NON-ENZYMATIC BROWNING
 Foods may develop a variety of brown colors, from
yellow-brown to red-brown to black-brown, during
handling, processing, and storage.
 These colors are desirable in certain foods (e.g., coffee,
beer, bread, maple syrup).
 In other foods, such as most dehydrated fruits and
vegetables, dried eggs, and canned or dried milk,
browning is detrimental.
 Even when desirable, browning should not be
excessive, as in potato chips, French fries, and apple
juice.
 Numerous reactions lead to browning in foods. Some
of these may also generate flavors and/or alter the
nutritional properties of foods.
BROWNING REACTION
ENZYMATIC
NON-ENZYMATIC
ENZYMATIC BROWNING
- occurs when fresh food or beverage products are exposed to
air and there are active enzymes present within the food or
beverage product. When an apple slice or banana turns brown,
it is usually due to polyphenol oxides enzyme activity.
NON-ENZYMATIC BROWNING
- can produce brown, fluorescent, highly cross-linked
pigments, such as melanoidin chromophores.
TYPES OF NON-ENZYMATIC BROWNING
1. Maillard Reaction
2. Caramelization
3. Ascorbic Acid Browning
4. Metal polyphenol Browning
CHANGES DURING NON-EZYMATIC BROWNING
This changes some times are desirable and sometimes
undesirable
 Produces flavor
 Produces color
 Produces antioxidant products
 Produces toxic products
 Loss and destroys nutrients (Lysine)
 Formation of undesirable products such as HMF
 (5-HYDROXYMETHYFURFURAL)
1. CARAMELIZATION
 This reaction leads to brown products when sugars are
heated dry or in solution.
 The large quantities of industrial caramel color that are
added to beverages (cola drinks), baked goods, and
confections are made by heating high-conversion corn
syrups in the presence of catalysts (acids, alkalis, salts).
 The chemical transformations involved in caramelization
are complex and poorly understood.
 They include dehydration, fragmentation, and
polymerization.
 On the heating of pentose, furfural is formed which
polymerizes to brown products.
 Heating hexoses results in hydroxymethylfur-fural,
which polymerizes similarly.
2. ASCORBIC ACID BROWNING
 When ascorbic acid is heated in the presence of
acids, furfural is formed.
 The latter, either by itself or after reacting with
amino compounds, polymerizes to brown products.
 Citrus juices, especially their concentrates, develop
browning, which has been attributed to ascorbic
acid degradation.
3. METAL-POLYPHENOL BROWNING
 Polyphenolic compounds form complexes with
certain metals. The polyphenols of fruits and
vegetables most commonly chelate iron. The
resulting iron complexes are bluish black pigments.
 Cutting apples with a non-stainless-steel knife
results in darkening of both the blade and the
surface of apple.
 This darkening is independent of the enzymatic
browning that might develop as a result of cutting.
 The iron of the tissue must first be oxidized to the
ferric state for the blackish complex to appear.
 Canned or pickled cauliflower may turn dark due to
the interaction of polyphenols in the tissue with iron
from external sources.
4. THE MAILLARD BROWNING
 M
a
i
l
lard reaction is caused by the condensation of an
amino group and a reducing compound, resulting
complex changes in biological and food system.
 This reaction was described for the first time by
Louis Maillard in 1912.
JOHN DEMAN
He stated that Maillard reaction is;
“The sequence of events that begins with reaction of the
amino group of amino acids with a glycosidic hydroxyl
group of sugars; the sequence terminates with the
formation of brown nitrogenous polymers or
melanoidins”.
MAILLARD REACTION MECHANISMS AND
PRODUCTS
 This reaction is actually a series of reactions
occurring from the first encounter of a carbonyl
compound with an amine compound to the
formation of brown pigments.
 It is also known as the carbonyl-amine reaction, and
its brown products are often called melanoidins,
including their visual similarity to the melanins of
enzymatic browning.
 The most common carbonyl compounds of foods
involved in the Maillard reaction are reducing
sugars, and the most common amine compounds
are amino acids.
 Among sugars, pentoses are more reactive than hexoses,
and hexoses are more reactive than reducing
disaccharides.
 When free amino acids react with sugars, lysine appears
to be the most active among them.
 Maillard reaction occurs when virtually all foods are
heated, and also occurs during storage.
 Maillard reaction form products that are desirable or
undesirable.
Desirable
 Caramel aromas
 Golden brown colors
Undesirable
 Foods darkness
 Off-flavor development
 Loss of nutrition component (Lysine)
 The Maillard reaction can seriously lower the nutritive
value of the food.
 Toasting, for example, may reduce to one-half the
protein efficiency ratio of bread.
HOW TO MEASURE BROWNING?
 As the thermal treatment resulted in the increase in
colored substances content, which is measured as an
increase in absorbance at 420 and 560 nm by reactance
colorimetry A420.
KINETICS OF MAILLARD BROWNING
- Kinetic of non-enzymatic browning
Fisrt-order and zero-order kinetic models have been used to
evaluate the development of non-enzymatic browning. These
kinetic models are expressed by the equations.
 It is not always possible to apply kinetics as simple as
first-order or zero-order to describe the colour changes
produced in fruit purses.
 Since these changes can be due not only to the Maillard
reaction but also to the thermal destruction of pigments
present in the samples.
 Fisrt-order kinetics has been suggested for the
destruction of natural fruit pigments.
 Based on data for the deterioration produced by
thermal treatments, a two stage mechanism is
proposed.
 The first stage, color formation, is zero-order and
the second stage, pigment destruction, is first-order.
 This can be written as
- sugars, Amino acids k0 colored polymers
- pigments k1 uncolored products
 This two-stage kinetic mechanism can be expressed
mathematically.
 If C is the variable used to measure the color
changes by non-enzymatic browning reactions, then
where the left-hand side represents the fractional
conversion at time t.
 Eqn (5) is the final expression for the kinetic model
of the two-stage mechanism proposed for the
evolution of color changes caused by non-
enzymatic browning.
 The value of K expresses the maximum color
difference (DE?) obtained for long treatment times.
 It was observed that K increase with treatment
temperature.
 Consequently, an increase in temperature implies a
greater increase in colour.
 According to the proposed kinetic model, K
represents the ratio of kinetic constant k0 (colour
appearance) and k1 (pigment destruction).
 It was observed that the kinetic constant values for
the colour formation stage increased with treatment
temperature, while destruction stage showed no
definite tendency.
 However, for higher temperatures the values of this
constant were similar.
 The kinetic constants for the colour formation stage
increased in value with increasing temperature.
 An analogous behavior was observed to describe
the increase in color.
 The value of the Kinetic constant increased with
treatment temperature, which indicates that the
yellowish hues decreased more rapidly with
increasing treatment temperature.
 The zero order model (eqn [1]) was the best model
to describe this variation.
CONTROLLING FACTORS OF THE MAILLARD
REACTION PRODUCTS
1. Water Activity (aw)
 Water is produced during Maillard reaction, thus the
reaction occurs less readily in foods with a high aw
values while, at low aw, the mobility of reactants is
limited, despite their presence at increased
concentrations.
 Aw is the most significance to the reaction in dried and
intermediate moisture foods (IMFs), which have aw
values in this range.
 Humectants, such as glycerol, can lower the aw value
for maximum browning.
2. pH
 Since the reaction itself has a strong influence on pH it
is hard to evaluate the pH influence.
 pH can have a little affect on final products and aroma.
 pH had a less dramatic effect on aroma than did
temperature, time pr water content.
3. Temperature
 The temperature dependence of chemical reaction is
often expressed as the activation energy (Ea).
 The activation energy is highly dependent on pH.
 The temperature dependence of the Maillard reaction is
also influenced by the participating reactants.
 So it is difficult to isolate the effect of temperature as a
single variable.
PREVENTION OF NON- ENZYMATIC BROWNING
 As already indicated, non-enzymatic browning is
desirable in certain instances and undesirable in others.
 The availability of reactants and the type of conditions
(temperature, pH, moisture) will determine the extent of
browning.
 A chemical preservatives often used to inhibit non-
enzymatic (and enzymatic) browning is sulfur dioxide.
 An obvious way to prevent metal-polyphenol browning
is to eliminate contact between susceptible tissues and
reactive metals and use inoffensive equipment (stainless
steel, glass-lined tanks, , etc.)
SUMMARY
 Non-enzymatic browning is desirable in some products
like bread crust and meat and undesirable in other
products like apple puri, there is many types of browning
like Maillard browning, Caramelization, Ascorbic Acid
and Metal-polyphenol browning.
 The Maillard reaction is actually known as the carbonyl-
amine reaction, and its brown products are often called
melanoidins. The most common carbonyl compounds of
foods involved in the Maillard reaction are reducing
sugars, and the most common amine compounds are
amino acids.
 Factors that influence the browning reaction are
temperature, pH, moisture level (aw), oxygen, metals,
phosphates, sulfur dioxide, and others inhibitors.
STRUCTURES, CLASSIFICATION AND PROPERTIES
OF FOOD COLORANT
FOOD COLOR
- "Food color is any substance that is added to food or drink to
change its color."
- Food coloring is used both in commercial food production
and in domestic cooking. Due to its safety and general
availability, food coloring is also used in a variety of non-food
applications, for example in home craft projects and
educational settings etc.
PURPOSE OF FOOD COLORING:
People associate certain colors with certain flavors,
and the color of food can influence the perceived flavor
in anything from candy to wine. For this reason, food
manufacturers add dyes to their products. Sometimes the
aim is to simulate a color that is perceived by the
consumer as natural. Color variation in foods throughout
the seasons and the effects of processing and storage
often make color addition commercially advantageous to
maintain the color expected or preferred by the
consumer.
SOME OF THE PRIMARY REASONS INCLUDE
 Offsetting color loss due to light, air, extremes of
temperature, moisture, and storage conditions.
 Masking natural variations in color.
 Enhancing naturally occurring colors.
 Providing identity to foods.
 Protecting flavors and vitamins from damage by
light.
 Decorative or artistic purposes such as cake icing.
CHEMICAL STRUCTURE OF FOOD COLOURING
Food coloring molecules are organic compounds
that have at least one chromophore and a conjugated
system, which is a structure with alternating double and
single bonds between atoms. Chromophores in food
coloring dye are responsible for giving the dye its colour.
The chromophores absorb some wavelengths of
light in the visible light spectrum, allowing
complementary colours, which are opposite in the color
wheel to be transmitted.
For example, if a chromophore were to absorb
wavelengths of light corresponding to the color red, the
light that will be transmitted, and that humans will be
able to see, will be green.
In our chemistry tuition, the concept of colors
would be taught in greater details. The Crystal Field
Theory (CFT) explains the mechanism behind
chromophores absorbing and transmitting certain
wavelengths of light.
CLASSIFICATION
There are major three classification of food colors:
 Natural colors
 Synthetic colors
 Lakes and dyes

NATURAL FOOD COLOR

- Natural Food Color is any dye, pigment or any other
substance obtained from vegetable, animal, mineral, or source
capable of coloring food drug, cosmetic or any part of human
body, colors come from variety of sources such as seeds,
fruits, vegetables, algae & insect.
MAJOR COLOR OF NATURAL FOOD COLOR
Natural color: Carotene
Description
The term carotene is used for several related
hydrocarbon substances having the formula CH., which
are synthesized by plants but cannot be made by animals.
Carotene is an orange photosynthetic pigment important
for photosynthesis.

Natural color: Annato

Description
Annatto, also called Roucou, is a derivative of the achiote
trees of tropical regions of the Americas, used to produce a
red food coloring and also as a flavoring.
Natural color: Carthamin
Description
Carthamin is a natural red pigment derived from
safflower (Carthamus tinctorius), earlier known as
carthamine. It is used as a dye and a food coloring. As a
food additive, it is known as Natural Red 26.
Natural color: Betanin
Description
Betanin, or Beetroot Red, is a red glycosidic food dye
obtained from beets; its aglycone. obtained by hydrolyzing
away the glucose molecule, is betanidin. As a food additive,
its E number is E162.

Natural color: Curcumin

Description
Curcumin is the principal curcuminoid of the popular
Indian spice turmeric, which is a member of the ginger
family (Zingiberaceael.
Natural color: Caramel
Description
Caramel color (150/E150) is a dark, rather bitter-tasting
liquid, the highly concentrated product of near total
caramelization that is bottled for commercial and industrial
use. Beverages such as cola use caramel coloring, and it is
also used as food coloring.
Natural color: Turmeric
Description
Natural color: Carmine Turmeric (coded as E100 when used as a food additive)
Description is used to protect food products from sunlight. The
Carmine also called Crimson Lake, Cochineal, Natural Red 4. oleoresin is used for oil-containing products. The
C.l. 75470, or E120, is a pigment of a bright red color curcumin/ polysorbate solution or curcumin powder
obtained from the carminic acid produced by some scale dissolved in alcohol is used for water-containing
insects, such as the cochineal and the Polish cochineal, and is products.
used as a general term for a particularly deep red color of the
same name.
SYNTHETIC FOOD COLORS
- Synthetic Food Colors also known as Artificial Food
Colours, are manufactured chemically and are the most
commonly used dyes in the food, pharmaceutical and
cosmetic industries. Seven dyes were initially approved under
the Pure Food and Drug Act of 1906, but several have been
delisted and replacements have been found.

DYES AND LAKES

- Color additives are available for use in food as either
"dyes" or lake pigments (commonly known as "lakes"). Dyes
dissolve in water, but are not soluble in oil. Dyes are
manufactured as powders, granules, liquids or other special
purpose forms. They can be used in beverages, dry mixes.
baked goods, confections, dairy products, pet foods, and a
variety of other products. Dyes also have side effects which
lakes do not, including the fact that large amounts of dyes
ingested can color stools.

Lakes are made by combining dyes with salts to make

insoluble compounds. Lakes tint by dispersion. Lakes are not
oil soluble, but are oil dispersible. Lakes are more stable than
dyes and are ideal for coloring products containing fats and
oils or items lacking sufficient moisture to dissolve dyes.
Typical uses include coated tablets, cake and doughnut mixes,
hard candies and chewing gums, lipsticks, soaps, shampoos,
talc, etc.