A Comparison between High-Performance Countercurrent Chromatography and Fast-Centrifugal Partition Chromatography for a One-Step Isolation of Flavonoids from Peanut Hulls Supported by a Conductor like Screening Model for Real Solvents.

Peanut hulls (Arachis hypogaea, Leguminosae), which are a side stream of global peanut processing, are rich in bioactive flavonoids such as luteolin, eriodictyol, and 5,7-dihydroxychromone. This study aimed to isolate these flavonoid derivatives by liquid-liquid chromatography with as few steps as possible. To this end, luteolin, eriodictyol and 5,7-dihydroxychromone were isolated from peanut hulls using two different techniques, high-performance countercurrent chromatography (HPCCC) and fast-centrifugal partition chromatography (FCPC). The suitability of the biphasic solvent system composed of n-hexane/ethyl acetate/methanol/water (1.0/1.0/1.0/1.5; v/v/v/v) was determined by the Conductor like Screening Model for Real Solvents (COSMO-RS), which allowed the partition ratio KD-values of the three main flavonoids to be calculated. After a one-step HPCCC separation of ~1000 mg of an ethanolic peanut hull extract, 15 mg of luteolin and 8 mg of eriodictyol were isolated with purities over 96%. Furthermore, 3 mg of 5,7-dihydroxychromone could be isolated after purification by semi-preparative reversed-phase liquid chromatography (semi-prep. HPLC) in purity of over 99%. The compounds were identified by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance spectroscopy (NMR).

Target-Guided Isolation of Progenitors of 1,1,6-Trimethyl-1,2-dihydronaphthalene (TDN) from Riesling Wine by High-Performance Countercurrent Chromatography.

High-performance countercurrent chromatography (HPCCC) was used for the target-guided isolation of precursors of 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) from Riesling wine. In separated HPCCC fractions of an Amberlite® XAD®-2 extract obtained from a German Riesling, TDN-generating fractions were identified by the acid-catalyzed hydrolysis of the progenitors at pH 3.0 and subsequent HS-GC-MS/MS analysis. The presence of multiple TDN-generating precursors in Riesling wine could be confirmed. From polar HPCCC fractions (11-13 and 14-16), 3,4-dihydroxy-7,8-dihydro-ß-ionone 3-O-rutinoside and 3,4-dihydroxy-7,8-dihydro-ß-ionone 3-O-ß-d-glucopyranoside were isolated as major TDN-precursors at a sufficient amount for structure elucidation by NMR spectroscopic studies. In the medium polar HPCCC factions (27-35), enzymatic hydrolysis liberated the aglycones 3-hydroxy-ß-ionone and 3-hydroxy-TDN in minor amounts. In further less polar TDN-generation fractions (36-44 and 45-50), glycosidic progenitors were absent; instead, a minor TDN formation most likely from non-conjugated constituents was observed.

Sustainable In Silico-Supported Ultrasonic-Assisted Extraction of Oligomeric Stilbenoids from Grapevine Roots Using Natural Deep Eutectic Solvents (NADES) and Stability Study of Potential Ready-to-Use Extracts.

Grapevine roots, as a side-stream of a vineyard, are a sustainable resource for the recovery of oligomeric stilbenoids, such as the bioactive r-viniferin. The aim of this study is to evaluate an in silico-supported method, based on the Conductor-like Screening Model for Real Solvents (COSMO-RS), for selection of environmentally friendly natural deep eutectic solvents (NADES) with regard to the extraction of grapevine roots. The most suitable NADES system for ultrasonic-assisted extraction of r-viniferin was choline chloride/1,2-propanediol. The optimal extraction parameters for r-viniferin were determined using single-factor experiments as follows: choline chloride/1,2-propanediol 1/2 mol/mol, 10 wt% H2O, biomass/NADES ratio 1/10 g/g, and 10 min extraction time. Under optimized conditions, the extraction yield of r-viniferin from grapevine roots reached 76% of the total r-viniferin content. Regarding stability, stilbenoids in choline chloride/1,2-propanediol remained stable during 128 days of storage at ambient temperature. However, fructose/lactic acid-based NADES were observed to degrade stilbenoids; therefore, the removal of the NADES will be of interest, with a suitable method implemented using Amberlite® XAD-16N resin. As green solvents, the NADES have been used as effective and environmentally friendly extractants of stilbenoid-containing extracts from grapevine roots for potential applications in the cosmetic and pharmaceutical industry or as nutraceuticals in the food industry.

In Silico-Assisted Isolation of trans-Resveratrol and trans-ε-Viniferin from Grapevine Canes and Their Sustainable Extraction Using Natural Deep Eutectic Solvents (NADES).

Grapevine canes are an important source of bioactive compounds, such as stilbenoids. This study aimed to evaluate an in silico method, based on the Conductor-like Screening Model for Real Solvents (COSMO-RS) to isolate stilbenoids from a grapevine cane extract by offline heart-cut high-performance countercurrent chromatography (HPCCC). For the following extraction of resveratrol and ε-viniferin from grapevine canes, natural deep eutectic solvents (NADES) were used as an environmentally friendly alternative to the traditionally used organic solvents. In order to evaluate a variety of combinations of hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs) for the targeted extraction of stilbenoids, COSMO-RS was applied. In particular, ultrasonic-assisted extraction using a solvent mixture of choline chloride/1,2-propanediol leads to higher extraction yields of resveratrol and ε-viniferin. COSMO-RS calculations for NADES extraction combined with HPCCC biphasic solvent system calculations are a powerful combination for the sustainable extraction, recovery, and isolation of natural products. This in silico-supported workflow enables the reduction of preliminary experimental tests required for the extraction and isolation of natural compounds.