Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)

Natural deep eutectic solvents (NaDESs) are emerging solvents for their yield when used for extraction of different molecules, including polyphenols. NaDESs are a cutting-edge technology that offers numerous advantages, including cheap cost, safety, effectiveness and environmental friendliness. Howe...

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Main Authors: Alessandro Frontini, Giulio Tarentini, Carmine Negro, Andrea Luvisi, Massimiliano Apollonio, Luigi De Bellis
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Separations
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Online Access:https://www.mdpi.com/2297-8739/12/6/148
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author Alessandro Frontini
Giulio Tarentini
Carmine Negro
Andrea Luvisi
Massimiliano Apollonio
Luigi De Bellis
author_facet Alessandro Frontini
Giulio Tarentini
Carmine Negro
Andrea Luvisi
Massimiliano Apollonio
Luigi De Bellis
author_sort Alessandro Frontini
collection DOAJ
description Natural deep eutectic solvents (NaDESs) are emerging solvents for their yield when used for extraction of different molecules, including polyphenols. NaDESs are a cutting-edge technology that offers numerous advantages, including cheap cost, safety, effectiveness and environmental friendliness. However, due to NaDES’ high boiling point, the recovery and separation of compounds after the extraction is the bottleneck of the process. In this work, two affordable methods were tested for the recovery of phenolic compounds from three binary NaDESs (composed of choline chloride mixed separately with lactic acid, tartaric acid or glycerol as hydrogen bond donors): the antisolvent and the liquid–liquid extraction methods. The former was assessed by diluting the extracts with different aliquots of water, employed as antisolvent, which was ineffective. For the liquid–liquid extraction method, ethyl acetate (EtOAc), acetonitrile (ACN), 2-chlorobutane (2-CB) and 2-methyltetrahydrofuran (2-MeTHF) were compared. Except for ACN, all solvents were perfectly immiscible with the three NaDESs, forming biphasic systems that were analyzed by colorimetric assays and HPLC/MS. 2-MeTHF applied on a 10-fold water dilution of the NaDES extract reached recovery percentages higher than 90% for most of the non-anthocyanin phenols and good recovery (up to 80%) for some anthocyanins. 2-MeTHF appears to be the first known solvent capable of extracting anthocyanins from NaDESs. Finally, a two-step liquid–liquid extraction performed firstly with EtOAc and subsequently with 2-MeTHF is proposed for the separation of different phenolic fractions.
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spelling doaj-art-585cbf11caf84c70a4999a387ecb3fdf2025-08-20T02:21:47ZengMDPI AGSeparations2297-87392025-06-0112614810.3390/separations12060148Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)Alessandro Frontini0Giulio Tarentini1Carmine Negro2Andrea Luvisi3Massimiliano Apollonio4Luigi De Bellis5Department of Biological and Environmental Sciences and Technologies (DiSTeBA), Salento University, Campus Ecotekne, Via Prov.le Lecce-Monteroni, 73100 Lecce, ItalyDepartment of Biological and Environmental Sciences and Technologies (DiSTeBA), Salento University, Campus Ecotekne, Via Prov.le Lecce-Monteroni, 73100 Lecce, ItalyDepartment of Biological and Environmental Sciences and Technologies (DiSTeBA), Salento University, Campus Ecotekne, Via Prov.le Lecce-Monteroni, 73100 Lecce, ItalyDepartment of Biological and Environmental Sciences and Technologies (DiSTeBA), Salento University, Campus Ecotekne, Via Prov.le Lecce-Monteroni, 73100 Lecce, ItalyApollonio Casa Vinicola, Monteroni di Lecce, 73047 Lecce, ItalyDepartment of Biological and Environmental Sciences and Technologies (DiSTeBA), Salento University, Campus Ecotekne, Via Prov.le Lecce-Monteroni, 73100 Lecce, ItalyNatural deep eutectic solvents (NaDESs) are emerging solvents for their yield when used for extraction of different molecules, including polyphenols. NaDESs are a cutting-edge technology that offers numerous advantages, including cheap cost, safety, effectiveness and environmental friendliness. However, due to NaDES’ high boiling point, the recovery and separation of compounds after the extraction is the bottleneck of the process. In this work, two affordable methods were tested for the recovery of phenolic compounds from three binary NaDESs (composed of choline chloride mixed separately with lactic acid, tartaric acid or glycerol as hydrogen bond donors): the antisolvent and the liquid–liquid extraction methods. The former was assessed by diluting the extracts with different aliquots of water, employed as antisolvent, which was ineffective. For the liquid–liquid extraction method, ethyl acetate (EtOAc), acetonitrile (ACN), 2-chlorobutane (2-CB) and 2-methyltetrahydrofuran (2-MeTHF) were compared. Except for ACN, all solvents were perfectly immiscible with the three NaDESs, forming biphasic systems that were analyzed by colorimetric assays and HPLC/MS. 2-MeTHF applied on a 10-fold water dilution of the NaDES extract reached recovery percentages higher than 90% for most of the non-anthocyanin phenols and good recovery (up to 80%) for some anthocyanins. 2-MeTHF appears to be the first known solvent capable of extracting anthocyanins from NaDESs. Finally, a two-step liquid–liquid extraction performed firstly with EtOAc and subsequently with 2-MeTHF is proposed for the separation of different phenolic fractions.https://www.mdpi.com/2297-8739/12/6/148circular economygreen chemistrygrape by-productsantioxidant extraction
spellingShingle Alessandro Frontini
Giulio Tarentini
Carmine Negro
Andrea Luvisi
Massimiliano Apollonio
Luigi De Bellis
Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
Separations
circular economy
green chemistry
grape by-products
antioxidant extraction
title Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
title_full Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
title_fullStr Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
title_full_unstemmed Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
title_short Effective Liquid–Liquid Extraction for the Recovery of Grape Pomace Polyphenols from Natural Deep Eutectic Solvents (NaDES)
title_sort effective liquid liquid extraction for the recovery of grape pomace polyphenols from natural deep eutectic solvents nades
topic circular economy
green chemistry
grape by-products
antioxidant extraction
url https://www.mdpi.com/2297-8739/12/6/148
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