BROWNING IN THERMALLY

PROCESSED FOODS: THE

MAILLARD REACTION

Food modifications during

thermal treatment (1)
Protein denaturation
Physical changes (starch gelatinization,
structural alterations of cell wall,
depolymerization of dietary fibre)
Lipid oxidation
Degradation of some bioactive
components

Food modifications during

thermal treatment (2)
Reaction between different components
generate new compounds.
Proteins-sugar: Maillard reaction
formation of Advanced Glycosilation
End-products (AGEs)
Lipid-protein: Advanced lipoxidation
end products (ALEs)

The same chemistry

The reaction is in both cases (sugars or oxidised

lipids) between a carbonyl moiety and an amino group

The same products

The final product of both reaction
patways (AGEs and ALEs) are polymeric
brown macromolecules

The Maillard Reaction in Foods

Produces aromas in heated
foods
Responsible for colour
formation
(non-enzymatic browning)
Maillard products have
antioxidant properties

Can cause loss of nutrients

Some products may be toxic

Temperatura e tempo di trattamento termico

Stadi iniziali

LATTE STERILIZZATO

BIRRA CHIARA

Stadi intermedi

PASTA

PRODOTTI DA FORNO
BIRRA SCURA
CACAO
CARNE ARROSTITA

CAFFE

Stadi avanzati

Diminuzione dellattivit dellacqua

LATTE UHT

Louis-Camille
Maillard
(1878 - 1936)
Photographed in
his laboratory
ca 1915
1912 1916:
He published 8 papers
on his observations of
colour changes on
mixing amino acids and
sugars.
No one else took much
interest in the
reaction until 1950s

John Hodge: 1914 -1996

Chemist at USDA in Illinois (1941 1980)
His proposed mechanism for the chemistry of
non-enzymic browning is largely unchanged
after 60 years.

Citations since 1970

Paper

Citations

Hodge, J. E.
Chemistry of browning reactions in model
systems.
J. Agric. Food Chem. 1953, 1: 928-943.

890

Maillard, L. C.
Action des acides amines sur les sucres:
formation des melanoidines par voie
methodique.
Compt. Rend. 1912, 154: 66-68.

634

Maillard-Hodge Reaction?

Hodge Scheme

Hodge J E. Dehydrated foods: chemistry of browning reactions in model systems.

J. Agric. Food Chem. 1:928-43, 1953.

First step: formation of Amadori

product
RNH

RNH

HC
(HCOH)n

CH
O

HC
CH2OH

Glicosilammina
N-sostituita

+H+

(HCOH)n
HCOH
CH2OH

Catione della
base di Schiff

-H+

RNH

RNH

CH

CH2

COH

CO

(HCOH)n
CH2OH

Forma enolica
del PA

(HCOH)n
CH2OH

1-ammino-1-deossi2-chetoso (PRA)
PRODOTTO DI
AMADORI

slow

fast

Formation of Carbonyl through Maillard Reaction

O
OH

OH

OH

H2O

RNH2

fast
R N
H

2,3-enolisation

OH

OH

OH

R N
H

OH
O

OH

OH

1-deoxyosone

OH
OH

Amadori compound

OH

1,2-enolisation

slow

R N
H

OH

OH

H+

OH

OH

- H2O
R

H2O

OH

H2O

RNH2
N+
H

OH

OH
3-deoxyosone

CHO

Strecker Degradation
Free amino acids with dicarbonyl compounds

R-CHO
Aldeide di Strecker

Flavour and Colour in the

Maillard Reaction
OH

OH

O
H

OH

OH

R NH2

OH

reducing sugar

OH

H 2O

NHR
H

rearrangement

OH OH

amino
compound

Amadori intermediate
H2O
RNH2
O

FLAVOUR
COMPOUNDS

OH

H
O

MELANOIDIN
PIGMENTS

HO
O

CHO

OH

amino
Aminoacids
acid

or
proteins

OH

OH
O

carbonyl compounds

CHO

General scheme of MR browning

Amine

Melanoidins
Brown colour

Ammonia
Phospholipids
Amino acids
Proteins

HEAT
Carbonyl

Aldehydes
Ketones
Reducing sugars
Polysaccharides
Oxidised lipids

Amides
Acrylamide

Amino Carbonyl
Interaction
(Amadori product)
Furans, Pyrroles,
Thiopenes, Thiazoles,
Oxazoles, Imidazoles,
Pyridines, Pyrazines

Food melanoproteins
R
O

HO

CHO

OH

Lysine

H
N
N
H

R'

R'
N
H

H
N
O

R'

H
N
N
H

HO

CH3

R'
N
H

H2N

N
H

R'

N
R'

Protein A

R'

N
O

R'

R'

O
N

N
O

R'

N
O

R'
N

N
O

N
H

R'

H
N

CH3

H
N

OH

R'

N
O

R'

R'

Protein B

Pronyl-lysine
This compound is formed on the lateral chain
of Lysine residues
Pronyl-lysine has a high antioxidant activity

Possible toxicants

Acrylamide
Furan
Heterocyclic amines
3-MPCD (Mono Chloro Propan Diol)
3-Methyl Imidazolone
Development of mitigation strategies to
reduce their concentration

A network of many reactions

giving thousands of products
Products formed depends on:

Chemical nature of the reactants

Time and temperature of heating
Technological conditions
Water activity, pH

Practice
Effects of reactants:
Sodium Carbonate (pH effects)
Protein and carbohydrates
Water activity (fibre addition)
Butter clarification
Control
Added with sodium bicarbonate