Enzymatic Browning

Several enzymes may initiate reactions that eventually produce brown colors in foods. For example, the action of ascorbate oxidase on ascorbic acid or of lipoxidase on lipids leads to carbonyl products that may either polymerize or react with amino compounds and form brown products. Phenolase (or phenol oxidase), however, is the principal browning enzyme. This enzyme oxidizes o-diphenols to o-quinones, which, by nonenzymatic processes, are ultimately converted to brown polymers known as melanins. Melanins are formed in both animal and plant tissues. A typical substrate of phenolase in animals is tyrosine. This amino acid is converted to melanin by a series of reactions, some of which are shown in Fig. 12.

In dark hair, skin, eyes, and other animal tissues, melanin is attached to proteins. Tyrosine is also a phenolase substrate in plant tissues (e.g., potatoes), but odiphenols and polyphenols are by far the most common substrates of enzymatic browning in foods of plant origin. The following phenolic compounds have been associated with enzymatic browning in some foods: chlorogenic acid, caffeic acid, and catechin in apples, apricots, peaches, and pears; 3,4-dihydroxyphenylethylamine in bananas; (−)-epicatechin, (+)-catechin, (+)-gallocatechin, and (−)-epigallocatechin galate in tea leaves and cocoa beans; catechins in grapes; and tyrosine and chlorogenic acid in potatoes. The structures of four of these phenolics are shown in Fig. 13.

Figure 12 Conversion of tyrosine to melanin, catalyzed in part by tyrosinase (T). DOPA, Dihydroxyphenylalanine. Only part of melanin is shown.

Figure 13 Four phenolic compounds involved in enzymatic browning.

Many fresh fruits and vegetables brown slowly as they senesce. The enzymatic browning of these commodities is more rapid when they are subjected to processing, such as the pressing of apples in making cider or the peeling and cutting of potatoes in preparing potato products. Since enzyme, substrate, and oxygen must all be present for the development of this type of browning, elimination of any one of the three agents will prevent the browning. Heat inactivation of the enzyme, the exclusion of oxygen (by keeping the commodity under water or packaging it under vacuum or inert gas), and the selection of varieties poor in substrate content or enzyme activity are ways of preventing this discoloration. Also, storage at lowtemperature and the addition of sulfur dioxide, ascorbic acid, citric acid, sodium chloride, or combinations of these compounds will inhibit browning.