Mechanism of formation of redox-active hydroxylated benzenes and pyrazine in 13C-labeled glycine/D-glucose model systems

To extend the analytical capabilities of the pyrolysis-gas chromatograph-mass spectrometry system that has been successfully utilized in the past as an integrated reaction, separation, and identification system to study label incorporation patterns in Maillard reaction products, a novel methodology was developed to analyze the composition of nonvolatile residues of the initial reaction products. This was achieved through a postpyrolytic in-situ derivatization technique using trimethylsilyldiethylamine. Application of this technique to the investigation of the nonvolatile products formed during pyrolysis of glucose alone and in the presence of glycine has indicated the formation of several redox-active hydroxylated benzene derivatives such as 1,2,3-trihydroxybenzene (pyrogallol), 1,4-dihydroxybenzene (hydroquinone), 1,2-dihydroxybenzene (catechol), and 2,5-dihydroxypyrazine. Labeling studies have indicated that the intact glucose carbon backbone was involved in the construction of the benzene ring of the hydroxylated benzene derivatives and that dimerization of glycine alone can lead to the formation of 2,5-dihydroxypyrazine.