BROWNING IN FOODS

The term browning in foods refers to any dark color development during processing, injury or
storage. Browning in foods can be conveniently divided into two types, viz.,

(i) Non-enzymatic browning, and

(ii) Enzymatic browning.
Browning reactions, whether enzymatic or non-enzymatic, have both desirable and
undesirable aspects, some of which are discussed below:

Desirable aspects

The desirable aspects include formation of attractive brown crust on bread, brown color of
roasted meat and nuts, coffee, soy sauce, etc.

Preparation of caramel color involves non-enzymatic browning and this color is used in many
alcoholic and non-alcoholic beverages.

Undesirable aspects

The undesirable effects of browning in food are related to esthetic, nutritional, and health
aspects. Browning that occurs in dried milk powder, liquid milk, egg powder, starch, and injured
or cut fruits & vegetables are some examples of undesirable aspects of browning that have to do
with esthetic quality of the food.

Browning reaction, depending on its type, reduces the nutritional value of food. For example, it
may reduce the absorption of zinc and availability of essential amino acid lysine in man.

Loss of essential amino acids like lysine, arginine, and histidine is known to occur during
browning reaction. There is speculation that browning also produces mutagenic chemicals.
Maillard reactions are also natural consequences of aging.

Non-enzymatic browning

There are four principle types of non-enzymatic browning, viz.

1. Maillard browning

2. Caramelization

3. Ascorbic acid browning

4. Lipid peroxidation

Maillard browning
Maillard reaction (first discovered by Louis Camille Maillard in 1912) is a type of non-
enzymatic browning which involves the reaction of simple sugars (carbonyl groups) with amino
acids, peptides and proteins (free amino groups).

The reaction occurs in a complex series of steps to ultimately form brown, nitrogenous polymers
and copolymers called melanoidins. Maillard reaction causes changes in color, flavor and
nutritive value in food.

A system that describes Maillard browning as a 5-step process is as follows:

Step 1: Formation of glycosylamine

Step 2: Intramolecular rearrangement of glycosylamine to form glycosamine

Step 3: Intermolecular rearrangements of aldosamine and ketosamine

Step 4: Degradation of amino sugars

Step 5: Condensation and polymerization into color and flavor compounds

Factors affecting maillard browning

The influence of reaction components and reaction conditions results in a wide variety of
reaction patterns. Many of these conditions are interdependent.

Concentration of reactants, and reactant type, pH, time, temperature, water activity, free radicals
and antioxidants are known to affect Maillard reaction.

Increasing temperature results in a rapidly increasing rate of browning. In model systems the
browning rate increases by 2-3 times for each 10°C rise in temperature. In foods containing
fructose, the increase may be 5-10 times for each 10°C rise.

Prevention of maillard browning

Methods of preventing Maillard browning could consist of measures intended to slow reaction
rates, such as control of moisture, temperature, or pH, or removal of an active intermediate.
Generally, it is easier to use an inhibitor.

One of the most effective inhibitors of browning is sulfur dioxide. The action of sulfur dioxide is
unique and no other suitable inhibitor has been found.

Caramelization

Caramelization is defined as the thermal degradation of sugars leading to the formation of

volatiles (caramel aroma) and brown-colored products (caramel colors).
Caramelization entails a series of complex reactions, some of which are still not well understood.
The reactions, in sequence, include intramolecular arrangement of sugar molecule, dehydration,
degradation, condensation, and polymerization.

Caramel is made by heating food grade carbohydrates, generally a high dextrosecontaining

starch hydrolysate or corn syrup. The process is acid- or base catalyzed and generally requires
temperatures >120°C at pHs between 3 and 9. Some of the reaction steps of caramelization are
similar to that of Maillard reaction.

Caramelization however does not require the presence of amino acids. The sugar does not have
to be a reducing one. If complex sugars and carbohydrates are used, they must of course be
hydrolyzed with acids (acetic, citric, phosphoric, or lactic acid) before high-temperature
caramelization.

The generation of flavors and colors in thermally induced caramelization requires that sugars,
normally monosaccharide structures, to first undergo intramolecular rearrangements. The
reaction causes the release of H+ . Thus the pH of the solution undergoing caramelization falls
with time, eventually into the slightly acidic region of pH 4-5.

Some typical components of caramel flavor are shown in Fig. 13-20. There are 4 general
categories: furans, furanones, pyranones, and carbocyclics.

The relative proportions of these compounds can be influenced by the temperature and whether
the conditions are acidic or basic. While the thermally and/or acidinduced dehydration and
cyclization reactions dominate, there is an increased tendency for cleavage of the carbon chain of
the sugar under basic conditions. Thus, depending on the reaction conditions, one finds
derivatives of furan, such as hydroxymethylfurfural (HMF) and hydroxyacetylfuran (HAF),
furanones such as hydroxydimethylfuranone (HDF), dihydroxydimethylfuranone (DDF) and the
pyranones (maltol) from disaccharides and (hydroxymaltol) from monosaccharides.

Ascorbic acid oxidation

Ascorbic acid is a reductone and therefore can participate in the browning reaction as in Maillard
reaction. The molecule is first oxidized to dehydroascorbic acid and then transformed into
diketogulonic acid. This acid is eventually decomposed to furfuraldehyde or related compounds
which then polymerize or react with nitrogen (as in Maillard reaction) to from brown pigments.

The color formation may also involve Strecker degradation. This type of browning is observed
during drying of vegetables. The following set of reactions is known as ascorbic acid browning:

This can lead to off flavors and to first red and then brown colors in food product
Enzymatic (enzymic) browning

Enzymatic browning is a chemical process involving polyphenol oxidase or other enzymes that
create melanins, resulting in a brown color. Enzymatic browning is an important color reaction in
fruits, vegetables, and seafoods.

Enzymatic browning of fruits and vegetables creates heavy economic losses for growers.
Enzymatic browning occurs in many tissues whenever they are injured. The injury can be the
result of bruising, cutting, freezing, or disease.

The discoloration is the result of oxidation of colorless native phenolic compounds by enzymes
collectively called polyphenol oxidase (PPO).

These enzymes are also frequently called catecholase, tyrosinase, phenolase, and polyphenolase
but the official name is ortho-diphenol: oxidoreductase.

The reaction requires oxygen for browning to take place but carbohydrates are not essential as in
non-enzymatic browning. Although termed enzymatic browning, the reaction is more often of
mixed type.

The amount of browning depends on the concentration and nature of polyphenol compounds that
are present. Enzymatic activity determines the amount of initial browning. Substrates also
determine what color the discoloration will be.

Apples, apricots, peaches, and pears will turn brown but never black. But bananas and potatoes
will first turn pink and then brown and will eventually turn black, which is the polymer melanin.
The maturity of a fruit is a factor in the amount of browning in a fruit or vegetable.

Persimmons, apples, potatoes and bananas have been shown to increase in browning as they
ripen, but then decrease as the amount of substrate decreases with maturity.

Different varieties of the same fruit or vegetable may brown at different rates. Different
preparation methods can affect the amount of browning. With potatoes, a sharp knife will cause
less tissue damage than abrasive peeling or steam peeling and so will not show as much
browning.

Freezing a fruit or vegetable will cause damage to tissues and so when the temperature rises and
enzymes are active again, more browning will occur.

Chemical reaction

Two reaction steps are involved in the phenolase catalytic reaction, viz.,

1. Hydroxylation

2. Oxidation
Hydroxylation of monophenols is slow and rate-determining step in reaction. Besides tyrosine,
major substrates of phenolases in plant include caffeic acid, chlorogenic acid and protocatechuic
acid which are abundant in plants.

But tyrosine and chlorogenic acid are the two most prevalent substrates for phenolase due to
their relatively high reaction rates. Phenolase is active in pH 5-7, and may be irreversibly
inactivated at pH lower than pH 3.

Prevention of enzymatic browning

O-quinones are very reactive and undergo spontaneous polymerization to form melanins. The
enzyme polyphenolase requires oxygen and copper for reaction. Some of the methods for
controlling browning are:

1. Use of chelating agents (e.g., EDTA) to bind and remove copper

2. Vacuum or inert gas packaging to avoid the effect of oxygen

3. Inactivation of polyphenolase by heat treatment (blanching)

4. Storage at low temperature to reduce the rate of enzyme action

5. Avoiding injury to foods during handling, storage, and transportation

6. Drying by physical or chemical (e.g., use of salts) means to reduce water activity below that
required for enzyme action

7. Irradiation

8. High pressure treatment

9. Use of browning inhibitors like SO2, ascorbic acid, phenolic antioxidants, acidulants (e.g.,
citric acid)