Simultaneous extraction of cocoa butter and antioxidants from defective cocoa beans by natural deep eutectic solvents

Defective purple cocoa beans from incomplete fermentation are an underutilized source of cocoa butter and phenolic antioxidants. Natural deep eutectic solvents (NADES) are used to extract polar bioactives, but their role in non-polar oil recovery through plant-matrix disruption remains underexplored. This study developed a NADES-assisted single-step extraction process for simultaneous cocoa butter and phenolic antioxidant recovery and examined whether oil release was associated with cell-wall disruption. Among six oil-immiscible NADES, choline chloride–lactic acid (ChCl–LA, 1:2) was selected for high cocoa butter recovery while retaining phenolic extraction. ChCl–LA recovered 63.02% of total extractable oil, exceeding anhydrous ethanol and acidified water but not screw pressing. Its oil showed a peroxide value (1.80 meq O₂/kg), lower than that obtained by Soxhlet, ethanol, and pH control extractions and comparable to screw-pressed oil. The aqueous NADES fraction showed a total phenolic content of 45.17 mg GAE/g dry weight, 44.46 mg TE/g dry weight DPPH activity, and 57.79 mg TE/g dry weight FRAP capacity. Reduced relative hemicellulose and lignin contents and SEM-observed morphological changes were consistent with cell-wall modification that may have contributed to oil release. These findings demonstrate the potential of oil-immiscible NADES for dual recovery of cocoa butter and phenolic antioxidants.