Targeted Recovery of Phenolic Antioxidants from Grape Stems: A Sequential Approach

Grape stems are an abundant by-product of winemaking and a promising source of phenolic antioxidants representing an underutilized biomass within the circular economy. Seven Vitis vinifera L. cultivars were analysed by HPLC DAD, with Merlot (Me), Cabernet Sauvignon (CS) and Italian Riesling (IR) identified as the richest sources. This comparative screening provided the basis for a multi-index optimization of extraction. A 2³ full factorial design (ethanol 30-60% v/v; 30-80 min; 25-65 °C) was used for optimization. The optimal green conditions-60% ethanol, 80 min, 65 °C-yielded 1.860 mg/g CA, 1.098 mg/g Q-gluc and 0.409 mg/g Q-glc, with the Merlot stems showing the highest extraction efficiency and Merlot consistently outperforming the other varieties. Kinetic modeling using an unsteady state diffusion model showed excellent agreement (R² ≈ 0.99, RMS < 2%), suggesting a leaching-diffusion mechanism. The thermodynamic parameters confirmed an endothermic, spontaneous and irreversible process with ΔH° between 19.5 and 36.6 kJ/mol, ΔS° between 69.1 and 131.6 J/molK and ΔG° between -1.1 and -9.2 kJ/mol, depending on the compound and grape stem variety. This study shows that grape stems can be efficiently utilised as a sustainable source of phenolic antioxidants, with potential applications in the production of functional foods and dietary supplements. This integration highlights the novelty of the study and supports the valorization of grape stems in the framework of sustainability and the circular economy.