Simple SummaryFatty acids, especially the representatives of essential mono- and polyunsaturated ones, play an important role in the human organism, as they are involved in the regulation of the immune and central nervous systems. Whole grain products are considered to be a rich source of multiple health-promoting phytochemicals, including fatty acids, where polyunsaturated fatty acids take prevalence over saturated ones. To improve the milling performance of grain and ensure the high-quality standards of flour, technologies presently utilized within the milling process, e.g., dehulling and debranning, generally aim at removing outer layers of cereal grain and result in substantial reduction of valuable nutrients along with loss of functionality. In spite of the relative abundance of valuable compounds in cereal bran, currently less than 10% of produced bran is used in the food industry. To valorize cereal bran for food and pharmaceutical applications, additional pre-treatment is required.The main intention of the present work was to investigate the ability of cellulose-degrading enzymes (C-DE) to release fatty acids (FAs) from complex matrices of cereal by-products during enzymatic hydrolysis (EH). For this purpose, three types of cereal bran (CB), i.e., wheat, rye, and oat, were used as lignocellulose substrates for three commercially available hydrolytic enzymes, i.e., Viscozyme L, Viscoferm, and Celluclast 1.5 L. The yield and composition of FAs after EH were assessed and compared with those obtained after either conventional Soxhlet extraction or after alkaline-assisted hydrolysis (A-AH) with 10% KOH in 80% MeOH and subsequent liquid–liquid extraction. The experimental results demonstrated that up to 6.3% and 43.7% higher total FA yield can be achieved by EH of rye bran using Celluclast 1.5 L than by A-AH and Soxhlet extraction, respectively. However, the application of Viscoferm for EH of wheat bran ensured up to 7.7% and 13.4% higher total FA yield than A-AH and Soxhlet extraction, respectively. The concentration of essential linolenic acid (C18:3) in lipids extracted after EH of rye bran with Celluclast 1.5 L was up to 24.4% and 57.0% higher than in lipids recovered by A-AH and Soxhlet extraction, respectively. In turn, the highest content of linolenic acid in wheat bran lipids was observed after EH with Viscoferm and Viscozyme L, ensuring 17.0% and 13.6% higher yield than after A-AH, respectively. SEM analysis confirmed substantial degradation of the CB matrix promoted by the ability of C-DE to act specifically on glycosidic bonds in cellulose and on xylosidic bonds in arabinoxylans, arabinans, and other arabinose-containing hemicelluloses. Structural alterations in cell integrity greatly contributed to the release of bound FAs and their better transfer into the extraction solvent. It has been shown that the proposed process of EH can be used for the efficient release of FAs from the CB matrix more sustainably and with a safer profile, thereby conveying greener production of FAs for certain purposes.
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