Browning

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MODIBBO ADAMA UNIVERSITY YOLA

FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

Presentation on

Browning in Food

Group Even
ID Numbers

CHE/20U/1158 CHE/20U/1160 CHE/20U/1164 CHE/20U/1166


CHE/20U/1168 CHE/20U/1170 CHE/20U/1172 CHE/20U/1174
CHE/20U/1176 CHE/20U/1178 CHE/20U/1180 CHE/20U/1182
CHE/20U/1184 CHE/20U/1190 CHE/20U/1196 CHE/20U/1206
CHE/22D/1020
INTRODUCTION

Browning, an important reaction generally occurring during processing and storage


of food. Sensory and nutritional qualities of fruits and vegetables are degraded and
even consumer’s purchase of fresh-cut products is discouraging due to browning.
Depending on the food type, quality of food is affected either positively or negatively
by browning. During enzymatic browning, phenolic compounds are oxidized by
PPO, this reaction incorporates a particular importance in fruits, vegetables, and
seafood. Non-enzymatic browning is referred as Maillard reaction, it takes place
between free amino and carbonyl group. Food browning occurring due to
degradation of carbohydrates is called as Caramelization. Various physical and
chemical treatments have potential to inhibit browning, in fruits and vegetables
products. Variety of natural products and their extracts are known to hinder
browning of certain products, such as onion, lemon etc. Browning results in
numerous significant implications on the food business concerning to nourishment,
technology and financial expenses.

In browning process common change observed in food during pre-preparation,


processing, or storage of food is development of brown colour. Degree of its
occurrence varies in some food material. Thus, the extent of reaction and the food
item, results in variation in food’s colour from pale yellow to dark brown or black.
During browning, in some food colour and flavour developed are highly desirable
and also associated with the delicious, highly acceptable, and quality product. In
various cases browning reactions even contributes in aroma, flavour and colour of
the product for instance, in bread, chips, roasted nuts and other processed foods.

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BROWNING

Browning is a chemical reaction that occurs in certain foods when they are exposed
to heat or other conditions that causes their surface to turn brown. Browning
reactions in food are widespread phenomena which take place during processing and
storage. These reactions occur during the manufacture of meat, fish, fruit, and
vegetable products, as well as when fresh fruits and vegetables are subjected to
mechanical injury. Browning affects the flavor, appearance, and nutritive value of
the food products involved. However, for certain foods, browning is an important
part of the preparation process. For example, in the manufacture of coffee, tea, beer,
and maple syrup, and in the toasting of bread, it enhances the appearance and flavour
of these products.

Types of Browning

There are basically two types of browning;

1. Enzymatic Browning (Enzymic).


2. Non-Enzymic browning.

Enzymatic Browning:

Enzymic browning is an oxidative reaction that occurs generally in fruits and


vegetables, by the enzyme polyphenol oxidase causing them to turn brown. For
enzymic browning to occur, action of enzyme and oxidation are required. So, when
tissue is exposed to air it results in brown coloured pigment ‘melanin’ production as
a result of series of biochemical reactions. Generally, enzymic browning is a
chemical reaction which involves polyphenol oxidase (PPO), catechol oxidase, and
other enzymes that result in formation of melanin and benzoquinone from natural
phenol. Enzymatic browning requires exposure to oxygen so it is also referred as
oxidation of foods. It begins with the oxidation of phenols by polyphenol oxidase
into quinines. For instance, in case of apple, enzyme phenolase and phenol are
present in the cell, and when apple is sliced, they are exposed to oxygen in the air.

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The phenol is converted into melanin which posses brown colour, by enzyme
phenolase.

Fig.1 Melanin production in presence of oxygen.

The quinone is initial product of oxidation, which frequently condenses and results
in production of melanin (insoluble brown polymers).
Polyphenol oxidase (PPO) was first discovered by Schoenbein in 1856 in
mushrooms. Polyphenol oxidase is a copper-containing enzyme that catalyses or
causes the oxidation of phenol compounds. It even speed up the process when pH
is between 5-7. PPO enzyme is present in some bacteria, fungi, arthropods, plants
and all mammals.
In fruit and vegetables rate of enzymatic browning is determined by following
factors:
• Concentration of PPO
• Concentration of phenolic compounds present
• pH level and temperature
• Oxygen accessibility of the tissue.

Enzymatic browning is common in:


• Fruits - Apple, Pear, Peach, Banana
• Vegetables - Potato, Brinjal, Lettuce
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• Cereals - Wheat flour
• Sea food - Shrimps, Spiny lobster, Crabs

Development of colour and flavour in coffee, cocoa beans, tea and even in dried fruit
such as figs and raisins shows beneficial effect of enzymatic browning, whereas,
apples, potatoes, bananas, brinjal, lettuce, avocados and some crustaceans such as
shrimp are examples of non-beneficial effect of enzymatic browning. Major enzyme
responsible for the formation of melanosis is polyphenols oxidases (PPO).

Non- Enzymatic Browning:


Non-enzymatic browning is a process in which brown coloured polymer is formed
in the food, but without the involvement of enzymes. Non-enzymatic browning has
two main forms:
 Caramelization.
 Maillard reaction.

Caramelization:
Caramelization or Sugar browning occurs during high temperature treatment
of different types of sugar over their melting point, providing a caramel-like flavour.
In other words, caramelization could be called as a process which involves pyrolysis
of sugar. It is widely used in various cooking processes to get the desired nutty
flavour and the brown colour. As caramelization process occurs, volatile chemicals
are emitted, and results in production of the characteristic caramel flavour.
The Maillard reaction occurs under mild conditions, but sugars are generally
caramelized at temperatures above 120oC. When sugar is heated via dry heat, the
granulated sugar molecules melt at circa 160oC with continued heating, the melted
sugar will gradually turn brown and form caramelized sugar. In this process heat
generated, pulls water out of the sugar molecules, resulting in formation of furfural
derivates and its surface reaches temperature above 100oC where the browning and
flavour development begin.

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For example, caramelization of table sugar to brown nutty flavoured substances such
as furan and maltol. Caramelization of table sugar (Fig 2) i.e. sucrose commence at
high temperature resulting in melting of sugar followed by foaming (boiling).
Firstly, glucose and fructose are formed by decomposition of sucrose, followed by
condensation where sugars lose water and react with one other, ultimately forming
hundreds of new aromatic compounds having a wide range of complex flavours.

Fig2: Sucrose decomposition leading to formation of caramel.

Flavours of Caramel
• Diacetyl (2,3-butanedione) is responsible for a buttery flavour.
• Esters and lactones give sweet rum like flavour.
• Furans have nutty flavour.
• Maltol responsible for toasty flavour.

Caramelization reaction occurs in several products such as, jams, canned fruit
products, fruit juices and concentrates, soft drinks, honey, and sugar syrups. Without
using additives aromatic caramel and caramelized sugar syrups are produced, while
some additives are used for caramel colour production. So, caramel colour is also
used as a colourant in beverages and food.

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Maillard reaction
Maillard reaction is a chemical reaction that takes place between the amine group
of a free amino acid and the carbonyl group of a reducing sugar, usually with the
addition of heat (above 60 ⁰C). It is browning of food on heating or on storage due
to chemical reaction. This reaction produces flavour when food is cooked.
During the Maillard reaction, the amino acids and sugars combine to form a
complex series of molecules called melanoidins. These molecules are responsible
for the brown color and the rich, nutty, or caramel-like flavour of foods that have
undergone the Maillard reaction.
Common examples of food products that undergo maillard reaction are breads,
steaks, and potatoes. Maillard reaction is one of the important sources for generating
artificial flavours for processed food within the flavouring industry. The sugars react
with the amino acid and results in production of variety of odors and flavours,
depending upon type of amino acid used.

Stages of Maillard Reaction


There are stages in the Maillard reaction
1. The early Stage (Initiation stage).
2. Intermediate stage.
3. Final Stage.
The early stage;
In this stage there is condensation of primary amino groups of amino acids
with the carbonyl group of reducing sugars (aldose), with loss of a molecule of
water, leading to formation of a Schiff’s base and Amadori rearrangement which
results in formation of so called Amadori compound. Amadori compound is used
as a source for several compounds which are essential for the development of
distinctive flavours, aromas, and brown polymers.

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The intermediate stage;
In this stage Amadori compound breakdown and there is formation of
degraded products, reactive intermediates (3-deoxyglucosone) and volatile
compounds (formation of flavour). The 3- deoxyglucosone is involved in cross-
linking of proteins to a large extent at faster rates than glucose itself and in addition
degradation results in formation of two known advanced products:
• 5-hydroxymethyl2-furaldehyde
• Pyraline
The final stage;
In this stage nitrogen-containing brown polymers and copolymers are
produced which are known as melanoidins.
During heat treatment, acrylamide is formed as an outcome of maillard reaction
between amino acids and reducing sugars of food component. Major amino acid in
potatoes and cereals i.e. asparagine is an essential contributor in acrylamide
production. At 180°C temperature when all 20 amino acids are heated separately
for about 30 min., formation of acrylamide will be observed in case of asparagine.
In fruit and vegetable products non-enzymatic browning can be inhibited by:
• Reduction of reducing sugar content in the products
• Controlling the water activity in dehydrated foods
• Using sulfites
• Giving glucose oxidase treatment
• Reduction of amino nitrogen content in the products
• Refrigerating the products
• Packaging the products with oxygen scavengers

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Fig 3: Three major stages of Maillard reaction

The non-enzymatic browning in food depends on products composition, e.g., pH,


water activity, heavy metal ions, moisture content, exposure to oxygen, presence of
inhibitors, maillard precursors or ascorbic acid, storage time, temperature etc.

Importance of Browning in Food.


1. Flavour: The Maillard reaction is responsible for the rich, complex flavors
that we associate with browned foods. This reaction creates a wide range of
flavour compounds including pyrazines, which give foods a nutty or roasted
flavour, furans which give foods a sweet honey-like flavour.
2. Appearance: Browned foods are often more appealing than non-browned
foods because they have a darker color and a glossy, shinny appearance. This
due to the presence of melanoidins, which are larger, complex molecules that
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absorb light in the visible spectrum and give browned foods their distinctive
color.
3. Nutritional value; Browning reactions can also create new nutrients such as
vitamin C, and antioxidants which can enhance the nutritional value of food.
4. Texture: Browning reactions can also impact the texture of food, making it
more tender or crunchy.

Factors affecting Browning


1. pH: the pH of the food affects the rate of the browning. Acidic foods brown
more slowly than alkaline foods.
2. Temperature: browning reactions occurs more rapidly at higher temperature
3. Moisture content: Foods with high moisture content such as fruits and
vegetables are more prone to browning than dry foods.
4. Presence of metal ions: metal ions such as copper and iron can catalyze
browning reaction.

Browning Control
The measures to control browning are classified as:
• Physical methods
• Chemical methods

Physical Methods
• Heat treatment:
Blanching or roasting are examples of heat treatment that destroy the reactants and
denaturates the enzyme which are responsible for browning in food. Blanching at
93°C for about 2 min. inactivate PPO enzyme and improves the transfer of water
vapour from the skin e.g. light coloured raisins. Blanching is an essential treatment
in manufacturing of wine, storing of nuts and bacon, processing of tea, preparation
of vegetables for freezing preservation and so on.

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• Cold treatment:
Refrigeration and freezing are the most widely recognized methods of storing food,
preventing it from decay. Browning enzymes activity such as rate of reaction, drops
at low temperatures. Thus, refrigeration helps fresh fruits and vegetables to retain
their initial appearance, colour and flavour. Refrigeration is also used during
retailing and distribution of fruits and vegetables.
• Oxygen elimination:
For enzymatic browning oxygen is essential, thus disposing of oxygen from the
surroundings enables to sluggish down the browning in food. Withdrawing air or
supplementing it with other gases (e.g. N2 or CO2) during preservation, such as in
vacuum-packaging or modified atmosphere packaging, wine or juice bottling, using
impermeable films or edible coatings, dipping into salt or sugar solutions and
keeping food away from direct contact with oxygen. Impermeable films composed
of plastic or other materials prevent exposure of food to oxygen and also avoid
moisture loss. There is an escalating activity in developing wrapping materials
impregnated with antioxidants, antimicrobial and antifungal substances, for
example, chitosan, butylated hydroxytoluene (BHT), lysozyme, butylated
hydroxyanisole (BHA), nisin, tocopherols and natamycin. Edible coatings can be
made of lipids, proteins, polysaccharides, vegetable skins, plants or other natural
products.
• Irradiation:
Food irradiation using gamma rays, x-rays and electron beams is another technique
to expand the food shelf life. Ionizing radiation suppresses the vitality of
microorganisms liable for food spoilage, and delays the sprouting and maturation of
fruits and vegetables. By managing the dosage of radiation, browning can be
reduced. If the dose of ionizing radiation is more than 1 kGy, it will introduce diverse
type of physiological disorders in food products. When food is treated with ionizing
radiation there is production of free radicals. These free radicals are capable of

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reacting with various food constituents and induce undesirable side effects, for
instance tissue darkening, lipid oxidation, and decreased vitamin content.

Chemical methods
• Acidification:
Browning enzymes, show dynamic results at a particular gamut of pH. For instance,
at pH 5-7 PPO shows optimal activity and is hindered beneath pH 3. Acidifying
agents and acidity regulators are widely used as food additives to retain a desired pH
in food products. Acidulants, for instance citric acid, ascorbic acid, and glutathione
are also used as anti-browning agents.
• Antioxidants:
Numerous antioxidants are used as food additives in food industry. They react with
oxygen and suppress the commencement of browning process. Antioxidants also
interfere with intermediate the products of following reactions and inhibit formation
of melanin. Some of the antioxidants that are also studied for their anti-browning
properties are ascorbic acid, 4-hexylresorcinol, N-acetylcysteine, cysteine
hydrochloride, L-cysteine, erythorbic acid, glutathione etc.
• Chelating agents:
Copper is required by polyphenol oxidase enzyme for its proper functioning, thus
copper-chelating agents restrain the activity of PPO enzyme. Numerous chelating
agents are used in various fields of food industry, such as, citric acid, polycarboxylic
acids, porphyrins, sorbic acid, polyphosphates, EDTA, hinokitiol. Hinokitiol is
utilized in coating materials for food packaging.
• Sulfites:
It is quite helpful in managing browning but due to their adverse effects on health
they are subjected to regulatory restrictions. Since ancient times numerous sulfiting
agents (sodium sulfite, sulfur dioxide, sodium and potassium bisulfites and
metabisulfites) have been added to food to prevent enzymatic and non-enzymatic
browning, control microbial growth in wine, grape and other products, act as

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bleaching agents such as in cherries, antioxidants, or reducing agents, carry out
various technical functions. As per Food and Drug Administration Act of 1988,
sulfiting agents are not mutagenic, teratogenic or carcinogenic in laboratory animals,
but some people are sensitive to sulfite due to acute allergic reactions.
• Ascorbic acid:
Before quinones undergo a reaction to form brown pigment, ascorbic acid convert
quinones back into phenolic compounds, thus inhibit enzymatic browning, by
hindering PPO. Ascorbic acid inhibits enzymatic browning even after having no
direct interaction with PPO enzyme that is by reducing oxidized substrates. In frozen
and fresh-cut fruits like, peaches and apples, ascorbic acid and its isomer erythorbic
are commonly utilized as enzymatic browning inhibitor. These compounds are
added to syrup or dipping in this solution is given to fruits. Sometimes the browning
inhibitors are present in combination with organic acid for instance, citric acid and
calcium salt. Penetration of ascorbic acid, enhance the browning inhibition by
treating under vacuum or pressure rather than dipping or spraying.
• Sulfhydryl-containing amino acids:
Stable-colourless compounds are formed in milk and in pear concentrate by cysteine
as it prevents formation of brown pigment by reacting with quinones to form
intermediates. For inhibiting browning cysteine is also used as an important
ingredient. Browning of apple, fresh fruit juices etc can be managed by N-
acetylcysteine which works as efficiently as sulfites.

Conclusion
Browning occurs particularly during manufacturing, processing and storage of food
(fruit, fish, meat and vegetable products). Browning is desirable in some products
like bread crust, meat, cocoa, coffee, raisins, prunes etc. and even prolong their shelf
life. In some products sensory properties such as colour, flavour and softness besides
nutritional properties are decreased due to browning. PPO is essential enzyme of
food industry, responsible for browning, resulting in decline of nutritive value and
acceptance among consumer’s leading to economic losses. So, managing browning

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is an important key to enhance the product value, to diminish post-harvest losses and
to preserve the quality of the food. Various physical and chemical methods have
been used for inhibiting browning such as blanching, freezing, irradiation,
acidification, refrigeration etc. However natural products like lemon, onion,
pineapple etc are also used for slowing down the browning. Inclusion of natural
resources, attention to health benefits, and sustainability should be considered
utmost important while developing anti-browning agents. Genetically modified
food, is a hope in food industries, for reducing the polyphenol oxidase activity and
thus ultimately decreases browning. Production of Arctic apples is an example of
such accomplishments in food engineering. Researchers are above all interested in
studying the management or control or inhibition of browning and the various
methods that could ultimately prolong the shelf life.

REFRENCES
Food Browning, Its Type and Controlling Measures: A Review Article by
Seerat Gupta, Monika Sood, Neeraj Gupta, Julie D. Bandral and Anjali Langeh,
division of Food Science and Technology, Sher-e-Kashmir University of
Agricultural Sciences and Technology of Jammu, 180009, India.

Browning Reactions in Foods by N. A. Michael Eskin, Chi-Tang Ho and Fereidoon


Shahidi, department of Human Nutritional Sciences, Faculty of Human Ecology,
University of Manitoba, Winnipeg, Canada

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