availability of food and agricultural wastes has adverse effects on the economy, environment, and human health. On the other hand, these materials are a precious source of bioactive compounds as polyphenols. Their recovery and reuse from wastes are according to the circular economy strategy, which has introduced the "zero waste concept." However, the process is convenient from an economic and environmental point of view only if the final products are standardized and obtained using sustainable and industrial technologies. In this panorama, this paper describes an industrial and sustainable platform for the production of micronized powders and extracts enriched in polyphenols from Olea europaea L. and Vitis vinifera L. wastes that are useful for food, cosmetics, and pharmaceuticals sectors. The platform is based on drying plant materials, extraction of polyphenols through membrane technologies with water, and, when necessary, the concentration of the final fractions under vacuum evaporation. All powders and extracts were characterized by high-performance liquid chromatography-diode array detector-mass spectrometry analysis to define the qualitative and quantitative content of bioactive compounds and insure their standardization and reproducibility. The chromatographic profiles evidenced the presence of secoiridoids, flavones, flavonols, anthocyanins, hydroxycinnamic acids, catechins, and condensed tannins. An overview of the biological activities of the main polyphenols present in Olea europaea L. and Vitis vinifera L. powders and extracts is reported because of biomedical applications.

A Pilot Study of a Natural Food Supplement as New Possible Therapeutic Approach in Chronic Kidney Disease Patients.

The identification of natural bioactive compounds, able to counteract the abnormal increase of oxidative stress and inflammatory status in chronic degenerative non-communicable diseases is useful for the clinical management of these conditions. We tested an oral food supplement (OFS), chemically characterized and evaluated for in vitro and in vivo activity. Vitamin C, analyzed by High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD), was 0.19 mg/g in rosehip dry extract and 15.74 mg/capsule in the OFS. The identification of polyphenols was performed by HPLC-DAD; the total antioxidant capacity was assessed by Folin-Ciocalteu test. Total polyphenols were 14.73 mg/g gallic acid equivalents (GAE) for rosehip extract and 1.93 mg/g GAE for OFS. A total of 21 chronic kidney disease (CKD) patients and 10 healthy volunteers were recruited. The evaluation of routine laboratory and inflammatory parameters, erythrocyte glutathione transferase (e-GST), human oxidized serum albumin (HSAox), and assessment of body composition were performed at two different times, at baseline and after 5 weeks of OFS assumption. In the study, we highlighted a significant decrease of traditional inflammatory biomarkers (such as C-reactive protein, erythrocyte sedimentation rate, platelet to lymphocyte ratio) and other laboratory parameters like e-GST, azotaemia, and albuminuria after OFS treatment in CKD patients. Moreover, we demonstrated a lipid profile improvement in CKD patients after OFS supplementation.

Antioxidant and anti-inflammatory effects of pomegranate peel extracts on bovine mammary epithelial cells BME-UV1.

Pomegranate peel extracts (PPE) were tested for the first time on BME-UV1, a valid cellular model to study the bovine mammary epithelial metabolism, to evaluate the effects on the oxidative stress and inflammatory status. Based on the statistical analysis of MTT data, PPE at 0.1, 1.0 and 10 µg/mL resulted not cytotoxic after 24 h, 48 h and 7 days of treatment. At the same concentrations, PPE induced a reduction of ROS production elicited by the addition of hydrogen peroxide or lipopolysaccharide evidencing an antioxidant effect confirmed also by a decrease of malondialdehyde. At 10 µg/mL, PPE reduced pro-inflammatory cytokines expressions showing an anti-inflammatory effect on BME-UV1 treated with lipopolysaccharide. Although in vivo experiments are necessary, the results of this study are promising for future applications of PPE as feed supplement for dairy cattle, in particular around calving, when the animals are more subject to oxidative stress and inflammatory diseases.

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

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

Biogenic Amines, Phenolic, and Aroma-Related Compounds of Unroasted and Roasted Cocoa Beans with Different Origin.

Biogenic amines (BAs), polyphenols, and aroma compounds were determined by chromatographic techniques in cocoa beans of different geographical origin, also considering the effect of roasting (95, 110, and 125 °C). In all samples, methylxantines (2.22-12.3 mg kg-1) were the most abundant followed by procyanidins (0.69-9.39 mg kg-1) and epicatechin (0.16-3.12 mg kg-1), all reduced by heat treatments. Volatile organic compounds and BAs showed variable levels and distributions. Although showing the highest BAs total content (28.8 mg kg-1), Criollo variety presented a good aroma profile, suggesting a possible processing without roasting. Heat treatments influenced the aroma compounds especially for Nicaragua sample, increasing more than two-fold desirable aldehydes and pyrazines formed during the Maillard cascade and the Strecker degradation. As the temperature increased, the concentration of BAs already present in raw samples increased as well, although never reaching hazardous levels.

In vitro studies on anti-inflammatory activities of kiwifruit peel extract in human THP-1 monocytes.

ETHNOPHARMACOLOGICAL RELEVANCE: Kiwifruit is native to eastern China and many are the references about the consumption of fruits and fruits extracts of the Actinidia plants in Chinese traditional medicine as therapeutic food supplements to prevent and/or counteract numerous disorders including inflammation-related diseases like cancer. AIM OF THE STUDY: Aim of the present work was to obtain a kiwifruit peel extract, rich in polyphenols, and to explore the anti-inflammatory potential by analyzing its capability to target multiple pathways involved in monocyte-mediated inflammatory response. MATERIALS AND METHODS: The extract was obtained from the fruit peel of Actinidia deliciosa (A.Chev.) C.F.Liang & A.R.Ferguson, cv Hayward and characterized by HPLC-DAD-ESI-MS. Lipopolysaccharide-stimulated THP-1 monocytes were used as a model of human inflammation in vitro. RESULTS: Analytical data evidenced that procyanidins resulted the main polyphenols present in the extract, representing the 92% w/w of the total. The extract inhibited the production of inflammatory molecules such as IL-6, IL-1ß, TNF-α pro-inflammatory cytokines, HMGB1 danger signal and granzyme B serine protease by activated monocytes. In particular, an inhibitory activity of 81%, 68%, 63%, 76% and 60% on the extracellular release of IL-6, IL-1ß, TNF-α, HMGB1 and granzyme B, respectively, was observed by western blot analysis. Moreover, the extract prevented STAT3 activation and promoted autophagy. CONCLUSIONS: The reported findings demonstrated a strong and broad anti-inflammatory profile of the kiwifruit peel extract, which makes it a promising preventive and therapeutic natural ingredient for nutraceutical, cosmetic and pharmaceutical formulations to counteract multiple inflammatory disorders.

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

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

Global Analysis of Type Three Secretion System and Quorum Sensing Inhibition of Pseudomonas savastanoi by Polyphenols Extracts from Vegetable Residues.

Protection of plants against bacterial diseases still mainly relies on the use of chemical pesticides, which in Europe correspond essentially to copper-based compounds. However, recently plant diseases control is oriented towards a rational use of molecules and extracts, generally with natural origin, with lower intrinsic toxicity and a reduced negative environmental impact. In this work, polyphenolic extracts from vegetable no food/feed residues of typical Mediterranean crops, as Olea europaea, Cynara scolymus, and Vitis vinifera were obtained and their inhibitory activity on the Type Three Secretion System (TTSS) and the Quorum Sensing (QS) of the Gram-negative phytopathogenic bacterium Pseudomonas savastanoi pv. nerii strain Psn23 was assessed. Extract from green tea (Camellia sinensis) was used as a positive control. Collectively, the data obtained through gfp-promoter fusion system and real-time PCR show that all the polyphenolic extracts here studied have a high inhibitory activity on both the TTSS and QS of Psn23, without any depressing effect on bacterial viability. Extracts from green tea and grape seeds were shown to be the most active. Such activity was confirmed in planta by a strong reduction in the ability of Psn23 to develop hyperplastic galls on explants from adult oleander plants, as well as to elicit hypersensitive response on tobacco. By using a newly developed Congo red assay and an ELISA test, we demonstrated that the TTSS-targeted activity of these polyphenolic extracts also affects the TTSS pilus assembly. In consideration of the potential application of polyphenolic extracts in plant protection, the absence of any toxicity of these polyphenolic compounds was also assessed. A widely and evolutionary conserved molecular target such as Ca2+-ATPase, essential for the survival of any living organism, was used for the toxicity assessment.

Hydrolyzable Tannins from Sweet Chestnut Fractions Obtained by a Sustainable and Eco-friendly Industrial Process.

Sweet Chestnut (Castanea sativa Mill.) wood extracts, rich in Hydrolyzable Tannins (HTs), are traditionally used in the tanning and textile industries, but recent studies suggest additional uses. The aim of this work is the HPLC-DAD-ESI-MS characterization of Sweet Chestnut aqueous extracts and fractions obtained through a membrane separation technology system without using other solvents, and the evaluation of their antioxidant and antiradical activities. Total tannins range between 2.7 and 138.4 mM; gallic acid ranges between 6% and 100%; castalagin and vescalagin range between 0% and 40%. Gallic Acid Equivalents, measured with the Folin-Ciocalteu test, range between 0.067 and 56.99 g/100 g extract weight; ORAC test results for the marketed fractions are 450.4 and 3050 µmol/g Trolox Equivalents/extract weight. EC50 values, measured with the DPPH test, range between 0.444 and 2.399 µM. These results suggest a new ecofriendly and economically sustainable method for obtaining chestnut fractions with differentiated, stable and reproducible chemical compositions. Such fractions can be marketed for innovative uses in several sectors.