Sequential extraction and purification stages are required to obtain extracts rich in specific polyphenols. However, both separation processes are often optimized independently and the effect of the integrated process on the global recovery of polyphenols has not been fully elucidated yet. We assessed the impact of hot-pressurized liquid extraction (HPLE) conditions (temperature: 90–150 °C; ethanol concentration: 15%–50%) on the global recovery of specific phenolic acids, flavanols, flavonols and stilbenes from Carménère grape pomace in an integrated HPLE/resin purification (RP) process. HPLE of phenolic acids, flavanols and stilbenes were favored when temperature and ethanol concentration increased, except for chlorogenic acid which showed an increment of its Gibbs free energy of solvation at higher ethanol contents. Ethanol concentration significantly impacted the global yield of the integrated HPLE/RP process. The lower the ethanol content of the HPLE extracts, the higher the recovery of phenolic acids, flavanols and stilbenes after RP, except for flavonols which present more polar functional groups. The best specific recovery conditions were 150 °C and ethanol concentrations of 15%, 32.5% and 50% for phenolic acids, flavanols and stilbenes, and flavonols, respectively. At 150 °C and 32.5% of ethanol, the extracts presented the highest total polyphenol content and antioxidant capacity. The integrated HPLE/RP process allows a selective separation of specific polyphenols and eliminates the interfering compounds, ensuring the safety of the extracts at all evaluated conditions.

Thermal degradation and generation of objectionable compounds such as hydroxymethylfurfural have been observed in hot pressurised water extraction of polyphenols. Addition of small amounts of ethanol can reduce process temperatures and retain extraction efficiencies. However, ethanol may reduce the recovery of polyphenols in the subsequent purification stage. The overall effect of increasing amounts of ethanol (0-15%) and reduced temperatures (90, 75, 60°C) in the extraction stage, as well as increasing amounts of ethanol in the desorption eluent (60-80%) were analysed in a combined hot pressurised liquid extraction-resin purification grape pomace polyphenols process for the first time. Without decreasing the polyphenols recovery (~24 mg GAE g À1 ), ethanol addition (15%) reduced the extraction temperature (from 130 to 90°C) which not only decreased the reducing sugar extraction (~25%) but also avoided the hydroxymethylfurfural generation in the extraction stage. Additionally, the combined hot pressurised liquid extraction-resin purification process preserved the proanthocyanidin oligomeric distribution and was selective to polyphenols. The operating conditions found for the combined process, efficiently produced purified polyphenols extracts (11 mg GAE g À1 ), free of hydroxymethylfurfural and reducing sugars.Carm en ere pomace polyphenols extracts M. S. Mariotti-Celis et al.

Hot pressurized liquid extraction has been used to obtain polyphenols; however, its operating conditions can generate hydroxymethylfurfural, a potential human carcinogen. The addition of ethanol can reduce process temperatures and retain extraction efficiencies, but the ethanol may reduce the recovery of polyphenols in the subsequent purification stage, affecting the antioxidant properties of the extracts. This study evaluates a combined hot pressurized liquid extraction—resin purification process to obtain polyphenol extracts from spent ground coffee reduced in hydroxymethylfurfural. A multifactorial design was developed to determine the combined effect of the extraction (ethanol content: 0–16% and temperature: 60–90 °C) and purification (ethanol: 60–80%) conditions on some chemical properties of the extracts. The highest recovery of polyphenols (~8 mg GAE/g dry coffee solids) and reduction of hydroxymethylfurfural (95%) were obtained at 90 °C and 16% of ethanol during extraction and 80% of ethanol during purification. These operating conditions retained the antioxidant capacity of the crude extract between 60% and 88% depending on the determination method and recovered 90, 98, and 100% of 4-feruloylquinic acid, epicatechin, and 5-feruloylquinic acid, respectively after purification. The combined process allows differential polyphenols’ recovery and enhances the safety of the extracts. Our computational chemistry results ruled out that the overall selectivity of the integrated process was correlated with the size of the polyphenols.

Glycerol is a co-solvent for water extraction that has been shown to be highly effective for obtaining polyphenol extracts under atmospheric conditions. However, its efficacy under subcritical conditions has not yet been studied. We assessed different water-glycerol mixtures (15%, 32.5%, and 50%) in a hot pressurized liquid extraction system (HPLE: 10 MPa) at 90 °C, 120 °C, and 150 °C to obtain extracts of low molecular weight polyphenols from Carménère grape pomace. Under the same extraction conditions, glycerol as a co-solvent achieved significantly higher yields in polyphenols than ethanol. Optimal extraction conditions were 150 °C, with 32.5% glycerol for flavonols and 50% for flavanols, stilbenes, and phenolic acids. Considering gallic acid as a model molecule, computational chemistry calculations were applied to explain some unusual extraction outcomes. Furthermore, glycerol, methanol, ethanol, and ethylene glycol were studied to establish an incipient structure–property relationship. The high extraction yields of gallic acid obtained with water and glycerol solvent mixtures can be explained not only by the additional hydrogen bonds between glycerol and gallic acid as compared with the other alcohols, but also because the third hydroxyl group allows the formation of a three-centered hydrogen bond, which intensifies the strongest glycerol and gallic acid hydrogen bond. The above occurs both in neutral and deprotonated gallic acid. Consequently, glycerol confers to the extraction solvent a higher solvation energy of polyphenols than ethanol.