Imidazoles Maillard reactions

The imidazole part of the IQ-compounds suggests creatinine as a common precursor. The remaining parts of the IQ-compounds could arise from Maillard reaction products, e.g., 2-methylpyri-dine or 2,5-dimethylpyrazine. These two compounds could be formed through Strecker degradation. In Maillard reactions, this is induced by a-dicarbonyl compounds derived from carbohydrates, which are thereby converted to pyrroles, pyridines, pyrazines, etc. (8). 

Many other compounds have been identified as products of the sugar-amino acid reaction. Amongst these are 2,3-butanedione,195 formaldehyde,196 pyruvaldehyde,20,195, 247, 248 3-hydroxy-2-butanone,248 hydroxy-2-propanone,248 and acetaldehyde.73 Imidazoles,196, 249-251 especially 4(5)-methylimidazole, have also been isolated from the reaction under mild conditions, and could have been formed from a-hydroxy ketones or aldehydes plus amino compounds. Following the early identification247 of pyru-valdehyde as a product of the Maillard reaction, much work was done in an attempt to show that this reactive compound plays a major role in the reaction,249 262 254 but, that this is so is by no means certain.7... 

Even though imidazoles comprise the second largest fraction of the volatile products obtained from Maillard reaction after pyrazines, they do not contribute any characteristic flavors to cooked foods (23). 

Formation mechanisms of imidazoles in the Maillard reaction are not as well understood as those of other heterocyclic compounds. The role of a-amino carbonyl fragments as intermediates in imidazole formation was suggested in the reaction of sucrose and ammonia (43). In a study of a L-rhamnose/ammonia model system, which produced fifty-two imidazoles, it was proposed that an amino-hydroxy fragment was responsible for imidazole... 

T. Hofmann, 4-Alkylidene-2-imino-5-[4-alkylidene-5-oxo-l,3-imidazol-2-inyl]aza-methylidine-l,3-imidazolidine —A novel colored substructure in melanoidins formed by Maillard reactions of bound arginine with glyoxal and furan-2-carboxaldehyde, J. Agric. Food Chem., 1998, 46, 3896-3901. 

A starch-glycine mixture, heated at 290°C, was significantly different from the starch control in its composition of alkoxyphenols and imidazoles in the involatile phase, and pyrazine, pyridine, methylpyridine, and dimeth-ylpyrroles in the volatile phase (Umano and Shibamoto, 1984). The neurotoxin 4(5)-methylimidazole appeared in the vapor phase when ammonia, but not amino acids, was the nitrogen source (Tomasik et al., 1989b). A corn starch-sucrose combination inhibited the Maillard reaction (Lee and Woo, 1988). 

Aldoses undergo the Amadori rearrangement and subsequently turn into caramels, the natural brown food colorants, and/or heteroaromatic compounds — derivatives of pyrrole, imidazole, and pyrazine. Ketoses react similarly into ketosylamino acids or ketosylamines, which, in the first step, undergo the Heyns rearrangement (5.17-5.23). These rearrangements are the first steps of either thermal or enzymatic (the Maillard reaction) reactions resulting in the browning of food and the aroma of roasted, baked, or fried foodstuffs. 

The Maillard reaction plays an important role in flavor development, especially in meat and savory flavor (Buckholz, 1988). Products of the Maillard reaction are aldehydes, acids, sulfur compounds (e.g., hydrogen sulfide and methanethiol), nitrogen compounds (e.g., ammonia and amines), and heterocyclic compounds such as furans, pyrazines, pyrroles, pyridines, imidazoles, oxazoles, thiazoles, thiophenes, di- and trithiolanes, di- and trithianes, and furanthiols (Martins et al., 2001). Higher temperature results in production of more heterocyclic compounds, among which many have a roasty, toasty, or caramel-like aroma. 

Some Amino Add-Specific Compounds. As listed in Table I, there were three pyrrolizines and one pyridoimidazole identified in the model systems. Pyrrolizines are a very in rtant class of volatile conpounds generated by the reaction of proline with reducing sugars. 2-Acetyl-pyrido(3,4-d)imidazole was another amino acid-specific Maillard reaction product identified in the model systems, which was derived fi om the reaction of histidine with dicaibonyls. 

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