Volatile lipid-derived components

Isolation and Concentration of Volatile Lipid-Derived Components... 

Volatile compounds generated by model systems of zeln, corn amylopectin and corn oil extruded at barrel temepratures of 120°C and 165°C were analyzed by GC and GC/MS. The largest quantities of lipid oxidation products were detected in systems containing all three components. In each system, the quantity of 2,4-deca-dienal was low relative to the quantities of hexanal, heptanal and benzaldehyde. Identification of the Maillard reaction products, 2-methyl-3(or 6)-pentyl-pyrazine, 2-methyl-3(or 6)-hexylpyrazine and 2,5-di-methyl-3-pentylpyrazine, suggested that lipid-derived aldehydes might be involved in the formation of substituted pyrazines. 4-Methylthiazole was identified as a major decomposition product of thiamin when corn meal containing 0.5% thiamin was extruded at a final temperature of 180°C. 

Virtually all volatile aromatic and flavorsome lipid-derived compounds are analyzed using gas chromatography-mass spectrometry (GC-MS). The components of interest are isolated initially, concentrated, then injected onto a suitable capillary column and detected using a mass spectrometer. 

To establish unambiguously the length of a hydrocarbon chain or the position of double bonds, mass spectral analysis of lipids or their volatile derivatives is invaluable. The chemical properties of similar lipids (for example, two fatty acids of similar length unsaturated at different positions, or two isoprenoids with different numbers of isoprene units) are very much alike, and their positions of elution from the various chromatographic procedures often do not distinguish between them. When the effluent from a chromatography column is sampled by mass spectrometry, however, the components of a lipid mixture can be simultaneously separated and identified by their unique pattern of fragmentation (Fig. 10-24). 

In meats, of course, there are components which arise from the protein which cannot be present in the products from pure fat. Table III shows some of the sulfur compounds and aromatic compounds which are also found in irradiated meats. Many of these can be postulated as arising from direct bond cleavage of amino acid moieties. Benzene and toluene may come from phenylalanine and phenol and p-cresol from tyrosine. Recent studies have been directed to considering the origin of some of the compounds from proteinaceous substances. Some of the sulfides, disulfides, and mercaptans can derive directly from cysteine or methionine, but those containing more than two carbon atoms in a chain require more than a superficial explanation. In order to evaluate the contribution of the volatiles from the protein as well as the lipid constituents of meat, volatile components produced in various protein substances have also been analyzed. 

A series of alcohols (C4 - Cll) were identified in the tail meat. Odor threshold concentrations were generally higher for alcohols than the aldehyde counterparts. Except for 1-pentanol, the remainder of alcohol peaks were very small and might not be significant in overall arctna of boiled crayfish tail meat. Josephson et al. (23-25) found l-octen-3-ol, an enzymatic reaction product derived from lipids, to be one of the volatile ccxnponents widely distributed in fresh and saltwater fish. The compound 2-butoxyethanol identified in crayfish tail meat (3) has been reported in beef products (26-27). GC aroma perception of standard 2-butoxyethanol gave a spicy and woody note, hence this compound could be an important flavor component of the boiled crayfish tail meat. 

Other investigators (7-9) have identified a large number of carbonyls from heated fat. The remaining meat aroma components derived by heating lipids are esters, lactones, alkan-2-ones (methyl ketones), benzenoids and other alkylfurans. Several investigators have analyzed volatile compounds formed during thermal degradation of fatty acids (10-12). 

Numerous techniques have been developed to isolate and concentrate aroma compounds derived from lipids or other components, from other constituents than dairy foods. The most widely used methods are based on volatility and/or solubility. 

Other compounds released during autolysis are present in lower amounts, such as lipids and nucleic acids, but could play an important role in the sensorial character of the final wine. Lipids may affect wine flavour in that the fatty acids released could give rise to volatile components with low sensory thresholds, either directly or through derivatives such as esters, ketones and aldehydes (Charpentier and... 

GABA. Dihydrovaltrate, hydroxyvalerenic acid, a hydroalcoholic extract containing 0.8% valerenic acid a lipid extract an aqueous extract of the hydroalcoholic extract, and another aqueous extract of V. officinalis (L.) were assessed for in vitro binding to rat GABA, benzodiazepine, and barbiturate receptors (18). The results indicated that an interaction of some component of the hydroalcoholic extract, the aqueous extract derived from the hydroalcoholic extract, and the other aqueous extract had affinity for the GABAa receptor. Because hydroxyvalerenic acid (a volatile oil sesquiterpene) and dihydrovaltrate (a valepotriate) did not show any notable activity, the investigators could not identify the specific constituents responsible for this activity. The lipophilic extract derived from the hydroalcoholic extract, as well as dihydrovaltrate, showed affinity for barbiturate receptors, and some affinity for peripheral benzodiazepine receptors. 

The major components, except for phenylacetaldehyde and possibly 2-hexyl-3-methylmalelc anhydride, seem to be derived from oxidative lipid breakdown In common with the volatiles of many other foods and plant materials. 

It is known that volatile compounds found in fruits are mainly derived from three biosynthetic pathways in many plants [25] The formation of the hedonically important short-chain aldehydes and alcohols, such as di-3-hexenol, takes place through the action of lipases, hydroperoxide lyases, and cleavage enzymes on lipid components, followed by the action of alcohol dehydrogenases [26]. 

Aldehydes foimd in various dairy products include those derived from the hydroperoxides of polyunsaturated fatty acid components, and further oxidation products of polyunsaturated aldehydes (Table 11.12). Havors imparted by these carbonyl compounds are described as oxidized, fishy, metaUic, cardboard, painty and tallowy. Higher alkanals and alkenals with more than six carbons and ketones are typical volatiles produced by lipid oxidation. A powerful technique, known as aroma extract dilution analysis, was used to... 

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