Maillard Mimetic Food-Grade Synthesis of N-(β- d -Deoxyfructos-1-yl)- l -glutamic Acid and N-(β- d -Deoxyfructos-1-yl)-β-alanyl- l -histidine by a Combination of Lyophilization and Thermal Treatment

A typical glycoconjugate of glutamic acid, namely, N-(β-d-deoxyfructos-1-yl)-l-glutamic acid, was successfully synthesized as the primary isomer in a yield of 96.08% using a food-grade preparation method, and its chemical structure was clearly demonstrated by mass spectrometry and 1D/2D NMR. The reaction kinetics of glucose and glutamic acid were systematically studied to investigate the effect of lyophilization and thermal treatment on the conversion of reactants to their corresponding Amadori rearrangement product (ARP). Interestingly, besides the initial pH value, temperature, and heating time, the initial concentration of glutamic acid also influenced the final yield because intramolecular dehydration occurred at the same time, competing with the Maillard reaction and degrading reaction. Moreover, a similar Amadori compound of carnosine was also prepared in a yield of about 66.38% and the yield could be further improved to 95% after condition optimization. One major isomer of the corresponding ARP of the peptide was confirmed to be N-(β-d-deoxyfructos-1-yl)-β-alanyl-l-histidine by structure characterization, indicating that this is a good method to prepare the N-(β-d-deoxyfructos-1-yl)-amino acid/peptide.