Oxidative pyrolysis and postpyrolytic derivatization techniques for the total analysis of maillard model systems: investigation of control parameters of maillard reaction pathways.

Factors that regulate various pathways of Maillard reaction leading to aroma, color, or carcinogen generation have not been identified, due to the difficulties associated with analyzing complex reaction mixtures. In particular, the role played by oxidation in directing aromagenic, chromogenic, or carcinogenic pathways is not well understood. In order to overcome the analytical difficulties, novel Py-GC/MS-based methodologies were developed to analyze volatile and nonvolatile residues of Maillard reaction products generated from the same model system under air or helium atmosphere. The analysis of nonvolatiles was achieved through a postpyrolytic in situ derivatization technique using hexamethyldisilazane, and pyrolysis under air was achieved through modification of the GC equipped with sample concentration trap to allow gas stream switching and subsequent isolation of the pyrolysis chamber from the analytical stream. In this approach label incorporation from the starting materials can be observed in both volatile and nonoxidative conditions for mechanistic studies. In addition, monitoring of redox potentials, oxygen consumption, and color generation of relevant model systems over time were also carried out at different temperatures. The data collected have indicated that perturbation in the redox potential of Maillard model systems by external (oxidizing conditions) or internal (formation of reductones) factors can alter the balance among the four critically important groups of precursors: alpha-dicarbonyl, alpha-hydroxycarbonyl, 2-aminocarbonyls, and 2-(amino acid)-carbonyl compounds and hence control the relative importance of aromagenic versus chromogenic pathways.