Maillard Reaction: Investigation of the Chemical Structure of Melanoioins Synthesized from D-Xylose and Glycine Using 13C and 15N Specifically Labeled Reactants

Abstract

Melanoldins were Isolated 1n 36% yield w/w from molar solution of D-xylose and glydne-2-¹³C (A); D-xylose and glycine-l-¹³C (B); D-xylose-1-¹³C and glydne (C); D-xylose and glyclne (D); D-xylose and glycine-¹⁵N (E). Each solutTon was kept at 68ddot]C until complete disappearance of xylose as evidenced by NMR. ¹³C and ¹⁵N solid state nuclear magnetic resonance and diffuse reflectance Infrared spectrometry were used in their structural elucidation before and after basic and add hydrolysis. Both C-1 and C-2 of glycine were Incorporated Into the polymers. In the ¹³C CP-MAS NMR spectra, C-1 gave a single peak in the polymer at 171.3 ppm, while C-2 gave three at 48.1, 31.2 and 22.5 ppm. Area measurements of the respective peaks Indicated that 50% of the Incorporated glycine had undergone decarboxylatlon. C-1 of xylose was Incorporated into the polymers mainly as two types of carbons at 68.8 ppm (CHOH, C-OH) and at 133.3 ppm (unsaturated C). Hydrolysis (6N HC1) led to a 20% reduction 1n weight of the melanoldlns, a decrease of 2% in C and 10% in N. ¹³C CP-MAS NMR revealed after hydrolysis of D, the disappearance of signals at 69, 110, 152, 172 and 200 ppm. Hydrolysis of A and B reduced all signals originating from C-1 and C-2 of glydne, while hydrolysis of C reduced only the signal of 68.8 ppm. ¹⁵N CP-MAS NMR of hydrolyzed E showed a greatly reduced amide resonance at 100 ppm, with more pyrrole or imino N. DR-IR showed a reduction 1n both the 1625 and 1550 cm^-1 bands with a concurrent appearance of a 1715 cm^-1 band.