Barley (Hordeum vulgare L.; Poaceae), the second most important grain after wheat, contains phenolamides, specifically hordatines and their agmatinated precursors. Hordatines are the unique compounds found in barley, consumption of which is associated with beneficial effects for human health. This study investigated the impact of germination on the concentrations of barley phenolamides by analyzing their kinetic changes in whole barley seedlings and their distribution across shoots, seeds, and roots over a 9-day germination period under light and dark conditions. To obtain authentic standards, hordatines A and C (HA and HC) were synthesized, while hordatine B (HB) and glycosylated hordatines A and B (HAG and HBG) were isolated from a standardized hordatine-rich fraction (HRF) developed using ion exchange resins. The chemical structures were established using 1H and 13C NMR, UHPLC-HR-ESI-MS, and literature comparison, validating the presence of trans double bonds in hordatines. Germination results exhibited that darkness promotes the accumulation of barley phenolamides, with a significant increase in hordatine aglycones, particularly HA and HB. Glycosylated hordatines were abundant in early germination (Days 0 and 1; ∼7-14mg/100g), while hordatine aglycones became more prevalent in later stages (Days 5, 7, and 9; ∼6.5-100mg/100g). HA and p-coumaroyl putrescine were identified as shoot-specific and root-specific phytochemicals, respectively, with higher rates of methylation and glycosylation of hordatines observed in roots compared to shoots.
Read full abstract