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Food Lipids: Chemistry, Nutrition, and Biotechnology

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of iron from the heme pocket by cooking [129,135] <strong>and</strong> release of iron from the iron<br />

storage protein, ferritin, by the reducing agents cysteine <strong>and</strong> ascorbate [136]. These<br />

increases are significant because concentrations of iron (2.2 �M) <strong>and</strong> copper (1.4<br />

�M) that were found in the low molecular weight fractions of fish muscle were<br />

shown to catalyze lipid oxidation in fish muscle sarcoplasmic reticulum model systems<br />

[137]. In addition, modifications in dietary iron level altered the development<br />

of lipid oxidation in turkey dark muscle <strong>and</strong> in pork muscles [138–140].<br />

Three general approaches have been taken to decipher the contribution of heme<br />

<strong>and</strong> nonheme iron to lipid oxidation of muscle foods:<br />

1. Evaluation of the levels of heme <strong>and</strong> nonheme in the muscle food <strong>and</strong><br />

relation of these values to the muscle’s oxidative stability during storage<br />

[54,141];<br />

2. Evaluation of the improvement in oxidative stability upon addition of inhibitor/chelator<br />

that will cancel out the contribution of one of the components<br />

[142–145]; or<br />

3. Evaluation of the level of oxidation induced upon addition of one of the<br />

iron sources to muscle or muscle model systems [142–148].<br />

From these studies, the following conclusions may be drawn:<br />

• In raw red meat <strong>and</strong> dark muscle fish, heme iron is the major catalyst.<br />

• In both raw <strong>and</strong> cooked white flesh fish, nonheme iron is the major catalyst.<br />

However, conflicting results make it difficult to draw a conclusion on the role of<br />

heme <strong>and</strong> nonheme iron in cooked red meat samples. Some factors that may modify<br />

the response are as follows:<br />

1. Concentration of catalysts used in the study.<br />

2. Distribution of catalysts in muscle system. Johns et al. [146] suggested that<br />

conflicting results from model system studies were due in part to the difficulty<br />

of evenly dispersing the catalysts in the system.<br />

3. Concentration of reducing substances in system. Nonheme iron is more<br />

active in the reduced state, whereas heme iron is more active in the oxidized<br />

state [149].<br />

4. pH of system. Heme catalysis is influenced less by increasing pH than<br />

nonheme iron [150]. Therefore, contribution of nonheme iron would increase<br />

with decreasing pH.<br />

5. Amount of heat applied to the cooked system.<br />

6. Presence of H 2O 2 in system.<br />

7. Presence of chelators. Endogenous chelators, such as citrate, phosphate,<br />

<strong>and</strong> nucleotides, modify the reactivity of low molecular weight iron by<br />

modifying its redox potential to different extents [151].<br />

8. Presence of one or more lipid classes. Oxidative response of chicken muscle<br />

model systems differed depending on the class of lipid(s) present [152].<br />

2. Singlet Oxygen Generation Systems<br />

While many different mechanisms have been proposed for the production of singlet<br />

oxygen, it is believed that the two most common mechanisms involve nonenzymatic<br />

photosensitization of natural pigments [153] or direct enzymatic production of singlet<br />

Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.

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