Browning Reactions

in Foods

Food Technology
Lecture 01
Learning Outcomes:
• To identify types of browning reactions
involved in foods.
• To study mechanism of action behind
each browning reaction.
• To identify significance of browning
reactions in food processing.
• To identify preventive measures to
control browning.
 Browning Reactions
• Change of food color into brown color after processing
• In certain instances it is favorable & in some cases it is
highly unfavorable
• Favorable : Bakery products
Coffee roasting
Honey products
• Unfavorable: Fresh fruits & vegetable processing
 Unfavorable

Favorable
Browning reactions occur in two ways.
• Enzymatic browning
• Non enzymatic browning

Non-enzymatic browning - different types

• Maillard Browning
• Caramalization
• Ascorbic acid browning
• Oxidation of lipids
 Enzymatic Browning

 Always occur in live tissues

Reaction:

O2
Enzyme + Substrate Product
(complex
cpd)
Enzymatic Browning

Phenols
(Inside the cell)

Oxygen Phenolases
(Air) (cell wall)

Brown Pigments
 Phenolase
• Phenolase is classified as an oxidoreductase.
• Substrates for phenolase: phenolic compounds present in
tissues of F&V.
• Phenolase hydroxylates monophenols to o-diphenol and
oxidizes o-diphenols to o-quinones.
• o-quinones then enter into a number of other reactions,
which produce “undesirable” brown discolorations.
• Quinone formation is enzyme and oxygen-dependent.
• Once quinones have formed, subsequent reactions occur
spontaneously and no longer depend on phenolase or
oxygen.
Examples for substrates:
• Rare at intact tissue, since phenolic substrates and
phenolase are separated.

• Common at the cut surface of light-colored F & V.

• Cut surface may rapidly change to brown color due to

oxidation of phenols to orthoquinones, which in turn
polymerize to form melanins (brown pigment).
• This phenomenon is favorable in certain instances.

– Tea, coffee, and cocoa: color and flavor

development.

– Raisins, prunes, dates and figs: development of

characteristic golden brown color in dried fruits

– Physiological roles: antibacterial and antifungal

activity of melanin assist to keep F & V
physiologically wholesome.
• In certain instances it is unfavorable & produce off
flavors & off colors
– Over 50% losses in fruit occur due to enzymatic
browning
– Lettuce, other green leafy vegetables, potatoes and
other starchy staples, breadfruit, yam, mushrooms,
apples, avocados, bananas, grapes, peaches, and a
variety of other tropical and subtropical fruits and
vegetables, are susceptible to browning and cause
economic losses for the agriculturist.
Enzymatic Browning is unfavorable due to:

• Make the food unappealing

• Soften the texture

• Loss of flavor

• Limit the shelf life of the product

• Decreasing the value of the product

• Economic losses.
 Prevention
• Immersing the “injured” food (for example,
apple slices) in cold water.

• Optimum temperature for enzymes to act is

43ºC (109ºF). Lower temperature decreases
enzyme activity, and water limits the
enzyme’s access to oxygen.
• Refrigeration slows enzyme activity even more, and boiling
temperatures destroy (denature) the enzyme.

• Heat treatment – mild heat treatment (blanching)

to inactivate enzymes

• Lowering of pH to 2.5-2.7 by addition of acids (ascorbic acid,

malic or citric acid)
Phenolase works very slowly in acidic environment created
by added acids.
• Chemical compounds (reducing agents) – due to blocking of
active sites of an enzyme (SMS, SO2)
• Use of anti-oxidants

Eg. Vitamin C (ascorbic acid) present in lemon juice

functions as an antioxidant.

It is more easily oxidized than the phenolic-derived

compounds, and its oxidation products are
colorless.

• Vacuum packaging or modified atmospheric storage

(eliminate O2)

• Use of high concentrated sugar or salt solutions

NON-ENZYMATIC
BROWNING
 1. Maillard Browning
• Non-enzymatic browning reaction .
• Caused by condensation of an amino group and a
reducing compound resulting complex changes in
biological and food system.
• Reaction was first described by Louis Maillard in
1912.
• Occurs when most foods are heated, or during
storage.

• Effects of Maillard reaction: caramel aromas and

golden brown colors, are desirable.

• Foods darkness and off-flavor development, are

undesirable.
 No involvement of enzymes or O2
 Not occur due to oxidation
 Happen in the presence of carbonyl compounds
(reducing sugars – glucose, fructose, pentose) & amines
(amino acids, proteins)
 In the presence of these two chemicals in high To cause
browning
 Formation of N-glycosides as well as numerous
consecutive reactions collectively called MB
 Maillard browning can result:
• Brown pigment melanoidins / melanoids
• Volatile aroma compounds – aldehydes,
alcohols, ketones
– This is favorable as it provide good smell
– Maillard reactions are important for desired
aroma during cooking, baking, roasting & frying.
– Sometimes it can produce off colors.
• Taste compounds
Bitter compounds in bread – unfavorable
• Produce compounds with highly reductive
properties
• Loss of amino acids
• Loss of sugars
 Maillard Browning Reaction
• Consist of 4 steps
– Condensation of amino acids with reducing sugar
(N-glycoside formation)
– Amadori rearrangement / Heyns re-arrangement
– Formation of primary products from amadori
products
– Formation of secondary products
 General scheme of MR browning:

Melanoidins Amides
Amine Ammonia
Brown colour Acrylamide
Phospholipids
Amino acids
Proteins
Amino Carbonyl
Interaction
HEAT (Amadori product)
Aldehydes
Carbonyl Ketones Furans, Pyrroles,
Reducing sugars Thiopenes, Thiazoles,
Polysaccharides Oxazoles, Imidazoles,
Oxidised lipids Pyridines, Pyrazines
1. Initial step- formation N glycoside: The carbonyl group of the
sugar reacts with the amino group of the amino acid,
producing N-substituted glycosylamine and water
 
2. After formation of N glycoside (imine / immonium ion) it is
isomerizes, this reaction is called Amadori rearrangement and
forms a compound called ketosamine:
3. Ketosamine products then act in various ways to
produce different end products:
reductones and dehydro reductones, dicarbonyls,

diacetyl, acetol or pyruvaldehyde (undergo Strecker

degradation and produce short-chain products,
brown nitrogenous polymers and melanoidins)
Factors influencing the browning rate:

• Source of nitrogen
- proteins or amino acids
• Source of carbon / carbonyl compound
- reducing sugars
- ketoses are less reactive than aldoses
• pH of the medium
- reaction fastest at moderately acidic pH (pH 4-7)
• Temperature
- Heating accelerate the reaction
- Browning faster in cooked foods
- Occurs slowly, but significantly at moderate To
• Water activity
- Reaction faster at moderate water levels
- Water promotes mobility of reactants
- Water participates at later stage of reaction
 Control of Millard Browning

• Remove reducing sugars or proteins

• Use of non-reducing sugars (sucrose)
• By keeping the To as low as possible
• Remove almost all water
• Keep pH below isoelectric point of the amino acid
or proteins (use strong acids)
• Add sulphites – Block dicarbonyl reactions
 2. Caramelization

Sugar (colorless)  
Anhydrous / Heat

Caramalan Heat

Heat
Caramalen

Humin (dark brown, bitter compound)

• Browning reaction formed by heating carbohydrates
(eg. sucrose or reducing sugars).

• Reactions facilitated by small quantity of acids, base

and certain salts.

• Different process from MB, though the results are

similar to the naked eye (and taste buds).

• Final product caramel contains a complex mixture of

polymeric compound, formed from unsaturated
cyclic compounds.
• Flavour and aroma compounds are also formed.

• Heating causes dehydration of sugar molecule with

introduction of double bonds or formation of
anhydro rings. Intermediates such as 3-deoxy
osones and furans are formed.
• Unsaturated rings may condense to form useful,
conjugated double-bond containing, brown colored
polymers.
• Catalysts increase reaction rate and used to direct
the reaction to specify types of caramel color,
solubility and acidities.
• The carbohydrates most often used are sucrose, but
fructose, glucose, invert sugar, malt syrups and
molasses may also be used.

• Acid used are food grade sulfuric, sulfurous,

phosphoric, acetic and citric acids.

• Bases - ammonium, sodium, potassium and calcium

hydroxides.

• Salts - ammonium, sodium, potassium carbonates,

bicarbonates, phosphates, sulphates or bisulphates.
Initial caramelization temperatures of common
pure carbohydrates
 3. Ascorbic acid browning
• Ascorbic acid can be oxidized & formed Brown
color

L-Ascorbic acid is biologically active & can be

converted to Dehydro-L-Ascorbic acid.

• DHAA then converts to 2,3 – diketogulonic acid

& finally converts to brown polymers
 4. Oxidation of Lipids

• Fats & oil at high To

• When To, >200oC –occur pyrolysis

• Give off colors & flavors (Acrolein)

Oxidation of lipids occurs at high T o in 2 steps:

• Hydrolysis of tri-glycerides

• Oxidation of unsaturated FA
Hydrolysis of fats:
Oxidation of fatty acids
 Oxidation of PUFA
• Oxidation of PUFA – primary source of flavor Dvt. In
heated oil.
• Occurs at elevated To – (100-200oC)
• Hydroperoxides are formed as the major initial
product
• Highly reactive & readily decomposed in to
aldehydes & Ketones at high To
• Those aldehydes further oxidized to form aromatic
acids.
 Pyrolysis:

• If the To of the frying oil above 200oC – pyrolysis takes

place & produce Acrolein as the major end product.
• Has a pungent & irritating odor.

• So, pyrolysis has a negative effect upon flavor

development during frying.
 Effects of frying condition on Flavor:

• Freshness of the oil

Fresh oil has few volatile compounds. So, flavor is not

optimum at beginning & it develop gradually upon
heating.
• Frying To - Normally To should be b/w 100-200oC

Above 200oC – pyrolysis occurs & give off flavor.

• Trace metals – Cu, Ni (Catalyse oxidation of lipids)
• Anti-oxidants
Prevent oxidation of lipids. Has a negative
effect on frying oil
• Anti-foaming agents - Prevent foam formation,
thus limiting O2 availability of frying oil.
• Negative effect on frying oil.