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Food Lipids: Chemistry, Nutrition, and Biotechnology

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II. ANTIOXIDANTS<br />

In foods containing lipids, antioxidants delay the onset of oxidation or slow the rate<br />

at which it proceeds. These substances can occur as natural constituents of foods,<br />

but they also can be intentionally added to products or formed during processing.<br />

Their role is not to enhance of improve the quality of foods, but they do maintain<br />

food quality <strong>and</strong> extend shelf life. Antioxidants for use in food processing must be<br />

inexpensive, nontoxic, effective at low concentrations, stable, <strong>and</strong> capable of surviving<br />

processing (carry-through effect); color, flavor, <strong>and</strong> odor must be minimal. The<br />

choice of which antioxidant to use depends on product compatibility <strong>and</strong> regulatory<br />

guidelines [2].<br />

Antioxidants not only extend product shelf life but reduce raw material waste,<br />

reduce nutritional losses, <strong>and</strong> widen the range of fats that can be used in specific<br />

products [3]. By extending keeping quality <strong>and</strong> increasing the number of oils that<br />

can be used in food products, antioxidants allow processors to use more available<br />

<strong>and</strong>/or less costly oils for product formulation.<br />

A. Classification<br />

Antioxidants can be broadly classified by mechanism of action as primary antioxidants<br />

<strong>and</strong> secondary antioxidants. Some antioxidants exhibit more than one mechanism<br />

of activity <strong>and</strong> are often referred to as multiple-function antioxidants. Chemical<br />

modes of action vary greatly, for these substances are able to function at all stages<br />

of the free radical reaction.<br />

1. Primary Antioxidants<br />

Primary, type 1, or chain-breaking antioxidants are free radical acceptors that delay<br />

or inhibit the initiation step or interrupt the propagation step of autoxidation. Initiation<br />

of autoxidation occurs when an �-methylenic hydrogen molecules is abstracted<br />

from an unsaturated lipid to form a lipid (alkyl) radical (R�) [Eq. (1)].<br />

RH → R� �H� (1)<br />

This highly reactive lipid radical can then react with oxygen to form a peroxy radical<br />

(ROO�) in a propagation reaction [Eq. (2)].<br />

R� �O2 → ROO� �H� (2)<br />

During propagation, peroxy radicals react with lipid to form a hydroperoxide <strong>and</strong> a<br />

new unstable lipid radical [Eq. (3)]. This lipid radical will then react with oxygen<br />

to produce another peroxy radical, resulting in a cyclical, self-catalyzing oxidative<br />

mechanism [Eq. (4)].<br />

ROO� �RH → ROOH � R� (3)<br />

R� �O2 → ROO� �H� (4)<br />

Hydroperoxides are unstable <strong>and</strong> can degrade to produce radicals that further accelerate<br />

propagation reactions. These reactions are typically referred to as branching<br />

steps [Eqs. (5) <strong>and</strong> (6)�.<br />

ROOH → RO� �OH� (5)<br />

RO� �RH → ROH � R� (6)<br />

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

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