Maillard products, amino acid specific

Formation of Amino Acid Specific Maillard Products and Their Contribution to Thermally Generated Aromas... 

Amino acid specific Maillard products were isolated from the extracts by preparative GC or HPLC and identified by MS-, IR-, 1 H- and c-NMR-spectroscopy. Proline derived components are important constituents in bread, malt and beer. More than 120 proline specific Maillard products were characterized. Cysteine and methionine derived components were predominant in roasted coffee and meat flavors. Thirty cysteine- and twenty methionine-specific Maillard products were identified for the first time. 

Formation of Amino Acid Specific Maillard Products... 

Sugar degradation products were determined as benzimidazole derivatives after reaction with o-phenylenediamine. More than 120 amino-acid specific Maillard products have been isolated and identified from the reaction of L-proline, hydixn roline, < teine and methionine with monosaccharides at 150° for 1-1.5 h, in connection with studies of thermally generated aromas. Proline derived components were important constituents of bread, malt and beer, and cysteine and methionine derived components were predominant in roasted coffee and meat flavours. The effects of temperature, pH, and the relative concentration of rhamnose and proline on the quantity of specific volatiles produced in the Maillard reaction of these substrates have been studied, and the data have been analysed 1 computer methodology. The glucosylated cyclopentenone (44) was one of the products of decomposition of the Amadori product 1-deoxy-l-piperidino-maltulose in warm water. ... 

Tressl, R., Helak, B., Martin, N., Kersten, E. Formation of amino acid specific Maillard products and their contribution to thermally generated aromas. ACS Symp. Ser. 409, 156 (1989)... 

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. 

Nutritional Effects Due to the Presence of the Maillard Products. Many physiological or antinutritional effects have been attributed to the Maillard products. Specific effects have been attributed to the Amadori products deoxyfructosylphenylalanine (a model substance not likely to be present in large quantities in foods) appears to depress the rate of protein synthesis in chicks (32) and to partially inhibit in vitro and in vivo the absorption of tryptophan in rats (33). The compound e-deoxyfructosyllysine inhibits the intestinal absorption of threonine, proline, and glycine and induces cytomegaly of the tubular cells of the rat kidneys (34) as does lysinoalanine. In parenteral nutrition the infusion of the various Amadori compounds formed during sterilization of the amino acid mixture with glucose is associated with milk dehydration in infants and excessive excretion of zinc and other trace metals in both infants and adults (35,36,37). 

A contamination with several C1-C4 alkylated pyrazines, cyclopentapyrazines and pyridines was discovered in the second extracts. These compounds are described in detail as primary products of the Maillard reaction, the non-enzymic browning reaction between carbohydrates and amino acids (e.g. Mulders, 1973 Chen et al., 1998). Therefore, the occurence of these specific pyrazines and pyridines suggested either contemporary degradation processes of carbohydrates with amino acids or ammonia within the deposit landfill or the emission of waste derived Maillard products generated already before deposition. 

Proline is the second most abundant amino acid (13-18%) contained in wheat gluten, and plays a very in rtant role in flavor formation during food processing. A great deal of work has been carried out by Tressl et aL (5) on the volatile conponents generated in proline-specific Maillard reactions. The most abundant proline-specific Maillard reaction products arc 2,3-dihydro-IH-pyrrolizines. 

In addition to the nutritional and physiological effects of Maillard browned protein as described in the previous section, it has been shown that the reduced nutritional value of the brown products does not seem to be limited to the loss of amino acids, since supplementation of the diet with those amino acids could not completely restore its biological value (15). This suggests the possible formation of some inhibitory or anti-nutritional compounds during the Maillard reaction, the presence of which cannot be detected with short-term nutritional feeding assays. Moreover, the short-term feeding effects reported in the literature (30) seem to be due in part to nutritional deficiency and not specifically the browning compounds. 

The Maillard reaction between reducing sngars and amino acids under specific conditions (pH, water activity, and temperature) is primarily responsible for the production of heterocyclic volatile compounds such as pyrazines, pyridines, pyrroles, furans, and the Strecker aldehydes. Maillard reactions produce many potent aroma compounds identified in some roasted tree nuts, including 3-methylbutanal, 2,3-butanedione, methional, phenylacetaldehyde, 2-ethyl-3,5-dimethylpyrazine, and 2,5-dimethyl-4-hydroxy-3(2//)-furanone, among others. 

The origin of meat flavor has been shown to arise from the combination of two primary sources. The first is the tissue fat, both extracellular and intracellular, which produces carbonyl and other lipid and lipid-oxidation products. The fat component of meat flavor is viewed as being responsible for the species specific flavor in meat (9). The second major component of meat flavor is the lean portion. The proteins, peptides, and amino acids of the lean, add not only to the muscle food s general meaty flavor, but also undergo Maillard reactions with sugars to produce Amadori and Heyns compounds having meat flavor characteristics. 

Phospholipids contribute specific aroma to heated milk, meat and other cooked foods through lipid oxidation derived volatile compounds and interaction with Maillard reaction products. Most of the aroma significant volatiles from soybean lecithin are derived from lipid decomposition and Maillard reaction products including short-chain fatty acids, 2-heptanone, hexanal, and short-chain branched aldehydes formed by Strecker degradation (reactions of a-dicarbonyl compounds with amino acids). The most odor-active volatiles identified from aqueous dispersions of phosphatidylcholine and phos-phatidylethanolamine include fra 5 -4,5-epoxy-c/5-2-decenal, fran5,fran5-2,4-decadienal, hexanal, fra 5, d5, d5 -2,4,7-tridecatrienal (Table 11.9). Upon heating, these phospholipids produced cis- and franj-2-decenal and fra 5-2-undecenal. Besides fatty acid composition, other unknown factors apparently affect the formation of carbonyl compounds from heated phospholipids. 

Modification of food proteins with reducing sugars through Maillard reaction has been evaluated by various analytical methods determination of free amino groups, amino acid analysis after acid hydrolysis, detection of brownish pigments and fluorescent compounds. Some Maillard products have also been analyzed immunochemically using specific antibodies. 

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