Deterioration oxidative

Fats and oils deteriorate rather rapidly by autoxidation of their unsaturted acyl residues (cf. 3.7.2.1). A number of analytical methods have been developed to determine the extent of such deterioration and to predict the expected shelf life of a fat or oil. 

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Other Specialty Chemicals. In fuel-ceU technology, nickel oxide cathodes have been demonstrated for the conversion of synthesis gas and the generation of electricity (199) (see Fuel cells). Nickel salts have been proposed as additions to water-flood tertiary cmde-oil recovery systems (see Petroleum, ENHANCED oil recovery). The salt forms nickel sulfide, which is an oxidation catalyst for H2S, and provides corrosion protection for downweU equipment. Sulfur-containing nickel complexes have been used to limit the oxidative deterioration of solvent-refined mineral oils (200). 

Sihcone-based coatings are well suited for high temperature and high speed appHcations. They are flexible, tough, and resistant to thermal and oxidative deterioration. They have good surface resistance and are fungus- and flame resistant. However, they possess a high coefficient of thermal expansion and have poor adhesion. 

Many antioxidants ia these classes are volatile to some extent at elevated temperatures and almost all antioxidants are readily extracted from their vulcanizates by the proper solvent. These disadvantages have become more pronounced as performance requirements for mbber products have been iacreased. Higher operating temperatures and the need for improved oxidation resistance under conditions of repeated extraction have accelerated the search for new techniques for polymer stabilization. Carpet backiag, seals, gaskets, and hose are some examples where high temperatures and/or solvent extraction can combine to deplete a mbber product of its antioxidant and thus lead to its oxidative deterioration faster (38,40). 

As with c -polyisoprene, the gutta molecule may be hydrogenated, hydro-chlorinated and vulcanised with sulphur. Ozone will cause rapid degradation. It is also seriously affected by both air (oxygen) and light and is therefore stored under water. Antioxidants such as those used in natural rubber retard oxidative deterioration. If the material is subjected to heat and mechanical working when dry, there is additional deterioration so that it is important to maintain a minimum moisture content of 1%. (It is not usual to vulcanise the polymer.)... 

An MAI composed of polycaprolactam was investigated on its thermal decomposition behavior to develop easy decomposable polymers, the addition of oxidative deterioration was needed [72]. 

There are also methods based on the detection of aldehydic substances, for the typical odor and flavor of rancidity seem to be associated with the liberation of aldehydic materials during the oxidative deterioration. The Kreis test (18), perhaps the best known of these methods, consists of treating the fat with concentrated hydrochloric acid and a solution of phloroglucinol. The red color formed is attributed to a condensation product of epihydrin aldehyde with phloroglucinol. Historically, the chief difficulty with this method has been that fats which are not rancid will often give a positive Kreis test. It has been shown that if this test is quantitatively correlated with the induction period... 

JACOBSEN C, HARTVIGSEN K, THOMSEN M K, HANSEN L F, LUND P, SKIBSTED L H, H0LMER G, ADLER-NissEN J and MEYER A s (2001) Lipid oxidation in fish oil enriched mayonnaise calcimn disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration, J Agric Food Chem, 49, 1009-19. 

TAPPEL A L (1956) Freeze-dried meat. 2. The mechanism of oxidative deterioration of freeze-dried beef, Food Res, 21, 195-206. 

The detection and quantification of one or more of the above lipid peroxidation produas (primary and/or secondary) in appropriate biofluids and tissue samples serves to provide indices of lipid peroxidation both in ntro and in vivo. However, it must be stressed that it is absolutely essential to ensure that the products monitored do not arise artifactually, a very difiScult task since parameters such as the availability of catalytic trace metal ions and O2, temperature and exposure to light are all capable of promoting the oxidative deterioration of PUFAs. Indeed, one sensible precaution involves the treatment of samples for analysis with sufficient levels of a chainbreaking antioxidant [for example, butylated hydroxy-toluene (BHT)] immediately after collection to retard or prevent peroxidation occurring during periods of storage or preparation. 

The identification and quantification of potentially cytotoxic carbonyl compounds (e.g. aldehydes such as pentanal, hexanal, traw-2-octenal and 4-hydroxy-/mAW-2-nonenal, and ketones such as propan- and hexan-2-ones) also serves as a useful marker of the oxidative deterioration of PUFAs in isolated biological samples and chemical model systems. One method developed utilizes HPLC coupled with spectrophotometric detection and involves precolumn derivatization of peroxidized PUFA-derived aldehydes and alternative carbonyl compounds with 2,4-DNPH followed by separation of the resulting chromophoric 2,4-dinitrophenylhydrazones on a reversed-phase column and spectrophotometric detection at a wavelength of378 nm. This method has a relatively high level of sensitivity, and has been successfully applied to the analysis of such products in rat hepatocytes and rat liver microsomal suspensions stimulated with carbon tetrachloride or ADP-iron complexes (Poli etui., 1985). 

It is now widely appreciated that polyunsaturated fatty acids (PUFAs) are highly susceptible to oxidative damage. Indeed, the process of lipid peroxidation was broadly defined as the oxidative deterioration of polyunsaturated lipids by Tappel (1979). The presence of a double... 

Many methods are available for determining food antioxidant capacity, which is an important topic in food and nutrition research. However, there is a great need to standardize these methods because the frequent lack of an actual substrate in the procedure, the system composition, and the method of inducing oxidation could limit their accuracy. In fact, antioxidant activities in complex systems cannot be evaluated satisfactorily using a single test, and several test procedures may be required. The search for more specific assays that can be more directly related to oxidative deterioration of foods and biological systems should be the objective of future investigations. 

Flavor is one of the major characteristics that restricts the use of legume flours and proteins in foods. Processing of soybeans, peas and other legumes often results in a wide variety of volatile compounds that contribute flavor notes, such as grassy, beany and rancid flavors. Many of the objectionable flavors come from oxidative deterioration of the unsaturated lipids. The lipoxygenase-catalyzed conversion of unsaturated fatty acids to hydroperoxides, followed by their degradation to volatile and non-volatile compounds, has been identified as one of the important sources of flavor and aroma components of fruits and vegetables. An enzyme-active system, such as raw pea flour, may have most of the necessary enzymes to produce short chain carbonyl compounds. 

Packing class, commercial codes, 621 Packing effect, dialkyl peroxides, 121 Palm olein, oxidative deterioration, 662 Pamctinal laser photocoagulation, 640 Paper, bleaching agents, 623 Parasites... 

Anandaraman (, ) has shown that there is a very strong protective effect of higher dextrose equivalent (DE) starches (corn syrup solids) against oxidative deterioration (Fig. 4). 

Lipid autoxidation in fluid milk and a number of its products has been a concern of the dairy industry for a number of years. The need for low-temperature refrigeration of butter and butter oil, and inert-gas or vacuum packing of dry whole milks to prevent or retard lipid deterioration, in addition to the loss of fluid and condensed milks as a result of oxidative deterioration, have been major problems of the industry. The autoxidation of milk lipids is not unlike that of lipids in other... 

The overwhelming consideration in regard to lipid deterioration is the resulting off-flavors. Aldehydes, both saturated and unsaturated, impart characteristic off-flavors in minute concentrations. Terms such as painty, nutty, melon-like, grassy, tallowy, oily, cardboard, fishy, cucumber, and others have been used to characterize the flavors imparted by individual saturated and unsaturated aldehydes, as well as by mixtures of these compounds. Moreover, the concentration necessary to impart off-flavors is so low that oxidative deterioration need not progress substantially before the off-flavors are detectable. For example, Patton et al (1959) reported that 2,4-decadienal, which imparts a deep-fried fat or oily flavor, is detectable in aqueous solution at levels approaching 0.5 ppb. 

Several methods have been introduced which express the degree of oxidation deterioration in terms of hydroperoxides per unit weight of fat. The modified Stamm method (Hamm et at 1965), the most sensitive of the peroxide determinations, is based on the reaction of oxidized fat and 1,5-diphenyl-carbohydrazide to yield a red color. The Lea method (American Oil Chemists Society 1971) depends on the liberation of iodine from potassium iodide, wherein the amount of iodine liberated by the hydroperoxides is used as the measure of the extent of oxidative deterioration. The colorimetric ferric thiocyanate procedure adapted to dairy products by Loftus Hills and Thiel (1946), with modifications by various workers (Pont 1955 Stine et at 1954), involves conversion of the ferrous ion to the ferric state in the presence of ammonium thiocyanate, presumably by the hydroperoxides present, to yield the red pigment ferric thiocyanate. Newstead and Headifen (1981), who reexamined this method, recommend that the extraction of the fat from whole milk powder be carried out in complete darkness to avoid elevated peroxide values. Hamm and Hammond (1967) have shown that the results of these three methods can be interrelated by the use of the proper correction factors. However, those methods based on the direct or indirect determination of hydroperoxides which do not consider previous dismutations of these primary reaction products are not necessarily indicative of the extent of the reaction, nor do they correlate well with the degree of off-flavors in the product (Kliman et at. 1962). 

In addition to the previously mentioned chemical tests, methods based on the carbonyl content of oxidized fats have also been suggested (Henick et al 1954 Lillard and Day 1961) as a measure of oxidative deterioration. The procedures determine the secondary products of autoxidation and have been reported to correlate significantly with the degree of off-flavor in butter oil (Lillard and Day 1961). The methods, however, are cumbersome and are not suited for routine analysis. 

Fluid milks have been classified by Thurston (1937) into three categories based on their ability to undergo oxidative deterioration (1) spontaneous, for those milks that spontaneously develop off-flavor within 48 hr after milking (2) susceptible, for those milks that develop off-flavor within 48 hr after contamination with cupric ion and (3) resistant, for those milks that exhibit no flavor defect, even after contamination with copper and storage for 48 hr. A similar classification has been employed by Dunkley and Franke (1967). 

With the advent of noncorrodible dairy equipment, oxidative deterioration in fluid milk as a result of copper contamination has decreased significantly, although it has not been completely eliminated (Rogers and Pont 1965). However, the incidence of spontaneous oxidation remains a major problem of the dairy industry. For example, Bruhn and Franke (1971) have shown that 38% of samples produced in the Los Angeles milkshed are susceptible to spontaneous oxidation Potter and Hankinson (1960) have reported that 23.1% of almost 3000 samples tasted were criticized for oxidized flavor after 24 to 48 hr of storage. Significantly, certain animals consistently produce milk which develops oxidized flavor spontaneously, others occasionally, and still others not at all (Parks et al. 1963). Differences have been observed in milk from the different quarters of the same animal (Lea et al. 1943). 

Despite reports of anomalous behavior in several aspects, sufficient evidence has been accumulated in recent years to establish that the susceptibility or resistance of milk to oxidative deterioration is dependent on the percentage and/or distribution of naturally occurring pro-and antioxidants. 

That copper, naturally occurring or present as a contaminant, accelerates the development of oxidative deterioration in fluid milk is evident. 

However, its presence is not the only determinant of whether or not oxidative deterioration occurs. Olson and Brown (1942) showed that washed cream (free of ascorbic acid) from susceptible milk did not develop an oxidized flavor when contaminated with copper and stored for three days. Subsequently, the addition of ascorbic acid to washed cream, even in the absence of added copper, was observed to promote the development of an oxidized flavor (Pont 1952). Krukovsky and Guthrie (1945) and Krukovsky (1961) reported that 0.1 ppm added copper did not promote oxidative flavors in milk or butter depleted of their Vitamin C content by quick and complete oxidation of ascorbic acid to dehydroascorbic acid. Krukovsky (1955) and Krukovsky and Guthrie (1945) further showed that the oxidative reaction in ascorbic acid-free milk could be initiated by the addition of ascorbic acid to such milk. Accordingly, these workers and others have concluded that ascorbic acid is an essential link in a chain of reactions resulting in the development of an oxidized flavor in fluid milk. 

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