Monitoring carbonyl-amine reaction between pyruvic acid and alpha-amino alcohols by FTIR spectroscopy--a possible route to Amadori products.

Abstract

The carbonyl-amine reaction between pyruvic acid and alpha-amino alcohols was monitored by Fourier transform infrared spectroscopy at a temperature range between 20 and 100 degrees C and under acidic and basic conditions. To avoid interference, the reactions were conducted in the absence of solvent using liquid reactants such as methyl pyruvate, pyruvic acid, ethanolamine, and 1-amino-2,3-propanediol. Analysis of the time- and temperature-dependent spectra indicated that under basic conditions and at room temperature, the initial imine formation and its subsequent isomerization through a 1,3-prototropic shift occur very rapidly and the reaction goes to completion within 12 min. Interestingly, the isomerization product of the initial imine is the so-called Schiff base intermediate formed when the corresponding amino acid and the reducing sugar react during a typical Maillard reaction. Furthermore, the detailed studies also indicated that during the first 30 s, the rate of formation of the initial imine was faster than the rate of its isomerization; however, after 60 s, its rate of isomerization becomes faster than the rate of its formation. The data also indicated that under acidic conditions, this isomerization was prevented from occurring and the reaction was terminated at the initial imine formation stage. In addition, temperature-dependent spectra indicated that the isomerization of the Schiff's base into eneaminol can be achieved at or above 60 degrees C and its subsequent rearrangement into Amadori product can be attained at temperatures above 80 degrees C even under basic conditions, thus providing a novel route to Maillard reaction products starting from a keto acid and an amino alcohol. This observation was also confirmed through identification of the common Amadori product in both keto acid/amino alcohol and sugar/amino acid mixtures, by the application of tandem mass spectrometry and chemical ionization techniques.