NON ENZYMATIC

BROWNING
 Two Major Types Of
Non-Enzymatic Browning Reactions

• Caramelization
• Maillard browning
 Reactions During Caramelization

• Anomeric equilibration (alpha, beta)

• Pyran, furan equilibration
• Sucrose inversion – Hydrolysis
• Aldose, ketose interconversions
pyran furan
• Inter- and intramolecular condensation
• Dehydration
• Skeletal fragmentation
• Browning
 CARAMELIZATION

Flavoring Caramelization

buffer
sucrose syrup inversion, fragmentation
heat
(maltol, etc)
 CARAMELIZATION

Caramel pigments

• Glucose Partially Heat Caramel

syrup neutralized colloid
pH

• Used to color colas. They are not naturally brown but have these
pigments added to color them.
 CLEAR COLAS

• See the Wikipedia entry on Pepsi Crystal here

http://en.wikipedia.org/wiki/Crystal_Pepsi

• A disaster-see the marketing section

of the Wikipedia entry
MAILLARD REACTION
 Amadori compounds
• Partial stability in comparison with imines (the cyclic molecular structures)

• Amadori rearrangement leads to furanose (hemiacetal) - has stability to mutarotation

• React further with second sugar molecule → glycosylamine formation + conversion to di-D-
ketosylamino acids (“diketose amino acids”) by an Amadori rearrangement

• Amadori products: intermediates formed in the course of the Maillard reaction. Eg.
Deoxyosones

• As an analytical indicator of the extent of the heat treatment of food.

• Amadori compounds are degraded to (1-, 3-, and 4-deoxydicarbonyl compounds /deoxyosones)
in the pH range 4–7

• - Vary concentration - depends on the reaction conditions (pH value, temperature, time, type
and concentration of the educts) → change in the product spectrum (Eg. color, taste, odor)
Degradation of Amadori compounds
 Strecker Reaction

α-dicarbonyl compounds (Eg. Deoxyosones) + amino acids

↓
Strecker aldehydes (aroma potential) + CO2 + α-aminoketones

• Occurs in foods at higher concentrations of free amino acids or drastic reaction

conditions (Eg. higher temperatures, under pressure)

• Strecker aldehydes: methional, phenylacetaldehyde, 3- and 2-methylbutanal and

methylpropanal

• Other compounds formed via the Strecker degradation and influence the aroma of
food: H2S, NH3, 1-pyrroline and cysteamine
MAILLARD BROWNING REACTION VARIABLES

Temperature
• Generally, the higher the temperature, the greater the browning

pH
• As pH goes down, so does browning. Due to protonation of the
reactive amino group, making it unreactive.
UNDER NEAR NEUTRAL CONDITIONS
UNDER ACIDIC CONDITIONS
CONT..
• Water
CONT..
Oxygen
• Seems to have little effect

Metal ions
• Cu(I), Cu(II) and Fe(II), Fe(III) speed up the reaction.
• Other metals seems to have little effect.
• Can control the with metal chelators (e.g., EDTA).
Sugar Open chain Melanoidin
Glucose 1 1
Fructose - 1.2
Galactose 3.4 2.0
Xylose 7.1 5.5
Arabinose 7.1 6.7
Ribose 354 Very high
A PRACTICAL EXAMPLE OF THE EFFECT OF
MAILLARD BROWNING IN COOKIES
 CONTROL OF BROWNING

• Create unfavorable conditions for the reactions to

take place

Water → low or high

pH → lower, decreases browning
Temperature→ the lower the temperature, the less
the browning
CONT..
Removal of substrates

• Glucose oxidase→ removes the open chain form by converting it to

gluconic acid.This technology is used in preserving dried egg whites.

• Ribose oxidase→ this enzyme activity occurs in Lactobacillus

pentoaceticum and is used to prevent fish from browning.
 SULFITE BROWNING INHIBITORS

• Principally sulfur dioxide or bisulfite.

• These sulfur compounds react with HMF near the end of

the decomposition of the Amadori compound and divert
it to a non-reactive product, that is one that cannot be
converted into melanoidin pigments.
SULFITE INHIBITOR REACTION
WHY WORRY ABOUT MAILLARD BROWNING

Aesthetics

• Overly browned foods are not aesthetically attractive and may

not be accepted

• Also, due to the pyrazines produced by the Strecker

degradation, these highly browned foods may have odd, off
flavors and also not be accepted
CONT..
Nutritional effects

• Amino acids that participate in the Maillard reactions are lost from a
nutritional point of view.

• This may be especially important where the amino acid is very

reactive and in foods where it is already in very low concentration.

• This would be the case for L- lysine in cereals.

REASON FOR THE REACTIVITY OF L-LYSINE
CONT..
Mutagenicity

• This is not yet settled in the literature. Some researchers find

mutagenic products in browned model systems, others do not.

• But there is still the possibility that highly browned food may
contain potential mutagens.