Nonvolatile Oxidation Products of Glucose in Maillard Model Systems: Formation of Saccharinic and Aldonic Acids and Their Corresponding Lactones

Abstract

By using pyrolysis-gas chromatography-mass spectrometry-based methodologies, nonvolatile oxidation products of isotopically labeled glucose/glycine model systems were studied through a postpyrolytic in situ derivatization technique by using trimethylsilyldiethylamine. Analysis of the data indicated that the known reactive sugar intermediates such as glucosone and its deoxy derivatives can undergo in Maillard model systems three types of transformations: oxidation of the aldehydic groups into carboxylic acids, oxidative cleavage of alpha-dicarbonyl moieties into aldonic acids, and benzylic acid rearrangement of 1-deoxy-glucosone into saccharinic acids. The aldonic and saccharinic acids were identified through silylation of their lactone derivatives, and their origin was verified through (13)C-labeling studies. The following lactones were identified in glucose and glucose/glycine model systems: trans-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3 H)-furanone, cis-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3H)-furanone, 2-C-methyl-2,3,5-tris-O-(trimethylsilyl)-D-ribonic acid gamma-lactone, 3-deoxy-2,5,6-tris-O-(trimethylsilyl)-D-ribo-hexonic acid gamma-lactone, 2-deoxy-3,5-bis-O-(trimethylsilyl)-pentonic acid gamma-lactone, and 2,3,5-tris-O-(trimethylsilyl)-D-arabinonic acid gamma-lactone. The observed reduction in color and aroma in Maillard reactions performed under oxidative conditions may be attributed to the oxidation of reactive dicarbonyls into the corresponding carboxylic acids or their corresponding lactones.