Food Chem Theory MRB

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Carbohydrates are a class of organic compounds containing carbon,

hydrogen and oxygen and have

a general formula C x(H₂O)y, where x and y are whole numbers.

Due to this formula they were once

considered to represent hydrated carbon or hydrates of carbon. This


meaning fits well with the name

carbohydrates (carbon hydrates).

However, it was realised later that there was no water molecule in the
molecular formula of a carbohydrate.

Accordingly, a new name viz. saccharide (derived from sakchron meaning


sugar) was proposed for these.

We continue to use the familiar term carbohydrate though it is not quite


apt.

The arrangement of atoms in carbohydrates in their simple linear form


contains a chain of carbon atoms in which except one, all the carbon atoms
carry on OH group each. One carbon atom carries a carbonyl group (C=O).

The carbonyl group may be located at the end of the carbon chain as an
aldehyde or inside the chain as a

ketone. This chain can have three to hundred of carbon atoms.

On the basis of this arrangement of atoms and groups, carbohydrates are


defined polyhydroxyaldehydes

or ketones or the substances which give aldehydes or ketones on


breakdown'.
Glucose, the most common simple carbohydrate, is polyhydroxyaldehyde
while fructose is a polyhydroxyketone.

The general linear structures of simple carbohydratesbalong with an


example each are represented in Fig.

The linear structure of glucose shown in Fig.6.1 could

explain many of its properties but could not account

for certain significant observations.

Notable among them being its existence in two different crystalline forms.
These are obtained by

crystallisation from concentrated solution of glucose

at different temperatures.

The two forms have different melting points, also. This fact could be
explained by proposing a cyclic

structure for glucose. This structure is obtained when one of the -OH groups
in the open chain reacts

with the -CHO group to form a cyclic hemiacetal structure.

In this structure, glucose forms a

six-membered ring in which -OH at C-5 is involved in ring formation.


These two cyclic forms exist in

equilibrium with the open chain structure as shown in Fig.

The phenomenon related to the existence of these two forms is called


mutarotation.

Classification of Carbohydrates :

Carbohydrates can be classified in several ways. The classification may be on


the basis of their chemical

structures, composition, nature of carbonyl function, reaction with oxidising


agents or physiological roles.

According to the Food and Agriculture Organization and the World Health
Organization, the carbohydrates should be classified primarily by molecular
size.

Accordingly, the carbohydrates are classified into sugars, oligosaccharides,


polysaccharides and polyols.

Each group can be further divided into various sub- groups. We however
would not go into these details here and be content with a broad
classification.

Sugars :-

Sugars are also called simple carbohydrates and consist of monosaccharides


and disaccharides.

The monosaccharides consist of a single polyhydoxyaldehyde or ketone unit


that cannot be hydrolysed into smaller such units.
Glucose and fructose are the common examples of monosaccharides.

Fructose or the fruit sugar is sweetest of all sugars.

These two monosaccharides are present in varying amounts in honey, maple


syrup, fruits, and vegetables

and in some processed foods.

Monosaccharides can have three, four, five, six or seven carbon atoms in
them and are called trioses,

tetroses, pentoses, hexoses and heptoses respectively.

The structures of some monosaccharides with different number of carbon


atoms.

The disaccharides consist of two molecules of monosaccharide units joined


by glycosidic bonds.

Sucrose or cane sugar, lactose or the milk sugar and maltose, the malt sugar
obtained from cereal grains

are the common disaccharides.


Sucrose consists of two six-carbon sugars, glucose and fructose linked
together while in lactose, a molecule each of glucose and galactose are
joined together.

The two monosaccharide units in maltose are glucose.

Sucrose is the most widely used natural sweetener. In fact, the sweetness of
different natural and

synthetic sweeteners is compared with sweeteners sucrose which has been


given an index of 100.

Fructose, the sweetest natural sweetener has a value of 173.3 while the
artificial sweetener, saccharin has a value of greater than \~30000.

Oligosaccharides: 3-9 Monosaccharide

The oligosaccharides consist of short chains of monosaccharide units or


residues, ranging from 3 to

9, joined by glycosidic bonds. These occur widely in small quantities in plant


food products like cereals, such as wheat and rye; vegetables, including
onions, garlic, asparagus, and chicory and in bananas and o

honey.

Raffinose is a trisaccharide found in free state in the sugar beet. It consists of


a molecule each of

galactose, glucose and fructose linked in the same sequence.

Verbascose is an example of a penta-saccharide.

Polysaccharides:

Polysaccharides consist of chains of monosaccharides containing more than


9 units and may extend to hundreds or thousands of units.
Some polysaccharide molecules such as cellulose are linear chains, whereas
others such as glycogen and starch are mixtures of straight and branched
chain molecules.

Starch is a mixture of two large polymers; amylose, which consists of linear


chains of glucose, and

amylopectin, which is a highly branched polymer with

a higher molecular weight.

Glycogen also has a structure similar to that of starch, the only difference
being that the chains are shorter

and there are more branches.

Polydextrose and inulin are the polymers of glucose and fructose,


respectively. These are used as bulking agents and as sucrose replacements
in food products.

The plant polysaccharides and lignin which are resistant to hydrolysis by the
digestive enzyme in human beings are loosely called dietary fibres.

The main components of dietary or the crude fibre are cellulose,


hemicelluloses, hexosans (gallactans and fructosans etc), pectic substances,
gums,

mucilage and lignin.

The dietary fibers are also called the non-starch polysaccharides (NSP).
Non-starch polysaccharides (NSP) :

These are composed of a mixture of different polysaccharides containing the


pentoses like xylose and arabinose or hexoses like mannose, glucose, and
lose segalactose, and uronic acids.

Mannose & Lycose galuctse, Vronic Acid In addition to the above plant cell
polysaccharides, 'gums' (the substances secreted by plants in response to
injury and algal polysaccharides), extracted from

algae are also included into NSP or dietary fibres.

Cellulose consists of an unbranched (linear) chain of several thousand


glucose units joined by ß glycosidic.

linkages.

Since the human digestive enzymes cannot hydrolyze them, these are
résistant to digestion.

Hemicelluloses include a range of different polysaccharides with structures


comprising linear and

branched chains of pentose and hexose units.

These have much lower molecular weights than cellulose and may be
present in plant foods in water soluble or insoluble forms.
Pectins are water-soluble carbohydrates consisting mainly of chains of
galacturonic acids and rhamnose which are branched with chains of
pentoses and hexoses.

These are present in vegetables and fruits and are prepared mainly from
waste citrus peel and apple skin.

Hydrocolloids consist of a wide range of mixed polysaccharides and are


derived from seaweed extracts, plant exudates, and seeds. These includes
gums and mucilage, like guar gum, locust bean gum, agar, and Gums,
Mucilage,

carrageenan.

Xanthan gum is a microbial gum consisting of glucose and glucuronic groups.

Effect on Starch :

Heating the food to cook it and cooling thereafter before consuming have a
significant effect on the

starchy components of the food. These can be understood in terms of two


important phenomenan.

These are as follows.

Gelatinization:

As mentioned earlier, on heating starch in the presence of water, the


crystalline structure of the starch granules is lost irreversibly by a process
alled gelatinization.
It is due to absorption of water by starch granules and turning into a jelly
like substance.

In this process, amylopectin forms the gel and amylase comes into solution.

When heating is continued in excess water, more soluble components of


starch come into solution and a paste results.

In the food processing, the starch granules are not completely dissolved
however, their partial

gelatinization is sufficient to allow a good part of the starch to be digested


rapidly.

In the steaming of food, the process of gelatinization occurs to a small


extent whereby a large proportion of slowly digestible starch is preserved.

Retrogradation:

The process of re-association of the starch granules on cooling of the


gelatinized starch or the starch paste is called retrogradation.

It depends on the relative proportions of amylose and amylopectin in starch


as linear amylose, molecules re-associate faster than the highly branched
amylopectins.

Reheating starchy foods also influences this process.

The digestibility of starch in the small intestine is reduced by the degree of


processing and
retrogradation.

The staling of bread is due to retrogradation of starch and the rate of staling
is temperature

dependent.

Effect on Dietary Fibre:

The cereal grains are usually milled to form refined flours which are
processed to prepare food products.

The milling process removes the fiber-rich outer layers of the grain, and
diminishes the total fiber content.

The flours of wheat, rye, and maize contain large amounts of cellulose and
hemicelluloses.

Oat and barley also lose some dietary fiber in the process of milling. Besides
the heat treatment can

also influence the physical structure and the functional properties of the
dietary fiber.

The pectic substances cause thickening of juices, also these are also
responsible for mushy nature of

vegetables.

Use of Sugars in Food:

The most obvious role of sugar in foods is to impart sweetness. However,


these have numerous other

functions as well, which make them important ingredients in many foods.


Some of these are given below:

Sweetness: The combination of sugars and fats in confections provide a


sweet taste and texture that

compliment each other. In beverages, sucrose provides sweetness without


altering the subtle flavours of the beverage.

Texture: Sugárs make an important contribution to the texture of foods,


commonly referred to as 'mouthfeel'.

For example, glucose syrups in ice-cream provide it a smooth texture by


preventing lactose crystallisation which may give a sandy feeling.

In bakery applications, sugars are used to impart flavour, aroma and colour.
Further, addition of sugar

ensures that the gluten maintains an optimal elasticity, allowing the dough
to expand and rise properly.

The crisp texture of the bakery products is due to recrystallization of sugar


on removal of water during baking.

Sugars also acts to tenderize bakery products by slowing the rate at which
starch molecules become interlinked and proteins break down.

Glucose, fructose, sucrose and maltose are used in bread making to increase
product and prevent

excessive stickiness.

Preservation:
In many products, sugars play an

important role in preservation. The addition of monosaccharides, such as


glucose or fructose, to jams

and jellies inhibits microbial growth and subsequent spoilage.

Sugars have a great affinity for water, thus slowing moisture loss in foods,
like baked foods and extending the shelf-life of these products.

Both honey and invert sugar help to retain moisture due to their high
fructose content, as do sorbitol (sucrose alcohol) and corn syrup.

Fermentation: The production of chemicals by fermenting various sugars has


been in practice since

long.

Ethanol has been made since ancient times by the fermentation of sugars.

All beverage ethanol and more than half of industrial ethanol is still made by
this process.

Zymase, an enzyme from yeast, changes the simple sugars into

ethanol and carbon dioxide.

The fermentation reaction can be represented by the following simple

equation.

C6 H12 O16 →2CH3 CH₂OH + 2C0₂


Appearance: You have read in Sec 6.4 that two major types of non-
enzymatic browning reactions i.e. Caramelization and Maillard reaction have
been recognised to occur in foods during processing.

The colour of bread crust is a result of Maillard reaction.

The golden brown crisp surface formed as a result of caramelization


enhances flavour and taste and also

helps in retaining the moisture.

Freezing Point

Suagrs are effective in lowering the freezing point. Monosaccharide and


corn syrups, containing a high proportion of low molecular weight sugars are
most effective at lowering the freezing point.

Reducing sugars such as glucose, fructose maltose and lactose are


recommended for icecream.

In frozen desserts, sugars give flavour and mouthfeel.

Antioxidants:

Many carbohydrates are excellent

scavengers of metal ions. Glucose, fructose and sugar alcohols (sorbitol and
mannitol) have the ability to block the reactive sites of ions, such as copper,
iron and to a lesser extent, cobalt.

This is characteristic of monosaccharides and aids in food preservation by


retarding catalytic oxidation reactions.

Furthermore, maillard reaction products are known to have antioxidant


properties in food systems.
For this reason, some mixtures of maillard reaction product have been
employed in the food industry as

food additives for biscuits, cookies and sausages.

Freezing Point: Sugars are effective in lowering the freezing point of a


solution. Monosaccharides and

Food Applications of Starch Polysaccharides:

Starches find numerous applications in food because of easy availability and


low cost. These include the cus

following.

Thickener:

You know that starch absorbs water and swells up. If the amylose content of
the starch is more, its long water soluble chains increase the viscosity and
thickens gravies, sauces and pudding.

Fat replacer: The water absorbing property of starches is also responsible for
the mouthfeel of many food products containing them and may be used as
fat substitutes e.g. in salad dressings and dairy

products.

Water binder:

As starch readily absorbs moisture,


it checks its escape from the food product and in some dishes like cakes, it
retains the moisture and

yet does not allow it to be wet.

The high water binding ability of starches leading to their swelling up can
provide body and texture to the food stuff.

The partial hydrolysis of starch yields dextrins (glucose polysaccharides of


intermediate size).

These are more easily digested than starch and therefore are extensively
used in the preparation of infant foods.

Besides these, starches find applications as adhesives (in stamps), binder (in
formed meats and breaded items)

bulking agent (in baking powder, fat).

Modified starch: The starches in their native form or as they are available in
nature do not fulfill all the desirable requirements.

In order to have better usefulness, starches are treated to alter one or more
original characteristic. These are called modified starches and are with
improved characteristics.

Modified starches find applications in instant desserts, jellies, salad


dressings, canned soups and many more.

Food Applications of Non-starch Polysaccharides:

Cellulose: The most important application of cellulose is in 'water retention'.


The dry amorphous

cellulose becomes soft and flexible on absorbing water.


Besides this, the cellulose finds applications as emulsifier, anticaking agents,
dispersing agent, thickener and gelling agent.

Cellulose also is used to reimprove the volume and texture of food. In


addition, an important derivative of cellulose i.e., earboxymethyl cellulose
(CMC) also finds many

applications as a stabilizer due to its being soluble in cold water.

Hemicelluloses: It finds applications as emulsifier, stabilizer and binder in


flavour bases, dressings and pudding mixtures. These are also used as
bulking agents and as fat replacer.

Pectins: These find extensive applications as gelling agents in jams and jellies
besides being water binders, thickeners and stabilizers.

Hydrocolloids:

Find applications as thickening,

gelling, stabilizing, or emulsifying agents in some food products. The


microbial gums are finding wide food

applications today, for example dextran gums are readily soluble in'water.

Nutritional and Clinical Importance :

A significant component of starches in the diet does not get degraded in the
stomach and is called resistant

starch. These are also grouped into dietary fibres and serve as substrate for
the intestinal microflora which
synthesise important vitamins.

Hemicelluloses are good sources of dietary fibre and stimulate the immune
system. These are also good for promoting weight loss, relieving
constipation and controlling carcinogens in the intestinal tract. These are
also helpful in reducing postprandial serum glucose level; reduce insulin
response and serum

cholesterol level.

Certain hydrocolloids also have positive health. These are good laxatives.
Dietary intake hydrocolloids are associated with the reduction of blood
glucose level, insulin response and cholesterol

lowering effect.

Some people are unable to digest lactose due to deficiency of enzyme


lactase, these people are lactose

intolerant. In such cases, some of the unhydrolyzed lactose passes into the
intestine and its presence tends

to draw fluid into interstitial rumen by osmosis. Intake of milk by them leads
to abdominal distention, cramps and diarrhoea.

From a nutritional standpoint, sugars should be consumed in relatively small


quantities as they provide no other nutrients than carbohydrates. This
recommendation is made so that individuals will avoid consuming a
disproportionate number of

calories without a corresponding proportion of vitamins, minerals and


proteins.

Further, excessive consumption of large amounts of carbohydrates,


particularly fructose and sucrose, over a long term are found to cause an
elevation in triglyceride

concentration, and LDL, production of low density lipoproteins (LDL and very
low DL) which may lead

to heart stroke.

Proteins:

Amino Acids :

Amino acids are organic molecules and as the name suggests, an amino acid
consists of an amino group

and a carboxyl group.

The carbon atom which has these two groups attached to it has a hydrogen
atom, and a distinctive

R group (called side chain) bonded to it. This carbon is called the a-carbon
because it is adjacent to the

carboxyl group.

The general formula of an a-amino acid can be represented as shown in Fig.

More than twenty natural amino acids are known. Different amino acids
contain different side chains

i.e.,-R groups, varying in size, shape, charge, hydrogen-bonding capacity and


chemical reactivity.

Essential and Non-essential Amino Acids:


On the basis of their source in the living system, the amino acids are
classified into essential and non-

essential amino acids.

Of the twenty standard amino acids, in case of humans, more than half of
these can be made by the body itself, while the others must come from the

diet.

The former are called the non-essential amino acids and the latter are called
the essential amino acids.

The essential amino acids (for human beings) are isoleucine, leucine, valine,
lysine, methionine, V

phenylalanine, threonine and tryptophan.

The classification of an amino acid as essential or non-essential does not


reflect its importance as all

the twenty amino acids are necessary for normal functioning of the body.

It simply reflects whether or not the body is capable of synthesizing a


particular amino acid.

The requirement of essential amino acids per kilogram of the dietary protein
is called the reference pattern of the amino acids and acts as a standard to
determine the quality of the protein being consumed.

Peptides :

Two or more, similar or different amino acids combine to give a


condensation product with elimination of a water molecule.
The product is called the peptide.

The amide linkage joining the carboxyl group of one amino acid to the amino
group of another amino acid is called a peptide

bond.

Two amino acids join to form a di-peptide, three form a tri-peptide, four
form a tetra-peptide and so on.

Accordingly, these contain one, two, three and more number of peptide
bonds.

In a peptide, the amino acid whose carboxyl group participates in the


formation of the peptide bond has a free amino group, and is called as the
N-terminal of the peptide.

Correspondingly, the amino acid with a free carboxyl group is called the C-
terminal of the peptide.

The N-terminal is conventionally written to the left while the C-terminal is


written to the right.

The number of amino acids in a peptide may vary from 2 to hundreds.


Peptides containing 3-10 residues are called oligopeptides.

When the number is very large then it is called a polypeptide.

A polypeptide with more than say about 50 amino acids is called a protein.

Structural Organization of Proteins:


The wide variety of functions performed by proteins is due to the possibility
of formation of a large number of proteins from a given number of amino
acids.

The large polymeric molecules of proteins acquire intricate three-


dimensional structures.

Primary structure:

The primary structure of a protein

is the sequence of amino acid residues in a completely assembled


polypeptide chain.

The chain begins with the first amino acid residue at the N-terminal end

and progresses in sequence to the last amino acid at the C-terminal end.

The primary structure of a protein

contains all the necessary information required for

manifestation of higher levels of a

dimensional structure.

The structural organization of proteins can be seen at four levels. These are,

primary (1°),

secondary (2),

tertiary (3°) and

quaternary (4°) structures.

Secondary structure:
The secondary structure of a protein is related twist to the way in which the
chain of amino acids fold back either twists, folds back upon itself to form a
helical, sheet like or a random arrangement.

Sheet The first two are respectively called the a-helix and the B-pleated
sheet structures.

The a-helix and the ß- pleated sheet structures are characteristic of fibrous
proteins like keratin, silk fibroin or collagen.

Tertiary Structure:

The tertiary structure of the protein refers to the overall three dimensional
structure of the protein.

The secondary structures of different regions of the polypeptide chain put


together give an overall shape to the polypeptide. This is called the native

structure of the protein.

In this tightly folded structure, the side chains of the amino acid residues
with polar groups are

exposed to the surface and non-polar groups are

buried inside.

The stability of the tertiary structure is maintained by hydrogen bonds,


attraction between positively and negatively charge side groups, van der
Waal forces, and polar and non-polar associations.
Quaternary Structure of Proteins:

Many proteins exist naturally as aggregates of two or more polypeptide


chains.

Each of these polypeptides is usually folded into an apparently independent


conformation.

These aggregated structures are called as quaternary structures of the


proteins.

Structure of haemoglobin depicting the quaternary structure of proteins is


given in Fig.

Functional Properties of Proteins:

The functional properties of the food constituents refer to their attributes


that make them useful for the food besides being nutritionally important.
These are the physico-chemical properties which influence the
characteristics of foods, e.g., texture, taste, appearance, etc.

Emulsification, viscosity, formation of foams and gels, binding to fats or


water molecules etc. are some foot

of the functional properties of proteins.

An understanding of these properties helps the food technologist to


improve the appearance, taste and

texture of the food by exploiting


These properties are related to the surface properties of the proteins or are
the result of the interaction of

proteins with its own molecules or water molecules.

Accordingly, the functional properties of proteins are classified into the


following three categories.

Hydration properties : related to protein-water interaction.

Structure formation properties : related to protein-protein interaction.

Surface properties related to protein-interface interaction.

Hydration Properties (protein-water interactions) :

The most of the foods are hydrated to some extent and the behaviour of the
proteins in it are influenced by the presence of water and water activity.

A number of the properties of proteins like swelling, solubility, precipitation,


viscosity, gel formation etc. are related to the interaction of protein
molecules with water molecules.

These are collectively referred

as the hydration properties.

The hydration takes place in a sequence of steps and is said to be


progressive in nature.

Different hydration properties like water absorption, swelling, wettability,


water retention, viscosity and solubility are dependent on the extent of
hydration.

Highly soluble proteins find applications where emulsification and whipping


etc. are important.
Soluble protein powders with high initial water absorption capacities give
relatively high viscosities

and find application in fluid foods like beverages, soups, sauces and creams.

The denatured protein molecules can aggregate to form an ordered network


called a gel. This is a result.

of a balance between protein-water and protein- protein interactions.

These gels can hold other food ingredients and find applications in
preparation of yogurt, tofu and bread dough etc.

The gelation of proteins may be exploited for water and fat absorption,
thickening, and for stabilizing of emulsions and foams.

Proteins provide the basis for the texture and structure of many food
products as a fibrous constituent per

say or in the soluble form which form a chewable fibrous product by a series
of texturization processes.

Structure Formation Properties (protein-protein interactions) :

The formation of a gel involves protein-protein interactions besides the role


of water. It involves interplay of attractive and repulsive interactions
between different polypeptide chains.

The gelation plays a role in water absorption, water control and thickening
etc.

Another crucial property of the proteins is dough formation.


The dough is nothing but a strongly cohesive and viscoelastic mass formed
from gluten, the proteins

present in wheat grain endosperm. This also has contributions from the
starch granules, some lipid and other soluble proteins.

The dough is stabilized by hydrogen bonding between different amino acid


side chains, hydrophobic interactions between apolar amino acids and
numerous disulphide (-S-S-) cross linkages. In other

words we can say that dough formation is a consequence of protein-protein


interactions.

Surface Properties (protein-interface

interactions) :

Proteins are surface active agents. You are aware that in the three
dimensional structure of the proteins

in aqueous solutions, the hydrophobic amino acids are buried inside in the
bulk, while the amino acids with hydrophilic side chains are on the surface.

The active surface of the proteins can interact with a wide variety of
molecules like water, lipids, volatile

flavours, carbohydrates and even other protein molecules.

Due to this, the proteins find extensive applications as emulsifiers in deserts,


whipped creams
and spreads etc.

The proteins also stabilize emulsions and contribute to the physical and
rheological properties like viscosity, thickness and elasticity etc.

Proteins are good at producing foams in cakes ice creams etc. where these
exist with varied textures.

The surface properties of the proteins may be exploited in binding the


desirable flavours on to it, though sometimes it may be disadvantageous as
these can also bind undesirable flavours causing to initiate de-odourisation.

In addition, the active surface of the proteins may provide site for the
binding of a number of other

substances like pigments, synthetic dyes and substances with mutagenic


activity. These binding interactions may lead to adverse nutritional or toxic
consequences.

Food Applications of Protein Concentrates, Isolates and Hydrolysates :

The protein concentrates and isolates are the products obtained by


selectively removing the non-protein

Non-Ingredients from a protein source so as to obtain a product that is rich


in its protein content.

The procedure is such that the nutritional and functional properties of the
proteins are retained. These find extensive applications in different
formulations so as to impart nutritional as well as

functional properties to them.

The protein hydrolysates, on the other hand are the products obtained on
treating the proteins with enzymes that hydrolyze them. These products
consist of mixtures of amino acids and small products.
These hydrolysates have superior nutritional qualities and higher
bioavailability.

The Soy Protein Concentrates (SPC) are prepared from high quality, sound,
clean, dehulled soybean

seeds by removing most of the oil and water soluble non-protein


constituents.

It contains not less than 70% protein on moisture free basis. The most
important application of SPC is in food industry primarily in comminuted
meat, poultry and fish products like patties, sausages and fish sticks etc.

The SPC increase the water and fat retention in these products. Besides
these, the SPC are also used as stabilized dispersions in milk, beverages and
simulated dairy products like sour cream analogues.

The Soy protein isolates (ISP) are the major proteinaceous fraction obtained
from dehulled soybeans and contain at least 90% protein on

moisture free basis.

The major food applications of ISP's are in meat products as a meat replacer,
in sea foods like fish,

sausages and in cereal, bakery and dairy products.

The Whey Protein Concentrate (WPC) is a highly nutritious product obtained


by selectively removing

water, minerals and lactose from whey.


These are removed by physical separation techniques like precipitation,
filtration or dialysis.

The WPCs find extensive applications in baked goods

and contributes towards the product browning, crust and flavour


development.

The concentrates with high viscosity are used in ice creams, processed
cheese and fresh dairy applications.

The protein hydrolysates are obtained by hydrolysis of food proteins by


using proteases like chymotrypsin, papain, thermolysin and trypsin.

The hydolysis process alters the composition and functional properties of


the proteins like gelation, foaming and emulsification.

The hydrolysates are used in soups

and sauces and are important for the people who cannot digest solid foods.

After having an understanding of the structure and properties of proteins it


will be easy for you to understand the behaviour of enzymes and their role
in food industry.

Enzymes :

Enzymes are the proteins that catalyze biochemical reactions.

Study of the important biochemical reactions was started many years ago,
from the time of Louis

Pasteur, who for the first time demonstrated the fermentation of glucose by
yeast.
The catalytic agent of yeast cell was subsequently identified and named as
ferment.

An enzyme can be a large protein made up of several hundred amino acids,


or several polypeptides that

act together as a unit.

Enzymes have molecular weights ranging from 10,000 to 2,000,000.

Enzymes may sometimes have a non-protein component attached to the


protein part. This may be an organic compound or a metal ion. While the
former is called as coenzyme, the later is best known

as cofactor.

The protein part and non-protein part together form the holoenzyme,

Sometimes, the non-protein part remains so tightly bound to the protein


part that it cannot be

dissociated. Such non-protein part is called as a prosthetic group.

When the non-protein component dissociates from the protein part, the
enzyme loses its catalytic function

and is called an apoenzyme.

Nomenclature and Classification of Enzymes :

Conventionally, the trivial or common names of the enzymes were derived


either from the names of the substrate they acted on, or on the reaction
they catalyzed or both.
These ended in a suffix -ase' for example, urease is an enzyme acting on
urea. However as the number of enzymes known went up, a need to have a
formal scheme of nomenclature was felt and accordingly, there is an
enzyme nomenclature system in place.

According to this system, the enzymes are groupedbinto six classes; each
class is subdivided into several subclasses, which are further subdivided.
Every enzyme is characterized by a code number.

The code numbers of the enzymes are prefixed by EC (Enzyme Commission)


and contain four numbers a separated by points, with the following
meaning:

the first number shows to which of the six main classes an enzyme belongs

the second figure indicates the subclass

the third figure gives the sub-subclass, and

the fourth figure is the serial number of the enzyme in its subclass.

For example, the EC number of the enzyme catalase

is EC 1.11.1.6

The major classes and the type of reaction catalyzed by them are given
below:

Oxidoreductases:

The enzymes of this class ( EC 1) catalyze oxidation-reduction reactions.

Common names include dehydrogenases, oxidases,

reductases and catalases.

Transferases:
These are the enzymes (EC 2) which catalyze the transfer of a group, e.g., a
methyl or glycosyl group, from one compound to another.

In many cases, the donor is a cofactor (coenzyme) carrying the group to be


transferred.

Common enzymes of this group include acetyltransferase, methylase,


protein kinase and polymerase.

Hydrolyases:

These enzymes (EC 3) catalyze the

hydrolytic cleavage of C-O, C-N, C-C and some other bonds, including
phosphoric anhydride bonds.

Their trivial names are formed by adding the suffix 'ase' to the substrate
which they hydrolyze.

Examples

include protease, nuclease, phosphatase.

Lyases:

These enzymes (EC 4) cleave C-C, C-O, and other bonds by elimination,
forming double bonds or conversely adding groups to double bonds.

Common examples include decarboxylase, aldolase,

dehydratase (if water is eliminated) or hydro-lyase


(if the reverse reaction is more important or the only;one which can be
demonstrated)

Isomerases: These enzymes (EC 5) catalyze geometric or structural changes


within a molecule.

According to the type of isomerism, they may be called racemases,


epimerases, cis-trans isomerases,

tautomerases, mutases or csycloisomerases.

Ligases: These are also called synthetases (EC 6) and catalyze the linkage of
two molecules coupled

with the hydrolytic breakdown of a pyrophosphate bond in ATP or an


analogous compound. The bonds

formed are often high energy bonds.

Monomeric and Oligomeric Enzymes :

On the basis of polypeptide units constituting the enzyme, these are


categorized into monomeric and

oligomeric enzymes.

As is evident from the name

itself, the monomeric enzymes contain a single polypeptide unit, while the
oligomeric enzymes

contain two or more such units.

The monomeric enzymes are primarily proteases i.e., they catalyze the
hydrolysis of peptide bonds of other protein molecules.

The examples being serine protease, thiol protease etc.


The oligomeric enzymes on the other hand, include a vast majority of
enzymes.

The examples being, lactose synthase, lactate dehydrogenase and pyruvate


dehydrogenase etc.

Enzyme Utilization in Food Industry:

The biocatalytic activity of the enzymes is of immense

importance in food technology.

Many reactions catalyzed by enzymes contribute towards the desired


attributes of the processed food.

At the same time, a number of enzymatic reactions produce undesirable


results.

Further, the enzymes may be used in industry as components of living cells


or after isolation in free or immobilized forms.

Let us take up some of the applications of enzymes in the food industry.

Bread making:

In baking bread, the preliminary process involves the mixing of wheat flour
(mainly starch and proteins) with yeast and water.

Starch gives glucose, maltose and some oligosaccharides.

Glucose and maltose are then metabolised by the enzymes in yeast, and
carbon dioxide is

formed.
This CO₂, then disintends the protein framework of the dough, ready for
baking.

Vegetable preservation:

The fresh vegetables contain a number of enzymes.

In the process of preservation of these vegetables, the enzymes must be


inactivated; else the vegetables would soon get deteriorated.

This inactivation is achieved by a process called blanching, blanching helps in


inactivating the enzymes in vegetables.

Therefore it is essential blanc the vegetables before their preservation.

Brewing industry:

Brewing refers to the manufacture of beer and other malt beverages like ale
and stout.

The process involves germination of barley under moist conditions which is


then dried and the malt so obtained is the main starting material.

The reserve starch is broken down by the amylase present to give, among
other products, glucose, maltose and soluble starch.

The grains are then roasted and the soluble component called wort is
extracted with water.

This wort is then fermented in presence of yeast to obtain alcohol.


The alcohol thus accrued is separated by distillation for making different
types of alcoholic drinks.

Cheese production:

Involves the conversion of the milk protein, k-casein to paracasein by a


defined, limited hydrolysis, catalyzed by chymosin (rennin).

Rennin the gastric enzyme of the calf is used in the form of a crude extract,
powder or paste.

In the presence of Ca²+, paracasein clots and may be separated from the
whey after which the clot is allowed to mature under controlled

conditions to form cheese.

Tenderizing of meat:

When meat is cooked fresh it is quite tender. However, with the passage of
time the muscle becomes inextensible and is tough when cooked.

The meat can be tenderized with the help of Pouteaser proteolytic enzymes
e.g. proteases. For this

purpose, the meat is kept at low temperature (\~4°C) for many weeks
whereby the enzymes

present in the meat tenderize it.

This process can be hastened by dusting proteolytic enzymes over the meat
before frying or boiling it.

Immobilized Enzymes :

The enzymes used to catalyze a given reaction in food processing normally


get inactivated in the

process and cannot be reused.


It was attempted to separate them from the product and put to use again.

It could be achieved by attaching the enzyme to a water-insoluble solid


support, called the matrix. This

is called enzyme immobilzation.

A wrong notion associated with this type of browning is that the change is
due to the presence of iron in that particular fruit or vegetable. This is
actually incorrect and has different reasons. In recent past the immobilized
enzymes have become an indispensable tool in food processing.

The immobilization of the enzyme can be achieved by chemical or physical


methods. In chemical

methods, the enzymes are bound to a solid support through covalent


bonding.

In case of physical methods, the enzymes are either adsorbed on the solid
support, entrapped in gels or

are encapsulated behind semi-permeable membranes.

The enzymes cannot be recovered from the immobilized enzymes, prepared


by chemical means whereas the physical immobilization of the enzymes is
reversible.

There are several of advantages of immobilized enzymes.

Some of these are given below:

Easy recovery of enzyme after the process:


The immobilized enzymes are added to the reaction mixture and removed
by filtration after the reaction is over. This leads to cost efficiency.

The greater efficiency and control of their catalytic activity,

Reusability of the enzyme,

Improved thermal stability of the enzyme allowing higher processing


temperatures.

Treatment of corn syrup with glucose isomerase gives high fructose syrup
that is 50 per cent more sweet. This is a result of conversion of glucose to
fructose

by the enzyme.

The high fructose syrup finds application in the manufacture of aerated


drinks.

Nowadays the immobilized glucose isomerase is used on a commercial scale


for the conversion of glucose

to fructose.

Enzymatic Browning :

A wrong notion associated with this type of browning is that it is due to the
presence of iron in that particular fruit of vegetable. This is actually
incorrect. It has different reasons.

The browning of some cut fruits and vegetables is called enzymatic


browning and is due to the activity

of a group of enzymes called phenolases.


The enzymatic browning is a result of two reactions. One being the
conversion o-dihydroxyphenols to o.

hydropheta quinones and the other is hydroxylation of some


monohydroxyphenols to dihydroxyphenols.

The browning of certain fruits on cutting is due to the polymerization of


Roth quinines which are formed

in the enzymatic reaction.

All the fruits do not brown on cutting. This may be due to the absence of the
browning enzymes or that of the suitable substrates.

Applying lemon juice on cut banana or dipping the cut fruits in ascorbic acid
or in dilute salt solution are some such interventions. These help by blocking
the contact with air or by reducing the enzymatic activity.

Classification of Lipids :

Lipids consist of a group of molecules having diverse structures.

Visible tat - Vejesti oil, butted

Food lipids are consumed in the form of visible and invisible fats.

Visible fats are called so because these are the fats that can be seen by us
after these are separated from

the original plant or animal source, e.g. vegetable, oils, butter, etc.

Invisible fats are constituents of basic foods as present in milk, cheese, meat
etc. and are consumed without being separated.

On the basis of their structure, lipids are generally classified into three main
classes.

simple lipids
complex lipids

derived lipids

Simple Lipids :

Chemically, simple lipids are esters of fatty acids with alcohols.

Oils and fats are common examples of this class of lipids which are the
esters of long chain fatty acids

with glycerol. These esters called triglycerides or triacylglycerols, compose


one of the major food

groups of our diet.

The triglycerides that are solids or semisolids at room temperature are


classified as fats and occur predominantly in animals.

These are generally the triglycerides containing saturated fatty acids.

On the other hand the triglycerides that are liquids are called oils.

These originate primarily in plants;

however triglycerides from fish are also largely oils. These are the esters of
unsaturated fatty acids with glycerol.

Waxes are also simple lipids and are esters of fatty acids with long chain
monohydric alcohols. These are widely distributed in nature.

For example, the leaves and fruits of many plants have waxy coatings, which
protect them from dehydration and small predators.
The feathers of birds and the fur of some animals have similar coatings
which serve as a water repellent.

Waxes are usually inert due to the saturated nature of the hydrocarbon
chain.

Carnauba wax obtained from carnauba palm of Brazil is an example of a


tough and water resistant wax.

It contains esterified fatty dialcohols (diols, about 20%), hydroxylated fatty


acids (about 6%) and

cinnamic acid (about 10%).

Rice bran obtained from milling of rice contains a wax mixed with
triglycerides.

Complex Lipids :

Complex lipids are also esters of fatty acids with alcohol.

However, in addition to these two

components, they contain other groups, such as a phosphate group or a


carbohydrate moiety.

Depending upon the moiety attached, this group comprises of the following
types of lipids.

Phospholipids:

These complex lipids contain a phosphate group, in addition to fatty acids


and an alcohol.
They frequently have nitrogen containing bases are and other substituents
as well.

Phospholipids that contain glycerol as the alcohol are known as


glycerophospholipids and those

having sphingosine as the alcohol moiety are called the


sphingophospholipids.

Phosphatidylethanolamine (PE), phosphatidylinositol (PI),

phosphatidylserine (PS), and phosphatidylcholine

(PC) are important phospholipids found in dairy

products.

Whereas sphingomyelin (SM), glucosylceramide (GLUCER), and


lactosylceramide (LACCER) are

important dairy sphingolipids.

The biological membrane of native milk fat globules consists of about one-
third phospho and sphingolipids, stabilizing the milk fat globules in

the serum phase of the milk.

In recent years, phosphor and sphingolipids have received renewed interest


because of the positive

biological effects.

They are found to have an ability to reduce blood cholesterol and to


enhance brain functioning.

Besides, these also have good anti-oxidative and bacteriostatic properties.

Glycolipids:
These lipids contain a carbohydrate group, in addition to fatty acids and an
alcohol.

The sugar group in glycolipids is usually galactose though sometimes these


may contain glucose.

The alcohol part is either Sphingosine or glycerol.

Sphingolipids are derivatives of sphingosine, which has a long hydrocarbon


tail, and a polar

domain that includes an amino group.

The amino group of sphingosine can form an amide bond with a fatty acid
carboxyl, to yield a ceramide. A ceramide with a monosaccharide

like glucose or galactose as polar head group is called cerebroside.

The cerebrosides are common constituents, of membranes of animals and


plants.

For example, galactosylceramide the principal is glycosphingolipid in brain


tissue and myelin.

Some glycolipids are involved in the antigenicity of blood group


determinants, while others bind

to specific toxins or bacteria.

Other complex lipids: The category comprises of lipids such as, sulpholipids,
aminolipids and

lipoproteins, containing sulphur, amino and protein molecules respectively


attached to these.
Derived Lipids :

It is another major class of lipids. These are obtained from the complex lipids
by hydrolysis and include fatty acids (saturated as well as unsaturated),
glycerol, steroids, lipid soluble vitamins i.e. A, D, E

and K and prostaglandins.

Another way of looking at derived lipids is that these are all those lipids
which do not belong to the simple

and complex lipid categories.

Structure of Lipids:

Fatty Acids:

Fatty acids are long chain hydrocarbons containing a terminal carboxyl


group.

These normally occur as their esters in natural fats and oils.

However, they do occur in the unesterifed form as fatty acids bound to


certain proteins.

Most of the fatty acids, especially those which occur in natural fats, contain
an even number of carbon

atoms; usually more than 14 carbon atoms.

While most of the fatty acids have either 16, 18 or 20 carbon atoms, fatty
acids with lesser number of

carbon atoms (4-8) are present in milk fat, whereas those of intermediate
chain length (10-14), and between 16-20 carbon atoms are found in most of
the animal and vegetable fats.
The hydrocarbon chain of the fatty acids is either saturated, i.e., without any
double bond or unsaturated, i.e., with one or more double bonds.

Respectively these are called saturated or unsaturated fatty acids.

A fatty acid with a single double bond is called monounsaturated fatty acid
(MUFA); when it contains two or more double bonds then it is called as a
polyunsaturated fatty acid (PUFA).

MUFA is obtained primarily from plant sources, such as Safflower or kardi oil
(13% MUFA), canola (62%

MUFA), peanut (49% MUFA) and olive (77%).

Olive oil has the highest content of MUFA among most vegetable oils. MUFA
is also found in olive oil

margarine, canola margarine, and peanut butter.

The natural sources of PUFA are nuts and seeds Cold water fishes like
salmon also contain a good amount of PUFA.

Unsaturated fatty acids exhibit geometric isomerism. Geometric isomerism


isomeric is depicted due to the presence of one or more double bonds.

The orientation of two hydrogen atoms attached to the carbon atoms joined
by double bond may differ.

If both the hydrogèns are on the same side it is called a cis isomer

When they are on either side of double bond, a trans isomer is formed.
Nearly all naturally occurring unsaturated fatty acids have a cis
configuration.

Essential Fatty Acids

Some of the PUFAs, such as linolenic, linoleic and arachidonic acids are not
synthesized by higher

animals and man.

These have to be supplied through

dietary sources, as they are essential for normal health and well being of the
organism. Such fatty acids are known as essential fatty acids (EFA).

Two fatty acids are essential to human health.

The first is a omega-6 fatty acid called linoleic acid (LA);

found abundantly in safflower, sunflower, corn and evening primrose oils.

The second, a o-3 fatty acid called alpha-linolenic acid (LNA) or ALNA, is
found abundantly in olive,

flax seeds, hemp seeds, walnuts, soybeans, andbfreshly ground wheat germ.

Acylglycerols :

Acylglycerols are the most abundant group of naturally occurring lipids.


These are the esters of fatty

acids with a trihydroxy alcohol i.e. glycerol.

The reaction between a fatty acid and glycerol during esterification can be
shown as below.
One, two or all the hydroxyl groups of glycerol can undergo esterification to
yield mono -, di -, and

triacylglycerols, respectively.

Triacylglycerols, the so called neutral fats as they do not carry a charge, are
also known as triglycerides.

The general structures of the three acylglycerols, wherein R, R and R


represent the fatty acid residues

is illustrated in Fig.

While most of the naturally occurring acylglycerols are triacylglycerols, the


mono-and diacylglycerols are formed as intermediates in the metabolism of
lipids.

Triacylglycerols from animal sources normally contain a higher percentage


of saturated fatty acids and are

solids at room temperature.

These are generally solids while those from vegetable sources are rich in
unsaturated fatty acids, and

remain generally in liquid form at room temperature.

Trans Fatty Acids:

The unsaturated fatty acids (MUFA and PUFA) found in vegetable oils are
generally liquids at room temperature.

The liquid vegetable oils can be converted into a solid & or semi-solid by
hydrogenation.
In the process of partial hydrogenation, the chemical structure of the natural
fatty acid is changed from their original cis- configuration to unnatural trans-

configuration and we get what are called trans-fatty acids.

These don't get spoilt easily and can also withstand repeated heating.

This is attractive characteristics for food makers especially for those

commercially engaged in baked goods and snack foods.

However, a strong relationship is found between the consumption of trans


fatty acids and heart disease.

While trans fatty acids may be classified as hydrogenated polyunsaturated


fats due to their

chemical structure, they generally are like saturated fats in terms of their
health effects.

Most, margarines, vegetable shortening, partially hydrogenated vegetable


oil, deep-fried chips, many

fast foods, commercially available baked goods are the sources trans fatty
acid foods.

Applications of Lipids in Foods and Nutrition:

Lipids play important role in food. They influence the texture, flavour and
aroma of foods.

The short chain fatty acids obtained as breakdown products of lipids are
responsible for the flavour in butter, milk and cheese.

Due to immiscibility of fats in water, the former separate out from an


aqueous medium on standing
i.e. form two layers. Therefore, to retain the fat in aqueous medium these
need to be emulsified.

vv

Fats and oils are extensively used in cookery as a cooking medium,


shortening and as seasoning.

Since fat and oils have a high boiling point as compared to water, the foods
get cooked faster in fat than in water.

In many preparations such as cakes, biscuits, chakali and chirote, fats or oils
are added to improve the

texture.

The fat covers the surface of the flour particles and prevents the sticking of
particles together.

Carnauba wax is used as glazes for candies, gums, fruit coatings etc.

The wax from rice bran is used as a constituent of chocolate enrobes various
fruits and vegetable coatings.

From nutrition point of view the fats and other lipids in the diet are
important for their energy value.

Fats have calorie content of approximately 9 kcal per gram which is high as
compared to other foods.

A high fat intake is said to be responsible for a rise in blood cholesterol level
as is indicated by a number of studies.
It is, therefore, advised to substitute oils with unsaturated fatty acids for the
ones with hydrogenated fats or the fats with saturated fatty acids.

Lipids are considered to have a role in the satiety value of food i.e. the
feeling of satisfaction on consumption of food.

The essential fatty acids are added to the diet through intake of foods
containing fats and oils.

Fats act as solvents for fat soluble vitamins which are vitamin A, D, E and K.
The vitamins as you know and will read later are very important for health.

Some dietary fats have some harmful effects also. For example, some cyclic
fatty acids inhibit the

desaturation of stearic acid to oleic acid.

This alters membrane permeability and leads to some diseases.

Some of the peroxidized products of polyunsaturated fatty acids could also


be toxic.

Adulteration of Fats and Oils :

Storage and processing causes deterioration of fats and oils. These


deteriorative changes are generally

not intentional, however the quality of oil gets affected due to this.

Maintenance of quality of any food product is of utmost importance keeping


in mind the health effects

Efforts are being made at the national level to maintain standards and
quality of foods.
When talking of quality we know that there are malpractices which are
followed in tampering with the original food to make monetary gains.

Oil is no exception to this malpractice of adulteration.

Cheap oils and inedible oils are mixed in edible oils for this purpose.

You might be familiar with thebbig adulteration of mustard oil with


argemone of obtained from argemone seeds grown widely in our

country.

Argemone oil is not only mixed in mustard oil but also in coconut, sesame
and ground nut oils. This

oil is highly poisonous and causes a disease named dropsy in human beings.

Another chemical orthotricresyl phosphate is also used for adulteration of


oils as it is insoluble in water but soluble in oils

This adulterant is a cause of permanent damage to nervous system.

Some other common adulterants include petroleum products, animal fats in


vanaspati and vanaspati in

ghee.

The Indian Prevention of Food Adulteration Act takes care of the


adulterations and their preventions in all food products.

Vitamins

Vitamins are organic, non-caloric micronutrients that are essential for


normal physiologic function.

Vitamins must be consumed through food with only three exceptions:


vitamin K and biotin can also be
produced by normal intestinal flora (bacteria that live in the intestines and
are critical for normal gastrointestinal function), and vitamin D can be self
produced with sun exposure.

No "perfect food contains all the vitamins in just the right amount; rather, a
variety of nutrient-dense

foods must be consumed to assure adequate vitamin

intakes.

Many foods (such as breads and cereals) have been fortified with some
nutrients to decrease the risk of vitamin deficiency. And some foods contain
inactive vitamins called provitamins. Fortunately, the human body contains
enzymes to convert these inactive Vitamins into

active vitamins.

Humans need 13 different vitamins, which are divided into two categories:
water-soluble vitamins and fat-soluble vitamins.

Thiamin, riboflavin, niacin, pantothenic acid, folate, vitamin B6, vitamin B12
biotin, and vitamin C are

the water-soluble vitamins. Their solubility in water which gives them similar
absorption and distribution

in the body) and their role as cofactors of enzymes involved in metabolism


(i.e., without them the

enzyme will not work) are common traits.


With the exception of vitamins B6 and B₁₂ water-soluble vitamins cannot be
stored in the body and

are readily excreted in urine. This decreases the risk of toxicity from
overconsumption and also makes

their regular intake a necessity.

Folate (vitamin B9; also known as "folic acid" in its supplement form)-named
for its abundance in plant foliage (like green leafy vegetables)-deserves
special

mention due to its crucial role during pregnancy.

Folate is essential for production of deoxyribonucleic acid (DNA), red and


white blood cell formation, neurotransmitter formation and amino-acid
metabolism.

Deficiency is relatively common, as folate is easily lost during food


preparation and cooking and because most people do not eat enough green
leafy vegetables.

Folate deficiency early in pregnancy can be devastating for a developing


fetus, leading to neural da tube defects such as spina bifida.

Deficiency also causes a megaloblastic anemia, skin lesions, and poor


growth. Notably, excessive

consumption of folate can mask a vitamin B12 deficiency.

Vitamins A, D, E and K are the fat-soluble vitamins.


Often found in fatcontaining foods and stored in the liver or adipose tissue
until needed, fat-soluble

vitamins closely associate with fat.

If fat absorption is impaired, so is fat-soluble vitamin absorption.

Unlike water-soluble vitamins, fat-soluble vitamins can be stored in the body


for extended periods of time and eventually are excreted in feces. This
storage capacity increases the risk of toxicity from

overconsumption, but also decreases the risk of

deficiency.

Choline, called a "quasi-vitamin" because it can be produced in the body but


also provides additional

benefits through consumption from food, is also important since it plays a


crucial role in neurotransmitter and platelet function and may help

to prevent Alzheimer's disease.

Minerals :

Serving roles as varied as regulating enzyme activity and maintaining acid-


base balance to assisting with

strength and growth, minerals are critical for human life.

Unlike vitamins, many minerals are found in the body as well as in food.

The body's ability to use the minerals is dependent on their bioavailability.

Nearly all minerals, with the exception of iron, are absorbed in their free
form-that is, in their ionic

state unbound to organic molecules and complexes.


When bound to a complex, the mineral is considered to not be bioavailable
and it will be excreted in feces.

Typically, minerals with high bioavailability include sodium, potassium,


chloride, iodide, and fluoride.

Minerals with low bioavailability include iron, chromium, and manganese.

All other minerals, including calcium and magnesium, are of medium


bioavailability.

An important consideration when consuming minerals, and particularly


when people take mineral supplements, is the possibility of mineral-to-
mineral interactions.

Minerals can interfere with the absorption of other minerals. For example,
zinc absorption may be

decreased through iron supplementation.

Zinc excesses can decrease copper absorption. Too much calcium limits the
absorption of manganese,

zinc, and iron.

When a mineral is not absorbed properly, deficiency may develop.

Serving a variety of functions in the body, minerals are typically categorized


as macrominerals (bulk

elements) and microminerals (trace elements)

Macrominerals include calcium, phosphorus, magnesium, sulfur, sodium,


chloride and potassium.
Microminerals include iron, iodine, selenium, zinc, and various other
minerals that do not have an

established DRI and will not be discussed here.

Food Additives

Food additives are the substances which are added to natural foods at
various stages of food production,

processing, storage, packing and preservation.

According to the Food and Agriculture Organisation (FAO) and World Health
Organisation (WHO),

The food additives are the non-nutritive substances added to foods, in small
qualities, to improve its flavour, texture, appearance and storage properties.

According to another widely accepted definition, Food additive is a


substance or a mixture of substances, other than the natural foods which is
present in food

as a result of any aspect of production processing,

storage or packing."

As you know, the preservation of food has an age old tradition and a
number of substances e.g., smoke,

alcohol, spices, sugar vinegar and salt etc. have been used for this purpose.
These are not included in the list of food additives.

Further, according to FAO and WHO, the nutritive substances like vitamins
and minerals which are added in order to supplement and enrich the food
are also excluded from the list of food additives.
These organizations have formulated international standards for defining
the quality of food additives. their permissible levels in foods and all other
technological related issues.

The above definitions do not include the substances which get added to the
food in the course of their

packing. These are called unintentional or incidental additives.

These are also called chance contaminants, for example, pesticides are one
such type of compounds which get added to foods unintentionally and

be hazardous to health. Many a times, insect parts, and antibiotics added to


animal feeds also show

up in the food.

The additives which are added in the food deliberately to have a desired
property and for a specific function

are termed as intentional additives. Since some additives may have


undesirable effects on the human

health, their usage has to be controlled and one must adhere to the
prescribed norms and standards while using them.

Many food additives are classified as GRAS meaning Generally Regarded As


Safe' additives. The GRAS

additives are supposed to be causing no harm for longer periods.

In India the Prevention of Food

Adulteration Act and Rules, 1954 are responsible for listing the additives
permitted in different foods and
their maximum permissible limits.

The various important applications of food additives in general are:

to maintain nutritional quality of food

to improve the nutritional quality of food by enriching and fortifying it with


vitamins and minerals. You have read about this in Unit 9

to protect against microbial growth in the food e.g. use of antioxidants,


antimicrobial agents etc.

to impart firmness to the food

to retard or speed up chemical reactions in food

to enhance stability of food resulting an increase in the shelf life of foods


and the reduction wastage of food. The waste is generated both by
microbial and chemical causes and can reduced by use of antimicrobial
agents and antioxidants.

to provide aids in processing, packing and transport of food. These include


acids, alkalis, buffers, sequestrants and other types of

chemicals.

to make food more attractive in the form of colouring agents, flavouring


agents, emulsifiers, stabilizers, thickeners, clarifiers and bleaching

agents

Today, a very large number of additives are being used in food industry.
On the basis of their functional properties, these can be classified into the
following types.

Preservatives

Antioxidants

Acidulants, neutralizers and buffers

Colouring agents

Flavouring agents

Sweeteners

Miscellaneous additives.

In the following sections, you will read about these different types and
categories of the food additives

and their uses.

Preservatives :

You are well aware that foods are subject to spoilage due to contamination
by microbes.

As the contamination depends upon the temperature besides moisture as


one of the factors, we have been

using a conventional method of keeping the food material in the refrigerator


to slow down this process.

However, this method will not work when storage for a longer time is
required.
We may need to use some chemical preservatives for this purpose. Though
a large number of preservatives are available, for economical and
convenience

reasons, salt, nitrites and sulphites have been in use for many years.

The antimicrobial activity of sodium chloride is essentially related to its


ability to reduce water activity

(aw) and create unfavourable conditions for microbial growth. Further,


though newer packaging techniques, processing and storage methods are
available

that can preserve foods without chemical preservatives, chemicals play a


significant role in protecting the food supply, again for convenience and
economy.

On the basis of their mode of action, the preservatives can be grouped into
three types. These are antimicrobials that inhibit growth of bacteria, yeasts,
or molds for example sorbates that inhibit

most of the species of yeasts, moulds and of some

bacteria; antioxidants that slow down the air oxidation of fats and lipids that
cause rancidity.

For example preservatives like tert-butylhydroquinone . (TBHQ), stop the


chemical breakdown of food that

happens in the presence of oxygen; and the third group which blocks the
natural ripening and enzymatic Re
processes in foodstuffs.

For example, the browning the exposed surface of cut apple due to the
enzyme phenolase can be checked by acids like citric acid and ascorbic acid
(vitamin C) that inhibit the enzyme by making the pH uncomfortably low for
it.

Enzyme Pherolase Sulphur dioxide serves all the three functions, which Asa
makes it along with the related sulphites as an important constituent of a
number of household products.

Class I and Class II Preservatives:

Under the prevention of food adulteration Act (PFA) rules, 1954,


preservatives are classified into Class I and Class II preservatives.

Class I preservatives, also called natural preservatives include common salt,


sugar, dextrose (glucose), spices, vinegar or acetic acid, honey, and
vegetable

oils. There is no restriction to the addition of Class I preservatives to any


food.

Brewed and synthetic vinegar (dilute acetic acid) are widely used as
antimicrobials in vinegar pickles.

Acetic acid is more effective against yeasts and bacteria than moulds.

Only acetic, lactic and butyric bacteria are markedly tolerant to acetic acid.
Like most of the preservatives, acetic acid is also more effective at lower pH.
Sugar and spice also help in preserving foods. Like salt, sugar also acts by
reducing the water activity of the medium to inhibit the growth of
microorganisms.

Many chemical substances in spices like terpenes have been shown to have
antimicrobial properties.

Class II preservatives are those which can be added in foods as specified by


regulations and not otherwise.

These can be added in foods as specified by regulations include, benzoic


acid, sulphurous acid and

their salts, nitrates, nitrites, sorbic acid and its sodium, potassium and
calcium salts, lactic acid, propionic acid, sodium or calcium propionate,
methyl or propyl-parahydroxy benzoic acid, sodium diacetate and sodium,
potassium and calcium lactate.

& Of these, benzoates and sulphites are most widely used for preservation
of fruit and vegetable products; however, recently sorbates have been
allowed for some products.

Benzoic acid is found naturally in cranberries, plums, prunes, cinnamon,


cloves and most berries. It is a strong antimycotic agent. Most yeasts and
moulds can be controlled using 0.05-0.1% benzoic acid.

Control of many bacteria requires much higher concentration. Due to low


solubility of benzoic acid

in water, sodium benzoate salt is preferred.

Antimycotic: An agent inhibiting the growth of fungi

Benzoic acid is permitted in several products like squashes, syrups, crushes,


fruit juices, jams, jellies,
marmalade, beverages, pickles and tomato products.

Sulphur dioxide and its various salts have a long history of use dating back to
the times of the ancient

Greeks. They have been used extensively as & antimicrobials and to prevent
enzymatic and non- enzymatic browning in a variety of food products.

Sulphurous acid inhibits yeasts, moulds and bacteria. Sulphur dioxide and
sulphites are permitted under

PFA for a number of products like fruit pulps, squashes, syrups, crushes,
cordials, wines, beverages,

and dehydrated fruits and vegetables. Sulphur dioxide.

is also used as an anti-browning agent.

Sorbic acid and its sodium, potassium and calcium salts are collectively
known as sorbates.

Sorbic acid is present in some berries like berries of the mountain ash berry
(rowanberry). These sorbates inhibit most of the species of yeasts and
moulds.

Several species of bacteria are also, inhibited by sorbates.

At present under PFA, sorbates are permitted for only a few fruit and
vegetable products. They include jams, jellies, marmalades, glazed or
candied fruits, fruit bars, fruit juice concentrates and prunes.
Some of the other products, include cheese, flour confectionary, smoked
fish, preserved chapattis and

fat spreads. Sorbic acid and potassium sorbate have

GRAS status.

Nitrites have been used in meat curing for many centuries. For meat curing,
nitrite is used along with

a mixture of salt, sugar, spices, and ascorbate.

Nitrite contributes to the development of the characteristic colour, flavour,


and texture

improvement and preservative effects.

Nitrite has a strong inhibitory action against Clostridium botulinum and


several other micro-organisms.

Antimicrobial substances (antibiotics) produced by microorganisms have


been known for many years. These are the products of the defence system
of the microbes themselves generated when they compete with each other
for space and nutrients.

Some of these, like nisin, and natamycin, the cheese preservatives called
bacteriocins have been allowed in some foods only in recent years.

Some other potential natural preservative sources include honey, milk, and
even dried plums.

Antioxidants :P.A. tut doil undago.

F·A·

oxidation → Rancidita

The unsaturated fatty acids in fats and oils can


undergo oxidation during storage leading to the

development of rancidity i.e., the characteristic

off-flavours indicating the spoilage of oils and fats.

The oxidative processes may also cause vitamin

destruction, discolouration and even some toxic

effects.

Vitamine destruction

Food antioxidants are substances that are able to inhibit or interfere with
the autooxidation reaction.

In other words, they get oxidized in preference to the fats and oils and thus
prevent the oxidation of the

latter.

It was explained in the previous Unit that tocopherols present in many


vegetable oils have antioxidant property.

Similarly, ascorbic acid and lecithin have antioxidant properties. However,


the major antioxidants

commercially used in foods, fats and oils are phenolic compounds and are
generally referred to as phenolic

antioxidants.

The most widely used phenolic antioxidants for fats and oils are
i) butylated hydroxy anisole (BHA),

ii) butylated hydroxy toluene (BHT), iii) propylgallate

and

iv) tert-butyl hydroquinone (TBHQ).

Certain metals like iron and copper present in foods are strong catalysts of
fat oxidation and may react with antioxidants to cause discolouration.

Food acids like citric acid have the ability to bind these metals. Therefore,
the antioxidants are usually added along with citric acid.

The antioxidants are perhaps the most widely used among the food
additives.

They are used in vegetable oils, meat products, confections and chewing
gums, cereal products like breakfast cereals, bakery products etc.

Use of the antioxidants in fruit and vegetable products though limited, is of


considerable commercial

importance.

Some of them include fruit nuts like walnut, almonds, cashew nuts; citrus
oils, dehydrated potato products

like powder, flakes and granules.

Under PFA, all the above mentioned phenolic antioxidants except BHT have
been permitted with restrictions.

Additionally, lecithin and ascorbyl palmitate are also permitted for specific
food products.
Acidulants :

As the name indicates acidulants are food additives that may lower the pH
of any food.

Since the microbial spoilage of food is inhibited at low pH, acidulants find an
application as an antimicrobial agent.

Acidulants contribute a variety of functional properties that lead to the


enhancement of food quality by imparting desired flavours and taste to it.

Most of the acidulants used in food are organic acids and their salts. For
example, the commonly used at

acidulants in foods are acetic, ascorbic, citric, lactic, malic and tartaric acids
and their salts.

Inorganic acids like phosphoric acid is also used extensively in cola type
beverages,

In general acidulants are used as flavouring agents, buffering agents,


preservatives, sequestrants, viscosity modifiers and meat curing

Citric acid, a tricarboxylic acid abundantly present in citrus and many other
fruits is perhaps the most widely used organic acid.

Though earlier it used to be produced from citrus fruits, presently


fermentation is employed for most

of the commercial citric acid production. It is used in carbonated soft drinks.

Malic acid (2-hydroxybutanoic acid), a dicarboxylic acid is the major acid in


apples and mango. It is a nonhygroscopic white crystalline powder, easily
soluble in water and finds application in dry food formulations.
Synthetic malic acid is available

commercially.

Tartaric acid a dicarboxylic acid found predominantly in grapes and


tamarind. It is a white crystalline water soluble solid, usually extracted from
the argol sediment formed during fermentation of grapes. It

finds application in baking powder and effervescent 'health salts'.

Most of the food acidulants are permitted under PFA with certain
restrictions.

anthocyanins exhibit most intense colour below a pH of 3.5 and thus are
suited for acidic foods only.

Further, these easily undergo discolouration in the presence of amino acids,


phenolic sugar derivatives etc. and are bleached by ascorbic acid and
sulphites.

Carotenoids: Carotenoids are responsible for the yellow, orange and red
pigments in a number of plants and animal foods.

Carotenes - These are hydrocarbons containing beta-ionone rings and


possess vitamin-A activity

for example, B-Carotene present in carrots, chillies, soybean

ii) Lycopenes - the carotenoids devoid of ß-ionone rings and do not possess
vitamin-A activity.

Lycopene is present in tomato, apricot, watermelon, and red guavas.


iii), Xanthophylls -the oxygenated derivatives of carotene. These do have ß-
ionone rings, but do not possess vitamin-A activity. These are

present in papaya, orange peel, and yellow maize.

iv) Alpha-Carotenes similar to ß-carotene in its biological activity.

Structurally, carotenoids are polyenes composed of isoprene units. These


are fat soluble, fairly heat stable and are stable in the pH range of 2-7.
However, during processing of fruits and vegetables, partial loss of carotene
takes place.

Due to their structure, carotenoids are very sensitive to oxidation therefore,


synthetic ß-carotene is

marketed in forms that confer protection from oxidation i.e., these are
oxidized in preference to the

item being protected.

Ascorbic acid can protect ß-carotene by serving as an antioxidant.

Betalains: Betalains are found in plants such as red beets, amaranthus


flowers, bougainvillea, cactus fruits etc. Betalain colours range from red to
yellow.

The red beet is the most common commercial source of these pigments.

Chlorophylls:

Chlorophylls, the most abundant naturally occurring plant pigments, are the
green and olive green pigments in green plants.
These are soluble in alcohol, diethyl ether, benzene, acetone etc. but
insoluble in water.

Some metal ions like iron, zinc and copper react with chlorophyll and the
green colour become brighter.

In alkaline pH, the colour of chlorophyll is better retained.

Chlorophylls are heat sensitive and during processing of fruits and


vegetables containing chlorophyll, the green colour is lost and turns

olive green.

When vegetables containing chlorophyll is cooked, the central magnesium


atom is replaced

by hydrogen atom and loses its colour forming pheophytin.

Curcumin is the main colourant (yellow) in the oleoresin obtained from


turmeric (Curcuma longa).

Curcumin is fat-soluble, has good tinctorial strength, but exhibit slight


sensitivity to light, air and pH.

Paprika oleoresin is the extract of mild capsicum (Capcicum annum) and is


orange red to deep red in

colour. Like curcumin, paprica oleoresin is also water insoluble. Paprika and
turmeric oleoresins are

available in various standardized forms.

Saffron is generally stable toward light, oxidation and pH and has a high
tinctorial strength.

Annatto is the color used in butter and cheese and is obtained from a plant'-
Bixa Orellana
Synthetic Colourants :

The colourants derived from synthetic dyes are called synthetic colourants.

Synthetic colourants were earlier manufactured from coal tar derivatives


and the gelatin desserts, candies and bakery goods were coloured with
them.

Although the colourants were highly purified before they were added to
foods, the negative connotation

of their association with coal tar resulted in much unfavourable publicity.

As a result, synthetic colourants are no longer manufactured from coal tar


derivatives but instead are developed from highly purified petrochemicals.

In fact the development of synthetic dyes came as a boon to the food


industry because these colourants

were superior to natural extracts in terms of their colour intensity, number


of shades, stability, easy

availability above all they were quite cheap.

However, it also brought in a new aspect of the safety in focus.

The toxicological studies have shown that many of the colourants are in fact
harmful; though a few

appear to be safe for use depending on the quantity consumed.

To add to the woes, these assessments of toxicity also vary and colourants
considered safe in one country may not be considered safe in another
country.
More so with further studies, the status of the colourants used in countries
throughout the world is

in a state of flux the number of permitted synthetic colourants is decreasing


year by year

Flavouring Agents :

Flavour like colour has no nutritional value but has a great bearing on
acceptance of foods and therefore,

has enormous commercial importance.

Some studies have indicated that taste can alter intestinal absorption of
glucose and fat metabolism.

Flavour is defined in several ways, according to one such definition the


flavour is, "the sensation produced

by a material taken in the mouth, perceived principally by the senses of


taste and smell, and also

by general pain, tactile and temperature receptors in

the mouth".

Flavouring agents include flavourings and flavour enhancers. The former are
added in foods to produce flavours or modify the existing ones, while the
latter

include the additives which intensify the flavours which are already present
and are weak in nature.
During the early days, people used spices, herbs, vinegar, smoke, honey etc.
to enhance or modify

the flavour of foods.

Along with the developments in synthetic chemistry and analytical


techniques like gas chromatography

and mass spectrometry, there was a spurt in synthetic flavour compounds


and identification of the flavour

compounds in various foods and processed products.

Besides this these are also of great importance in the drug industry.

For making the medicines favourable

to the patients often the former is coated with flavours.

Many medicines with their usual taste could cause vomiting or nausea
therefore these are camouflaged with suitable flavouring agents.

Food flavourings are classified into three groups.

Natural flavours and natural flavouring substances:

These are flavour preparations and

single substances respectively acceptable for human consumption. These


are obtained exclusively by physical means from vegetable,

sometimes animal raw materials, either in their natural state or processed


for human consumption.

Some of the foods contain single

compounds giving flavour e.g., menthol in peppermint, benzaldehyde in


bitter almond,
citral in lime peel, amyl acetate in ripe banana, cinnamaldehyde in cinnamon
etc.

The natural flavours include spice oleoresins and oils, essential oils like citrus
oils; fruit aroma concentrates like apple aroma concentrate etc.

Nature-identical flavouring substances:

These are the substances chemically isolated from aromatic raw materials or
obtained synthetically, they are chemically identical to substances present in
natural products intended

for human consumption, either processed or not.

Artificial flavouring substances:

These are the substances, which have not been identified in natural
products and are intended for human

consumption whether processed or not.

Sweeteners :

Sweetness is one of the important taste sensations. The Importance of


sweetness is reflected in huge

production of sugar (sucrose) world over.

Like any other carbohydrate, sucrose is also a nutrient providing energy to


the human system.

Over the years, sucrose has been implicated in obesity development and
associated diseases and also with dental caries.
Besides, diabetes has become a common disease among large sections of
the population. As a result there is a general trend towards reducing energy
intake

in the form of sugars.

This has resulted in development of sucrose alternatives or artificial

sweeteners.

There are two types of sucrose alternatives viz.

nutritive and nonnutritive sweeteners.

Nutritive sweeteners also called calorie sweeteners are usually


carbohydrates or carbohydrate derivatives.

Nonnutritive sweeteners include a range of natural products which are not


carbohydrates in nature and

some synthetic chemicals.

Nutritive Sweeteners :

Sorbitol:

Sorbitol is a six carbon sugar alcohol that was originally found in the berries
of mountain ash.

It is chemically produced from glucose for commercial use. It is highly


soluble in water (72%. 25 at 25°C).

Sorbitol has about half the sweetness of sucrose. Since it has a much lower
caloric content compared to sucrose, sorbitol is used as a sweetener for
diabetic foods, sugar-free candies and chewing gums.
Xylitol:

Xylitol (xylit) is a pentiol found in most fruits and berries as well as xylan (a
polysaccharide) containing plant materials. It is also produced

by microbiological methods.

Xylitol is a crystalline substance, having good water solubility (64% at 25°C).

It has sweetness and caloric content equal to sucrose. However, because


xylitol is absorbed slowly, it does not cause increase in blood glucose level as
glucose or sucrose.

Therefore, it is used in diabetic foods also.

Isomalt:

Isomalt is also called hydrogenated isomaltulose.

It is an equimolar mixture of 6-O-B-D-

glucopyranosyl-D-glusitol and 1-0-B-D- glucopyranosyl-D-mannitol.

It is of about half the sweetness of sucrose and is stable in acid and alkaline
media under conditions normally occurring in food processing.

It has no impact on blood sugar.

Isomalt is used as a sugar substitute in confectionaries, chewing gum, soft


drinks and desserts.

Non-nutritive Sweeteners

Saccharin:
Saccharin was synthesised way back in 1879. During the two world wars, the
use of saccharin as a sweetener increased due to the scarcity of sugar and
became an accepted sweetener for special dietary

and dietetic foods even though its safety has repeatedly been questioned.

It was at the centre of controversy when it was shown that rats got urinary
cancer after being fed with saccharin. But it was later related to too high a
dose saccharine.

Nowadays it is unlikely to get such a dose as saccharine is used only in


processed drinks like coffee and food.

However, saccharine should be avoided by pregnant or breastfeeding


women.

The Acceptable Daily Intake (ADI by WHO) of saccharin is fixed at 2.5 mg/Kg
body weight.

Saccharin and sodium saccharin are white crystalline powders soluble in


water. They are about 500 times

sweeter than sucrose.

It has good stability during cooking and baking of food products but leaves a
slight bitter metallic after taste. It is permitted as a sweetener in several
countries including India with restrictions.

Cyclamates: Although sodium cyclamate was synthesized in 1937, its actual


use as a sweetener started only in 1950. Cyclamates is a group
used for cyclamic acid, sodium cyclamate and calcium cyclamate. They are
not found in nature.

Cyclamates are stable at high temperatures, are easily soluble in water. They
are about 30 times sweeter than sucrose and can be used as a non-calorie
sweetener in a variety of products. Some times it is

used as a mixture along with saccharin.

Cyclamates are not without safety questions. Therefore its usage

is only allowed with restrictions like most other non-nutritive sweeteners.

The use of cyclamates is not permitted under PFA.

Aspartame (Nutrasweet):

Aspartame was discovered only in 1960. It is the methyl ester of L- aspartyl-


L-phenylalanine.

Aspartame is produced from the amino acids phenylalanine and aspartic


acid. It is an odourless white crystalline powder, slightly soluble in water and
almost 150-200 times

sweeter than sucrose.

Since 1981, it has been used in innumerable food items and diet soft drinks
as it is devoid of any carbohydrates, calories, proteins or

fats.

Aspartame provides 4 Kcal/g energy. It provides sugar like sweetness in


foods, but under certain moisture, temperature and pH conditions, it is

hydrolyzed and loses its sweetness.

Therefore, aspartame is more suitable for dry products or as a


table top sweetener although it is widely used in soft drinks, dairy products
etc.

Like saccharine, aspartame has also been implicated in a number of

health related issues but these have not been proved to be correct beyond
doubt.

However, person with

'phenylketonuria' disorder must avoid it.

Acesulfame K:

Acesulfame K is one of the most

recently introduced (1967) non-nutritive sweeteners.

Acesulfame K is the potassium salt of 6-methyl-1,2,3- oxathizine-4(3)-one-


2,2-dioxide.

It is a white crystalline powder, freely soluble in water, non hygroscopic and


150-200 times sweeter than sucrose.

Acesulfame K is used in soft drinks, chewing gum and as a table-top


sweetener.

More food applications are being investigated.

Sucralose (Splenda) - is produced by chlorinating sugar and is comparable to


aspartame in terms of it not containing any fat, protein, calorie or

carbohydrates and also in not influencing the blood sugar level.


This is about 600 times sweeter than

sucrose and finds applications in soft drink, candy bars and many other food
products.

Rebiana is another non-nutritive sweetener derived from the herb stevia of


the sunflower family. Stevia

extracts are 250-300 times sweeter than sucrose.

These are heat stable pH stable and non-fermentable. Rebiana is used as a


natural sweetener for the diabetics

Allergens (Informative purpose) :

An allergen is normally, any harmless substance that causes an immediate


allergic reaction in a susceptible

person. Food allergens are almost always proteins although other food
constituents, such as certain additives, are known to have allergenic (allergy-
causing) properties.

Food allergy is a potentially serious immune response to eating or otherwise


coming into contact with

certain foods or food additives.

A food allergy occurs when the immune system:

Identifies a particular food protein as dangerous and creates antibodies


against it

The next time the individual eats that food, immune system tries to protect
the body against the danger by releasing massive amount of

chemicals including Histamine.


Histamine is a powerful chemical that can cause a reaction in the respiratory
system, gastrointestinal tract, skin or cardiovascular system.

In the most extreme cases, food allergies can be fatal.

Although any food can provoke an immune response in allergic individuals, a


few foods are

responsible for the majority of food allergies.

The following foods and ingredients are known to cause hypersensitivity and
shall always be declared Cereals containing gluten; i.e., wheat, rye,

barley, oats, spelt or their hybridized strains and products of these;

Crustaceans and products of these;

Eggs and egg products;

Fish and fish products;

Peanuts, soybeans and products of these;

Milk and milk products (lactose included);

Tree nuts and nut products; and

Sulphite in concentrations of 10 mg/kg or more.

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