Amino acid degradation dehydration

Several mechanisms have been reported for pyrazine formation by Maillard reactions (21,52,53). The carbon skeletons of pyrazines come from a-dicarbonyl (Strecker) compounds which can react with ammonia to produce ot-amino ketones as described by Flament, et al. (54) which condense by dehydration and oxidize to pyrazines (Figure 6), or the dicarbonyl compounds can initiate Strecker degradation of amino acids to form ot-amino ketones which are hydrolyzed to carbonyl amines, condensed and are oxidized to substituted... 

The most efficient method for the clean hydrolysis of sucrose is by the use of invertase, leading to an equimolar mixture of glucose and fructose (invert sugar). The presence of salts increases the rate of thermal degradation of sucrose.337 The reaction is also possible in the presence of such heterogeneous acidic catalysts as zeolites.338 The hydrolysis of the glycosidic bond is the first step of a number of subsequent reactions that can occur on the glucose and fructose residues, such as dehydrations, combinations with amino acids (Maillard reaction), and many other chemicals or fermentation processes.339... 

Maltol 337 is one of the degradation products in monosaccharide solutions with amino acids forming Amadori compounds but not in the solution of monosaccharides alone. Heated solutions of monosaccharides yield 335, the logical precursor of 337, but not 337 itself. On the basis of the molecular mechanics calculation indicating that 335 adopts the conformation unfavorable for dehydration into 337, a possible route via the dehydrated product 336, an ortho-elimination product, has been postulated as a more favorable alternate reaction pathway [277]. 

Isoleucine and valine. The first four reactions in the degradation of isoleucine and valine are identical. Initially, both amino acids undergo transamination reactions to form a-keto-/T methyl valerate and a-ketoiso valerate, respectively. This is followed by the formation of CoA derivatives, and oxidative decarboxylation, oxidation, and dehydration reactions. The product of the isoleucine pathway is then hydrated, dehydrogenated, and cleaved to form acetyl-CoA and propionyl-CoA. In the valine degradative pathway the a-keto acid intermediate is converted into propionyl-CoA after a double bond is hydrated and CoA is removed by hydrolysis. After the formation of an aldehyde by the oxidation of the hydroxyl group, propionyl-CoA is produced as a new thioester is formed during an oxidative decarboxylation. 

The economical value and high popularity of meat lead to the production of meat-like flavors through process chemistry. Several heat-induced reactions lead to the formation of meat flavors. These reactions are the pyrolysis of peptides and amino acids, the degradation of sugars, the oxidation, dehydration, and decarboxylation of lipids, the degradation of thiamin and ribonucleotides, and interactions involving sugars, amino acids, fats, H2S, and NH3 [110],... 

The thermal properties of diastereomers of mixed cobalt(III) complexes with aromatic amino acids and diamine were studied by Miodragovi and coworkers [140] to obtain information about stereochemical effects on their thermal stability. The thermal decompositions of these complexes were shown to be multi-step degradation processes, some of which can be satisfactorily separated into individual steps, depending on the molecular symmetry. For diastereomers which crystallize with water molecules, preliminary dehydration occurs. 

Proteic materials used in traditional tempera painting, for instance, are subject to condensation and cross-linking reactions with other components such as lipids. Gas chromatography-mass spectrometry (GC-MS) investigations have shown that the oxidative degradation of amino acids such as cysteine, serine, and phenylalanine leads to the formation of amino malonic acid. The latter compound has been identified via the analysis of aged paint samples [7]. Other modifications are caused by the pH variation of the paint surface that contributes to the hydrolysis of peptide bonds and the partial dehydration of serine and threonine. 

Strongly alkaline treatments can cause degradation of some amino acids and formation of nonphysiological, potentially toxic molecules. Some of these transformations occur through dehydroalanine, a reactive molecule that is formed via p-elimination of HjS from cysteine or via dehydration of serine. Dehydroalanine can condense with the -amino group of lysine, whereby the unnatural amino acid lysinoalanine is formed, or react with a second molecule of cysteine to give lanthionine (Fig. 4) (33,34). 

Monoaminomonocarboxylic a-amino acids with a primary amino group produce sensory active aldehydes called Strecker aldehydes. Strecker degradation of P-amino acids yields alkan-2-ones known as methylketones (see Section 8.2.4.1.2). By analogy, alkane-3-ones (ethylketones) are formed from y-amino acids. The general reaction is schematically indicated in Figure 2.43. The reaction mechanism, however, varies considerably depending on the type of oxidant and amino acid. 2-Imino acids and 2-oxoacids can in some cases apparently form as intermediates, analogous to enzymatically catalysed transamination and oxidative deamination of amino acids (see Section 2.5.1.3.2). Some Strecker aldehydes readily decompose, such as methional, or yield cyclic products, such as 5-aminopentanal, which dehydrates to 2,3,4,5-tetrahydropyridine. 

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