Amino compounds, lipid oxidation products

Interaction of lipid oxidation products and amino compounds. Amino acids and primary amines may be involved in other reactions which could lead to the formation of compounds having the potential to undergo N-nitrosation. Malonaldehyde, produced as a result of oxidation of lipids, particularly polyunsaturated fatty acids, has been shown to react with amino acids to produce... 

Lipids play an important part in the development of aroma in cooked foods, such as meat, by providing a source of reactive intermediates which participate in the Maillard reaction. Phospholipids appear to be more important than triglycerides. The addition of phospholipid to aqueous amino acid + ribose mixtures leads to reductions in the concentrations of heterocyclic compounds formed in the Maillard reaction. This effect could be due to lipid oxidation products reacting with simple Maillard intermediates, such as hydrogen sulfide and ammonia, to give compounds not normally found in the Maillard reaction. The precise nature of the odoriferous products obtained from lipid - Maillard interactions is dictated by the lipid structure and may depend on the fatty acid composition and the nature of any polar group attached to the lipid. 

Lipid oxidation products react with proteins and other amino compounds to form brown substances, similar to melanoidins. The formation of such brown substances was reviewed already at the first Maillard Symposium.150 The pigments formed are partly soluble in chloroform-methanol and partly insoluble, whereas true melanoidins are largely water-soluble. As most brown pigments of fish muscle are soluble in benzene-methanol and only to a lesser extent in water, the implication is that here oxidised lipid-protein interactions are more important than Maillard browning due to ribose-amino acid interactions. 

Pyrroles are common products in the reaction of different lipid oxidation products with primary amino groups of amines, amino acid, and protein (Zamora et al., 2000). For example, when squid microsomes were oxidized with iron and ascorbate, TEARS increased simultaneously with the -value (yellowness) and pyrrole compounds, concomitantly with a decrease in free amines. Off-color formation in squid muscle could be due to the nonenzymatic browning reactions occurring between aldehydic lipid oxidation products and the amines on phospholipids head groups... 

Maillard reactions between components of the fried food (sugars and amino acids) are responsible for the golden color of fried products. Lipid oxidation products also contribute to the main reactions. Reactive oxidation products include aldehydes, epoxides, hydroxyketones, and dicarbonylic compounds, which react with lysine, proline, and other amino acids. 

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. 

Sugars and carbonyl compounds interact with amino acids or proteins in a sequence of complex reactions known as the Maillard reaction or as non-enzymatic browning. The browning products from this reaction have a marked influence on lipid oxidation. They generally retard lipid oxidation in foods, and contribute to meat flavors. Lipid oxidation products can also react with proteins and amino acids, leading to the loss of essential amino acids with impact on the oxidative stability and the nutritional quality of foods. 

Lipid oxidation products and their reaction products with amino acids (proteins) have a considerable influence on the typical odour and taste of meat. Particularly significant aminocarboxylic acids include glutamic acid, alanine, threonine and lysine, guanidine compounds (creatine and creatinine), quaternary ammonium compounds (choline and carnitine), peptides (P-alanylhistidine peptides and some products of proteolysis), free nucleotides, nucleosides and their bases (especially inosine 5 -monophosphate, IMP), proteins, carboxylic acids (especially lactic acid), sugars (mainly glucose, fructose and their phosphates, ribose formed by hydrolysis of free nucleotides) and some vitamins (especially thiamine). Some of these compounds, such as glutamic acid and IMP, are additionally used as food additives, namely as flavour enhancers. 

The major cause of deterioration of food products is lipid oxidation, from which low-molecular-weight, off-flavor compounds are formed. This deterioration is often caused by the oxidation of the unsaturated lipids present in foods. Off-flavor compounds are created when the hydroperoxides, formed during the initial oxidation, are degraded into secondary reaction compounds. Free radicals are also formed which can participate in reactions with secondary products and with proteins. Interactions with the latter can result in carbonyl amino... 

It has been observed that the content of secondary oxidation products, such as malonaldehyde (MA), decreases with increased lipid oxidation, which can be explained by further reaction of MA with proteins. MA reacts with compounds containing primary amino groups (proteins, amino acids, DNA, phospholipids) to form fluorescent products (Figure 5) (37). A fluorescence assay has been successfully used to assess lipid oxidation in muscle foods and biological tissues. 

The Maillard reaction and the oxidation of lipids are two of the most important reactions for the formation of aromas in cooked foods. Interactions between lipid oxidation and the Maillard reaction have received less attention, despite the fact that lipids, sugars, and amino acids exist in close proximity in most foods. Lipids, upon exposure to heat and oxygen, are known to decompose into secondary products, including alcohols, aldehydes, ketones, carboxylic acids, and hydrocarbons. Aldehydes and ketones produce heterocyclic flavor compounds reacting with amines and... 

Schiff base compounds formed by the interaction of oxidation products with proteins, phospholipids and nucleic acids produce chromophores showing characteristic fluorescence spectra. The Schiff base formed between malonaldehyde and amino acids is attributed to the conjugated structure -NH=CH-CH=CH-NH-. Lipid-soluble fluorescence chromophores are produced from oxidized phospholipids and from oxidized fatty acid esters in the presence of phospholipids. These chromophores have fluorescence emission maxima at 435-440 nm and excitation maxima at 365 nm. The Schiff base of malonaldehyde and phospholipids has a higher wavelength maximum for emission (475 nm) and excitation (400 nm). The interaction between oxidized arachidonic acid and dipalmityl phosphatidylethanolamine produce similar fluorescence spectra (maximum excitation at 360-90 nm and maximum emission at 430-460 nm). The products from oxidized arachidonic acid and DNA have characteristic fluorescence spectra, with excitation maximum at 315 nm and emission maximum at 325 nm. Similar fluorescence spectra, with excitation maximum at 320 mn and emission maximum at420 nm, are obtained from the interactions of either lipid hydroperoxides or secondary oxidation products with DNA in the presence of metals and reducing agents, or different aldehydes, ketones and dimeric compounds from oxidized linolenate. Therefore, the Schiff base produced from various oxidized lipids and phospholipids and DNA may be considered to be due to a mixture of closely related chromophores. 

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. 

Carbonyl compounds typically are significant to the flavor of most fermented food products. As has been shown, these carbonyls may arise due to carbohydrate or citrate metabolism, lipid oxidation or amino acid degradation. 

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