REACTIVITY OF FOOD COMPONENTS DURING MANUFACTURE

By Dr J. Madzimure (CUT, CUAP 202)

Carbohydrates
Maillard reaction, Caramelisation, Solubilisation, Resistant starch formation

Proteinaceous material
Maillard reaction, Lysinoalanine (LAL) or lanthionine (LAN) formation, Deamination, D-
amino acid formation, Iso-peptide formation, Denaturation

Lipids
Auto oxidation, thermal degradation, CIS/trans isomerisation, Polymerisation, Formation
of Maillard reactants.

Importance of the Reactions

1. Produce chemical products that imparts flavor and aroma.
2. Improve palatability
3. Destroy anti-nutritional factors e.g toxic trypsin inhibitors, aflatoxins, gossypol
poisoning, non-toxic lignin
4. Improves quality
N.B Quality control: to avoid lowering of feed quality

Details
• Reducing sugars take part in caramelisation and Maillard reactions during moist
heat treatments.
• This has a profound effect on the flavor of feed and results in loss of nutritional
value
• With Starch granules, moist heat treatments causes them to swell or gelatinize
• In certain conditions, resistant starch is formed and this is not digestible in
monogastric animals.

Amino acids
• Amino acids, peptides and protein containing lysine take part in Maillard
reactions.
• Heat treatment in alkali conditions cause cross-linking of amino acids in proteins
• When the cross-linked amino acids are hydrolysed, LAL (lysioalanine) and LAN
(lanthionine) are formed. LAN and LAL are resistant to digestion such that this reaction
is undesirable.

Other undesirable reactions

• Formation of non-nutritive D-amino acids from the L-configuration
• Semi to dry heating at pH 7 causes cross linking which results in iso-peptides
• Heating inactivates bioactive proteins like enzymes

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Maillard reaction
The Maillard reaction is a chemical reaction between an amino acid and a reducing
sugar, usually requiring heat.
Is a form of non-enzymatic browning.
The reaction is named after the chemist Louis-Camille Maillard who first described it in
the 1910s while attempting to reproduce biological protein synthesis.
The reactive carbonyl group of the sugar reacts with the nucleophilic amino group of the
amino acid, and forms a complex mixture of poorly characterized molecules responsible
for a range of odors and flavors.
This process is accelerated in an alkaline environment as the amino groups are
deprotonated and, hence, have an increased nucleophilicity.
The type of the amino acid determines the resulting flavor.
This reaction is the basis of the flavoring industry. At high temperatures, however, the
harmful acrylamide can be formed.
In the process, hundreds of different flavor compounds are created.
These compounds, in turn, break down to form yet more new flavor compounds, and so
on.

Caramelization
Is an entirely different process from Maillard browning, though the results of the two
processes are sometimes similar to the naked eye (and tastebuds). Caramelization may
sometimes cause browning in the same foods in which the Maillard reaction occurs, but
the two processes are distinct. They both are promoted by heating, but the Maillard
reaction involves amino acids, as discussed above, whereas caramelization is simply
the pyrolysis of certain sugars. The following things are a result of the Maillard browning
reaction:
 Caramel made from milk and sugar, especially in candies: Milk is high in protein
(amino acids), and browning of food involving this complex ingredient would most likely
include Maillard reactions.
 Chocolate and maple syrup
 lightly roasted peanuts
In making silage, excess heat causes the Maillard reaction to occur, which reduces the
amount of energy and protein available to the animals that feed on it.

The process of Maillard Reactions

1. The carbonyl group of the sugar reacts with the amino group of the amino acid,
producing N-substituted glycosylamine and water
2. The unstable glycosylamine undergoes Amadori rearrangement, forming
ketosamines
3. There are several ways for the ketosamines to react further:
o Produce 2 water and reductones
o Diacetyl, aspirin, pyruvaldehyde and other short-chain hydrolytic fission
products can be formed

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o Produce brown nitrogenous polymers and melanoidins

The Maillard Reaction:

The Maillard reaction occurs in three main steps:
1. initial step: formation N glycoside

       
2. After formation of N glycoside the immonium ion is formed and then isomerize,
this reaction is called Amadori rearrangement and forms a compound called
ketosamine:

            
The ketosamine products then either dehydrates into reductones and dehydro
reductones, which are caramel, or products short chain hydrolytic fission products such
as diacetyl, acetol or pyruvaldehyde which then undergo the Strecker degradation.

Factors affecting Maillard reactions

High temperature, low moisture levels, and alkaline conditions all promote the Maillard
reaction. 
The rate of Maillard reactions increases as the water activity increases.

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However, as the Maillard reaction produces water, further increases in water activity
may inhibit Maillard reactions.
Pentose sugars react more than hexoses, which react more than disaccharides.
Different amino acids produce different amounts of browning.

LIPIDS
Are very prone to oxidation especially when the feed contains unsaturated fatty acids.
Heat treatment
• Speeds up chemical oxidation
• Prevents enzymatic oxidation by rendering lipoxygenase inactive
• Products formed in chemical oxidation can take part in Maillard reaction
Results in off flavours
Oxidised lipids can react with proteins and reduce their digestibility
Increased viscosity occurs due to isomerisation of double bonds from the Cis to the
trans-configuration, dimerisation and polymerisation

Protein Denaturation
Occurs during thermo-mechanical treatments. This is a change in the configuration of
protein that does not involve the breaking of bonds.
In most case – proteins undergo structural unfolding, aggregation. Due to moist heat
and shear effects
The 3-dimensional structure is distabilised as a result of heat and shear, by breaking
hydrophobic groups

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 Reaction of lipids
Unsaturatedlipids/
Unsaturated lipids/
Fattyacids
Fatty acids

O2 Nutritive value
Proteins
Texture Peroxides Vitamins
Cross linked
Protein Derivaties Taste
Changed
Functionality nutrients
y
Colour

Malon aldehyde Scission products

NH2 compounds

Colour
Aroma

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Maillard Reactions

Lipid oxidation Reducing sugars

Oxidised polypeptides
products

NH2: Proteins

Lipid soluble Peptides Vitamin C

Vit A, D, E Amino acids

Maillard
Reaction

Browning Loss of nutritive Other (un) desirable

Aroma, antioxidants value effects