Controlled Selective Formation of Amadori Compounds from α/ε Mono- or Di-glycation of Lysine with Xylose

Three Amadori rearrangement products (Xyl-α-Lys-ARP, Xyl-ε-Lys-ARP, and diXyl-α,ε-Lys-ARP) were observed in the xylose-lysine (Xyl-Lys) Maillard reaction model. They were separated and characterized by liquid chromatography with tandem mass spectrometry and NMR. The crucial roles of reaction temperature, pH, molar ratio of Xyl to Lys, and reaction time in the formation of different Xyl-Lys-ARPs were investigated. The proportion of Xyl-α-Lys-ARP among all Xyl-Lys-ARPs was increased to 48.41% (its concentration was 25.31 μmol/mL) after the reaction at pH = 5.5 and a molar ratio of 3:1 (Xyl: Lys) for 9 min, while only Xyl-ε-Lys-ARP was generated at a higher pH (7.5) and a lower molar ratio of 1:5. Moreover, the much higher activation energy (84.08 kJ/mol) of diXyl-α,ε-Lys-ARP than Xyl-α-Lys-ARP (34.19 kJ/mol) and Xyl-ε-Lys-ARP (32.32 kJ/mol) indicated a pronounced promoting effect on diXyl-α,ε-Lys-ARP formation by high temperatures. A complete conversion from Xyl-α-Lys-ARP and Xyl-ε-Lys-ARP to diXyl-α,ε-Lys-ARP was achieved through the reaction time prolongation and Xyl concentration increase at a higher temperature; the concentration of diXyl-α,ε-Lys-ARP was 39.05 μmol/mL at a molar ratio of 5:1 for 40 min. Accordingly, the selective preparation of Xyl-α-Lys-ARP, Xyl-ε-Lys-ARP, and diXyl-α,ε-Lys-ARP could be achieved through adjusting the Xyl-Lys ratio, pH, and reaction time.