Food Chemistry

0711-2101
Carbohydrates

Department of Nutrition & Food Engineering

Daffodil International University
 Contents
• Introduction to carbohydrates and its functions
• Classification of carbohydrates
• Monosaccharides and changes
• Introduction to common Oligosaccharides
• Polysaccharides and its classifications
• Starch- structure, gelatinization, retrogradation
• Modified starches
• Glycogen
• Chitin
• Cellulose
• Carbohydrate digesting enzymes
 Carbohydrates
Introduction
Carbohydrates are the most abundant and diverse class of organic
compounds occurring in nature. They are also one of the most versatile
materials available.
Carbohydrate-related technologies have played a critical role in the
development of new products ranging from foods, nutraceuticals,
pharmaceuticals, textiles, paper, and biodegradable packaging materials.
Carbohydrates are produced during the process of photosynthesis:

The first carbohydrates studied contained only carbon (C), hydrogen (H), and
oxygen (O), with the ratio of H:O the same as in water, 2:1, hence the name
carbohydrates or hydrates of carbon, Cx(H2O)y, was given. The composition
of some carbohydrates is indeed captured by the empirical formula, but most
are more complex.
 Carbohydrates
Introduction
Carbohydrates are widely distributed both in animal and plant tissues, where they function as:
• Energy reserves (e.g., starch, fructans, glycogen).
• Structural materials (e.g., cellulose, chitin, xylans, mannans).
• Protective substances. Some plant cell wall polysaccharides are elicitors of plant antibiotics
(phytoalexins). In soybean, fragments of pectic polysaccharides (α-4-linked
dodecagalacturonide) induce synthesis of a protein (protein inhibitor inducer factor) that
inhibits insect and microbial proteinases. Arabinoxylans have been postulated to inhibit
intercellular ice formation, thus ensuring winter survival of cereals.
• Cell recognition moieties. Oligosaccharides conjugated to protein (glycoproteins) or to lipids
(glycolipids) are important components of cell membranes and can be active in cell to cell
recognition and signaling. It is recognized that oligosaccharide moieties serve as probes
through which the cell interacts with its environment. In addition, the environment delivers
signals to the interior of the cell through the cell surface oligosaccharides.
• Information transfer agents (nucleic acids)
 Carbohydrates
According to a more comprehensive definition of Robyt (1998),
carbohydrates are polyhydroxy aldehydes or ketones, or compounds
that can be derived from them by-
• Reduction of the carbonyl group to produce sugar alcohols
• Oxidation of the carbonyl group and/or hydroxyl groups to sugar
acids
• Replacement of one or more of the hydroxyl moieties by various
chemical groups, e.g., hydrogen (H) to give deoxysugars,
aminogroups (NH2 or acetyl-NH2) to give amino sugars
• Derivatization of the hydroxyl groups by various moieties, e.g.,
phosphoric acid to give phosphor sugars, sulphuric acid to give
sulpho sugars
• Their polymers having polymeric linkages of the acetal type
 Food Carbohydrates
Classifications
Food carbohydrates encompass a wide range of molecules and can be
classified according to their chemical structure into three main groups:
• Low molecular weight mono- and disaccharides
• Intermediate molecular weight oligosaccharides
• High molecular weight polysaccharides
Nutritionists divide food carbohydrates into two classes:
• Available, or those which are readily utilized and metabolized. They
may be either mono-, di-, oligo- or polysaccharides, e.g., glucose,
fructose, sucrose, lactose, dextrins, starch.
• Unavailable, or those which are not utilized directly but instead
broken down by symbiotic bacteria, yielding fatty acids, and thus not
supplying the host with carbohydrate. This includes structural
polysaccharides of plant cell walls and many complex
polysaccharides, e.g., cellulose, pectins, beta-glucans.
 Food Carbohydrates
Classifications
Monosaccharides (1 unit), e.g.
Glucose (Glu), Fructose (Fru), Galactose (Gal)

Disaccharides (2 units), e.g. Sucrose (Glu-Fru),

Maltose (Glu-Glu), Lactose (Gal-Glu)

Oligosaccharides (3 – 10 units), e.g. Maltotriose

(Glu-Glu-Glu), Raffinose (Gal-Glu-Fru), Lacto-oligos
(Gal-Gal-Glu
Polysaccharides (10+ units), e.g. Starch, Cellulose, Pectin, Carrageenan, Alginates,
Locust bean gum
 Food Carbohydrates
Sources & Basic Functions in Food
Plants
• Sugar: Sugar cane, sugar beet etc.
• Starch: Potatoes, grains etc.
• Cellulose: Cell walls
• Pectin: Fruit pomace and peels
• Gum: Arabic – acacia tree
Animals
• Glycogen: Chitin and chitosan
• Algae and microbes: Gums - agar, carrageenan, alginate, xanthan
Functions in Food
• sweetening
• gel or paste-forming
• thickening agents
• stabilizers precursors for aroma and coloring substances
 Food Carbohydrates
Monosaccharides
Monosaccharides are chiral polyhydroxy aldehydes and polyhydroxy ketones that often exist
in cyclic hemiacetal forms. They are monomeric in nature and cannot be depolymerized by
hydrolysis to simpler sugars.
Monosaccharides are divided into two major groups according to whether their acyclic forms
possess an aldehyde or a keto group, that is, into aldoses and ketoses, respectively. These, in
turn, are each classified according to the number of carbons in the monosaccharide chain
(usually 3 to 9), into trioses (C3), tetroses (C4), pentoses (C5), hexoses (C6), heptoses (C7),
octoses (C8), nonoses (C9). By adding the prefix aldo- to these names, one can define more
closely a group of aldoses, e.g., aldohexose, aldopentose. For ketoses it is customary to add
the ending -ulose
 Food Carbohydrates
Monosaccharides-Aldoses
The simplest monosaccharide is the three-carbon glyceraldehyde (aldotriose). It has one
asymmetric carbon atom (chiral center) and consequently, it has two enantiomeric forms. The
two forms are D- and L-glyceraldehydes These two compounds have the same empirical
formula, C3H6O3, but are distinct, having different chemical and physical properties. For
instance, D-glyceraldehyde rotates the plane polarized light to the right (+) and has a specific
optical rotation ([α]D) at 25°C of +8.7°; whereas L-glyceraldehyde rotates the plane polarized
light to the left (-) and has a different specific optical rotation, [α]D, at 25°C of –8.7°. Carbon C-2
in glyceraldehyde corresponds to the chiral center. If the OH group attached to the highest
numbered chiral carbon is written to the right in the vertical structure as shown above, a sugar
belongs to the D-chiral family; if the OH is written to the left, a sugar belongs to the L-chiral
family. R (Latin, rectus, right) should be used instead of D. S (Latin, sinister, left) instead of L
The higher aldoses belonging to the D- and L-series are derived from the respective D- and L-
aldotrioses by inserting one or more hydroxymethylene (–CHOH) groups between the first
chiral center and the carbonyl group of the corresponding isomer. The insertion of the
hydroxymethylene group leads to creation of a new chiral center. The number of chiral carbon
atoms (n) in the chain determines the number of possible isomers. Since each chiral carbon
atom has a mirror image, there are 2n arrangements for these atoms.
In a six-carbon aldose with 4 chiral carbons, there are 24 or 16 different arrangements,
allowing formation of 16 different six-carbon sugars with aldehyde end. Eight of these belong
to the D-series the other eight are their mirror images and belong to the L-series.
 Food Carbohydrates
Monosaccharides-Aldoses (D/R)
.
 Food Carbohydrates
Monosaccharides-Ketoses (D/R)
The ketotriose (dihydroxyacetone) has no
chiral center, the first monosaccharide in the
ketose series is erythrulose.
 Food Carbohydrates
Monosaccharides-Structures & Stereochemistry

Isomer: One of two or more molecules that

have the same chemical formula but have a
different stereochemical (special) arrangement
of their atoms.

Epimer: Diastereomeric monosaccharides that

differs at only one carbon position

Enantiomer: A pair of chiral isomers

(stereoisomers) that are direct, nonsuperimposable
mirror images of each other.
 Food Carbohydrates
Monosaccharides-Physical Properties
Most monosaccharides have a sweet taste (fructose is sweetest; 73% sweeter than sucrose).
• They are solids at room temperature.
• They are extremely soluble in water.
The presence of large numbers of OH groups make the monosaccharides much more water
soluble than most molecules of similar MW. Glucose can dissolve in minute amounts of water
to make a syrup (1 g / 1 ml H2O).
 Food Carbohydrates
Monosaccharides- Occurrence
The majority of the naturally occurring carbohydrates have the D-
configuration. L-monosaccharides are less abundant in nature,
although L-arabinose and L-galactose are present as
carbohydrate units in many carbohydrate polymers
(polysaccharides).
The pyranose forms dominate in aqueous solution of most
monosaccharides, it is quite common to find furanose form when
the sugar is incorporated into a biomolecule.
The popular names of sugars often indicate their principal
sources and their optical rotary properties.
Synonyms for D-glucose are dextrose, grape sugar, and starch
sugar.
Synonyms for fructose are levulose, honey sugar, fruit sugar.
 Food Carbohydrates
Monosaccharides-Ring Forms of Sugar
The structure of D-glucose is not the only one in existence. It was found that a relatively high
initial value of specific rotation of glucose in solution (+112°) changed to a much lower value
(+52°) after a period of time. Two forms of D-glucose, designated α and β, were isolated; they
had almost the same melting point but vastly different values of specific rotation (+112° and
+19°), which changed with time, to +52°.

These forms of D-glucose result from an intramolecular Nucleophilic attack by the hydroxyl
oxygen atom attached to C-5 on the carbonyl group, and the consequent formation of a
hemiacetal. Because cyclization converts an achiral aldehyde carbon atom (C-1) into a chiral
hemiacetal carbon atom, two new discrete isomeric forms, called anomers are produced; they
are designated α and β. The six membered ring is related to tetrahydropyran and is called
pyranose.
 Food Carbohydrates
Monosaccharides-Ring Forms of Sugar
A five-membered ring can also be formed from the intramolecular nucleophilic attack by the
hydroxyl oxygen atom attached to C-4 on the carbonyl group and hemiacetal formation. The
five-membered ring is related to tetrahydrofuran and is, therefore, designated as furanose.

The anomeric carbon of ketoses is C-2.

 Food Carbohydrates
Monosaccharides- Mutarotation
When sugar molecules are dissolved in aqueous solutions, a series of reactions,
involving molecular rearrangements around rearrangements are associated with the
change in optical rotation, and lead to formation of a mixture of products that are in
equilibrium. This process, first observed for D-glucose, is called mutarotation. If one
dissolves α-Dglucopyranose ([α]D +112°) or β-D-glucopyranose ([α]D +19°) in water,
an equilibrium is formed with the [α]D of the resultant solution being
+52.7°.Theoretically, the mixture contains five different structural forms of glucose: α-
D-glucopyranose, β-D-glucopyranose, α-D-glucofuranose, β-D-glucofuranose, and
open-chain free aldehyde. The four ring structures are transformed into each other
via the open chain form. The process will take place if the starting material
represents any of the five forms.
The mutarotation process is slow (it may take several hours to reach equilibrium) if
conducted in water at 20°C. The rate of mutarotation increases, however, 1.5 to 3
times with each 10°C increase in the temperature. Both acids and bases increase the
rate of mutarotation. Certain enzymes, such as mutarotase will also catalyze the
mutarotation reactions. The rate and the relative amount of products are also
affected by the polarity of the solvent, with less polar solvents decreasing the rate of
mutarotation.
 Food Carbohydrates
Monosaccharides- Mutarotation
.
 Food Carbohydrates
Monosaccharides- Enolization and Isomerization
In the presence of alkali, sugars are relatively easily interconverted. The
transformation involves epimerization of both aldoses and ketoses as well as aldose
ketose isomerization.
The enolization reaction is a general reaction of a carbonyl compound having an α-
hydrogen atom. Starting with aldehydo-D-glucose, the 1,2 enediol is first formed,
which can be converted into another aldose (with opposite configuration at C-2) and
the corresponding ketose. Therefore, by enolization and isomerization, D-glucose, D-
mannose, and D-fructose can be easily interconverted. Either a base or an enzyme
catalyzes isomerization, and it will also occur under acid or neutral conditions,
although at a much slower rate.
 Food Carbohydrates
Monosaccharides- Chemical Modifications
In
 Food Carbohydrates
Oligosaccharides- Formation of Glycosidic Linkage
The hemiacetal form of sugars can react with alcohol to produce a full acetal
according to the following reaction.

The two products are more commonly referred to as glycosides — more specifically,
as methyl α- and β-D-glucopyranosides. The carbohydrate (glycon) portion of the
molecule is distinguished from the noncarbohydrate aglycon. The acetal linkage is
formed from a glycosyl donor and a glycosyl acceptor.
 Food Carbohydrates
Oligosaccharides-Disaccharides
Disaccharides are glycosides in which the aglycon constitutes another
monosaccharide unit.
Alcohol groups of one carbohydrate (monosaccharide) can react with a
hemiacetal hydroxyl group of another carbohydrate (monosaccharide)
and form a glycoside between two carbohydrate units.
Disaccharides can be divided into heterogeneous and homogeneous
types according to their monosaccharide composition, and into
reducing or non-reducing disaccharides, depending whether they
possess a free anomeric carbon.
Homodisaccharides contain two identical monosaccharide units,
whereas heterodisaccharides are composed of two different
monomers.
Reducing disaccharides, in contrast to non-reducing ones, contain a
reactive hemiacetal center that can be easily modified chemically (e.g.,
via oxidation or reduction).
 Food Carbohydrates
Oligosaccharides-Disaccharides
The two most important naturally occurring heterodisaccharides are sucrose and
lactose.
Sucrose (commonly known as sugar or table sugar) occurs in all plants, but it is
commercially obtained from sugar cane and sugar beets. It is composed of an α-D-
glucopyranosyl unit and a β-D-fructofuranosyl unit linked reducing end to reducing
end, thus it is a non-reducing sugar. Its chemical name is α-D-glucopyranosyl-β-D-
fructofuranoside.

Sucrose is the world’s main sweetening agent. Sucrose is common in many baked
products, breakfast cereals, deserts, and beverages. Sucrose is hydrolyzed into D-
glucose and D-fructose by the enzyme sucrase, which is present in the human
intestinal tract, and therefore can be utilized by humans for energy. Monosaccharides
(D-glucose and D-fructose) do not need to undergo digestion before they are
absorbed. The plant enzyme invertase is able to hydrolyze sucrose into its two
constituent sugars in equimolar mixture of D-glucose and D-fructose; the mixture
has a different value of specific rotation, and is termed invert sugar.
 Food Carbohydrates
Oligosaccharides-Disaccharides
Lactose occurs in the milk of mammals, where it serves as an energy source for
developing mammals. The concentration of lactose in milk may vary from 2 to 8%,
depending on the source. Lactose is also a by product in the manufacture of cheese.
Lactose is composed of two different sugar residues: β-D-galactopyranose and D-
glucopyranose linked via β-1→4 linkage. Its chemical name is β-D-galactopyranosyl-
D-glucopyranoside.

Other common naturally occurring disaccharides are maltose and Cellobiose.

 Food Carbohydrates
Oligosaccharides-Disaccharides
.
 Food Carbohydrates
Oligosaccharides
According to the International Union of Pure and Applied Chemistry (IUPAC),
oligosaccharides are compounds containing 3 to 9 monomeric sugar residues. The
number of sugar residues determines the degree of polymerization of
oligosaccharides. A number of oligosaccharides occur naturally as free compounds
in some plants. Raffinose is a non-reducing trisaccharide that is formed from
sucrose by the addition of α-Dgalactopyranose to the C-6 of the glucose moiety of
sucrose. It is widely distributed in many plants and commercially prepared from beet
molasses and cotton seeds. Stachyose is another derivative of sucrose; it occurs as
a free oligomer in many legumes and pulses.
 Food Carbohydrates
Oligosaccharides
.
 Food Carbohydrates
Polysaccharides
Polysaccharides are the carbohydrates which contain more than 10
monosaccharide units. They can be hydrolyzed into hundred or
even thousands of monosaccharide units. The suffix –ose in sugar
is changed to –ans to describe the corresponding polysaccharide.
Examples:
(1) Pentosans - (a) Arabans, (b) Xylans
(2) Hexosans - (a) Glucans- starch, dextrin, glycogen, cellulose,
inulin; (b) Mannans; (c) Galactans
(3) Complex polysaccharides- (a) Pectins or pectic substances, (b)
Gums, (c) Mucilages, (d) Algal polysaccharides- Alginic acid and
carrageenan, (e) Bacterial polysaccharides- Xanthan gum.
Polysaccharides commonly present in foods are starch, glycogen,
cellulose, hemicellulose, pectic substances, gums.
 Food Carbohydrates
Classification of Polysaccharides
Polysaccharides occur in an infinite variety of different structural types which can be
broadly classified into homopolysaccharides and heteropolysaccharides
Homopolysaccharides: They contain the same structural units throughout. For
example, the glucans (starch and glycogen), fructans, mannans etc. These polymers
can possess either simple linear structure or branched structures of varying
complexity with more than one type of inter unit linkage.
Perfectly linear polysaccharides: They compounds with single neutral
monosaccharides structural unit with only one type of linkage are denoted as
perfectly linear polysaccharides. They are usually insoluble in water and can be
solublized only under drastic conditions. They also have tendency to precipitate from
solution retrogradation.
Branched polysaccharides: They are more soluble in water than linear
polysaccharides as the chain-chain interaction are less pronounced. Compare to the
linear polysaccharides of equal molecular weight and concentration, solution of
branched polysaccharides have the lowest viscosity and lower tendency to
precipitate. They have the ability to form the sticky paste at higher concentration,
probably due to side chain – side chain interaction. So they are suitable as binder or
adhesives.
 Food Carbohydrates
Classification of Polysaccharides
Linearly branched polysaccharides: They are polymers with long
backbone chains and with mainly short chain viz. alkyl cellulose. They
have properties, which are a combination of perfect linear and
branched polymers. The long backbone chain is responsible for high
viscosity of the solution. The presence of numerous short-side chains
weakens the interaction between molecules and thereby gives it good
solubility and rehydration rates and also provides stability to highly
concentrated solutions.
Modified Polysaccharides: The properties of polysaccharides can be
modified by physical and chemical methods that result in products
suitable for specific purposes in the food industry. The solubility in
water, viscosity and stability of solutions are all increased by binding
neutral subsituents to linear polysaccharide chain e.g. hydroxypropyl
cellulose. Binding acid groups (carboxymethyl, sulphate groups) also
results in increased solubility and viscosity.
 Food Carbohydrates
Classification of Polysaccharides
Heteropolysaccharides
They contain two or more types of different monomer units. For
example, the arabinoxylans, glucomannans etc.
These biopolymers can be linear or branched to varying degrees with
different types of branch points. Typical sugars units found in
heteropolysaccharides which occur in food are D- Fructose (Fru), D-
mannose (Man), D-Glucose (Glc), D-Mannuronic acid (Man A), D-
Glucuronic acid (Glu A), D-Xylose (Xyl), D-Galactose (Gal), L-
Arabinose (Ara), D-Galacturonic acid (Gal A), L-Rhamnose (Rha)
 Food Carbohydrates
Homopolysaccharides Occurring/Used in Foodstuffs
 Food Carbohydrates
Heteropolysaccharides Occurring/Used in Foodstuffs
 Food Carbohydrates
Starch
Starch is a natural polymer of the sugar D-glucose. Starch occurs widely in the
vegetables kingdom.
The important of starch in food processing is based on the fact that it provides a very
high proportion of the world’s food energy intake; over 80 % of all food crops are
composed of cereals and starchy – food crops.
Starch occurs in nature in the form of microscopically small, spherical particles or
granules whose size and shape are characteristic for each species. The granules can be
shown by ordinary and polarized light microscopy and by X-ray diffraction to have a
highly order crystalline structure.
It is formed in plants by the condensation of a large number of glucose molecules (few
hundred to several thousand units) into two types of polymers.
One of these is a linear polymer, amylose, that is made up of more than 2000 glucose
units. The individual glucose units are connected to each other by α-1,4-glycosidic
linkage.
A second starch component, called, amylopectin, has a highly branched structure, with
each branch consisting of 20 to 30 glucose units, and each molecule containing several
hundreds of these branches. The glucose units in each linear branch are connected by α-
1,4 linkage. The branch points, are connected through α-1,6-glycosidic linkages.
 Food Carbohydrates
Starch
Both amylose and amylopectin molecules are deposited in starch
granules in an orderly radial pattern.
The important sources of starch are (i) Cereals and millets (65 to 85 %)
e.g. maize, wheat, rice; (ii) Roots and tubes (19 to 35 %) e.g. potato,
tapioca
Cereal starches differ from root and tuber starches in their physical
properties. A cereal starch paste (5%) sets to a thick jelly on cooling
whereas a turber starch paste (5%) remains as a fluid and does not set
to a thick jelly.
In cereals moisture content is low and the starch granules are
embedded in a hard, proteinaceous matrix, which requires preliminary
softening before starch extraction. Potato contains high moisture and
no preliminary softening is required.
 Food Carbohydrates
Starch-Amylose
This is a long unbranched chain of D-glucose molecules linked
together by α-1,4 linkage, similar to that present in maltose.
Molecular weight of amylose range from 105 to 106 daltons and one
molecule of amylose may contain 500 to 5000 glucose molecules.
The solution on keeping turns turbid due to the precipitations of
amylose by a process known as retrogradation. Amylose is mainly
responsible for the stiffening of cooked rice on standing.
Amylose gives a blue color with iodine. Amylose content of a starch
can vary considerably depending on the botanical species. Cereal
starches such as wheat starch contains 25 – 30% amylose, corn starch
(amylomaize) contains 40 – 80% amylose. Waxy maize contain 0%
starch.
 Food Carbohydrates
Starch-Amylopectin
Amylopectin is branched chain polysaccharide component of starch.
In this polysaccharide short chains (20 to 30 molecules) of D- glucose
linked by α-1,4 linkages. These chains are linked to each other by α-1,6
linkages. Molecular weight of amylopectin range from 107 to 108
daltons, and one molecule of amylopectin may contain 50000 to 500000
molecules of D-glucose. Amylopectin gives a purple color with iodine.
 Food Carbohydrates
Starch-Gelatinization
Starch gelatinization is a process that breaks down the intermolecular bonds
of starch molecules in the presence of water and heat, allowing the hydrogen
bonding sites (the hydroxyl hydrogen and oxygen) to engage more water.
This irreversibly dissolves the starch granule. Penetration of water increases
randomness in the general granule structure and decreases the number and
size of crystalline regions.
Crystalline regions do not allow water entry. Heat causes such regions to
become diffuse, so that the chains begin to separate into an amorphous
form. Under the microscope in polarized light starch loses its birefringence.
Gelatinization is influenced by a number of factors. The gelatinization
temperature and the length of heating, plant type (wheat and corn starch
show different behavior patterns) and the amount of water present, pH, size
of starch granule.
Some type of unmodified native starches start swelling at 55 °C, other types
at 85 °C.
 Food Carbohydrates
Starch-Retrogradation of Starch
In dilute solutions, starch molecules will precipitate, with the insoluble
material being difficult to redissolve by heating.
The process of dissolved starch becoming less soluble is called
retrogradation.
Retrogradation of cooked starch involves amylose and amylopectin,
with amylose undergoing retrogradation at a much more rapid rate
than does amylopectin.
The rate of retrogradation depends on several variables, including
molecular ratio of amylose to amylopectin; botanical source of starch;
temperature; starch concentration; salts; surfactants.
Bread staling is due to starch retrogradation. Staling is due to the
gradual transition of amorphous starch to a partially crystalline,
retrograded state.
 Food Carbohydrates
Modified Starches
The behavior of pastes of the common native starches when subjected
to the effects of heat and shear used in modern food technology is
often unsatisfactory.
Consequently modified starches and starch derivatives with more
sophisticated stability characteristics have been developed. Modified
starches include-

• Acid modified starches

• Pre-gelatinized starches
• Cross-linked starches
• Esters & ethers of starch
• Starch phosphates
• Hydroxyalkyl substituted starch
 Food Carbohydrates
Acid Modified Starches
Acid modified or thin boiling starches are prepared by heating starch granules with
diluted hydrochloric acid at temperature below that of gelatinization.
The resultant superficially uncharged granules fragment appear to swell less during
gelatinization, with a consequent reduced volume and lower maximum hot paste
viscosity.
The solubility in hot water is increased, the extent depending on the degree of acid
treatment.
Acid-degraded starch, particularly the non-waxy cereal type, is widely used in the
manufacture of fruit gums on account of the strength and clarity of the resultant gel
which is much improved in comparison to an unmodified, thick-boiling starch.
The viscosity of the gel prepared from acid-modified starch is much lower than that
prepared from the corresponding concentration of the unmodified starch.
As a result hot gel can be easily poured into moulds. The acid treatment causes an
increase in the resultant gel strength, probably because of the preferential
degradation of amylopectin. The gel clarity is also improved.
 Food Carbohydrates
Pre-gelatinized Starches
For many food uses, a water holding or thickening agent is required to function
without the application of heat. For this purpose a pre-gelatinized starch is often
used. Pre-gelatinized starch is prepared by destroying the granular structure on
cooking, which simultaneously causes a considerable reduction in paste
viscosity.
The cooked paste is then dried on rollers or with a spray-drier. The powdered
product will easily rehydrate in cold water but, the resultant dispersions are not
equivalent to freshly prepared paste. This is due to the starch degradation which
has taken place.
The largest use of pre-gelatinized starch is in the instant puddings – a packaged
powder which only needs to be mixed with cold milk and allowed to stand for a
few minutes, producing a simple pudding. The powders are mixture of pre-
gelatinized starch with sugar and flavorings, together with salts which produce
sufficient viscosity increase in the milk to keep the starch suspended until
hydration can take place.
Another widespread use is in frozen fruit-pie fillings where a pre-gelatinized
starch keeps the fruit suspended and helps retain the flavor without the need for
heating.
 Food Carbohydrates
Cross-linked and Other Derivatized Starches
A great number of esters and ethers of starch, with an infinite range of physicochemical properties (particularly
with regard to the heat stability), can be prepared.
But use of such derivatives in food is restricted and only a few of these are important in the food industry. Starch
phosphates, which have a analogues in the amylopectin fraction of root and tuber starches, are examples of
starch derivatives which are suitable as food additives. The introduction of free-acid groups in starch phosphates
both increases and stabilizes the paste viscosity by the
• Negatively charged phosphate groups expand the molecule in solution
• Coulombic repulsion
• Prevent the formation of aggregates
Because of their high viscosity and paste clarity, starch phosphates are put to extensive use in foods as
thickness and texturizing agents. Their resistance to molecular aggregation is of importance in the formulation of
frozen foods.
The swelling and ultimate breakdown of starch granules during cooking can be controlled by introducing a
suitable number of cross-linkages between the molecules.
Cross linked phosphate esters may be prepared commercially by esterification with trimetaphosphate. The extent
of cross linking is measured by the change in the pasting properties of the derivatives. Starch with low level of
phosphate cross linking is also used in textural modification of food e.g. Cross bonded phosphate starches are
used as thickeners in salad cream and fruit-pie fillings.
The introduction of hydroxyalkyl substituent increases the solubility of starch and prevents molecular
aggregation e.g. hydroxypropyl starch. Hydroxyalkyl starches gelatinize at lower temperature than the parent
starch and paste show little tendency to form gels.
 Food Carbohydrates
Glycogen
Glycogen the reserve carbohydrate is a polysaccharide found in the animal body. It is found mainly in the
muscles (0.5 to 1 percent) and liver (3 to 7 percent). Glycogen resembles starch in its chemical properties.
It is formed by the condensation of a large number (5000-10000) of glucose molecules. It is a branched
chain polysaccharide, resembling amylopectin. The chain length varies from 8 to 12 glucose units. The
molecular weight of glycogen from different sources range from 105 to 108 daltons.
 Food Carbohydrates
Cellulose
Cellulose is the most abundant polysaccharide in nature, since one-third of all higher
plants consists of this biopolymer which functions as the main structural material. It
is a linear polymer of D-glucose units linked (1, 4) in the β – configuration. The
cellulose chains are unbranched and may contain as many as 5000 glucose units.
Because of the β- linkage, the glucose units in the chain alternate, and the molecule
is effectively a rigid and straight chain.
Cellulose molecules can readily align themselves side-by-side in an arrangement
which is stabilized by intermolecular hydrogen bonding and form crystalline regions.
Intermolecular bonding is so strong that cellulose is insoluble in water, and even in
strong sodium hydroxide solution.
The cellulose is responsible for the form and gross texture in all foodstuffs prepared
from plants. Being insoluble, it is little affected by any cooking process and does not
disperse. On ingestion, it is unaffected by enzymes in the digestive tract and does
not hydrate.
 Food Carbohydrates
Chitin
Chitin is a homopolysaccharide that occurs as a structural compound in lobster,
shrimp, and crab shells as well as in some insects, and fungi.
The shells contain calcium carbonate, proteins, and other compounds, but this
polysaccharide is mainly responsible for the rigidity of the tissue.
It is easily extracted. The repeating unit in chitin is 2-N-acetyl glucosamine, linked β-
1,4.
 Food Carbohydrates
Pectins
The pectins or pectic substances are found universally in the primary cell walls & intercellular layers in
plants.
They are most abundant in young tissue. They are characteristic constituent of fruits e.g. citrus fruits
contain 30% pectin. The pectic substances are a family of very closely associated polysaccharides which
are very difficult to separate. The term ‘pectin’ is used in relation to water-insoluble polysaccharides.
D-galacturonic acid is the principal constituent which is esterified as methyl ester and possess
considerable gelling power.
Other constituents include D-galactose, L-arabinose, D-xylose, L-rhamnose and L-fucose. Three types of
homopolysaccharides are also present – D-galacturonan, D-galactan, and L-arabinan.
Typical heteropolysaccharides associated with pectic substance include the soyabean L-arabino-D-
galactan.
• Preparations in which more than half of the carboxyl groups are in the methyl ester form are classified
as high-methoxyl pectins, the remainder of the carboxyl groups will be present as a mixture of free acid
and salt forms.
• Preparations in which less than half of the carboxyl groups are in the methyl ester form are called as
low-methoxyl pectins.
Pectin is widely used in marmalade and jelly preparation. High-methoxyl pectin solutions gel sufficient
acid and sugar are present. Low-methoxyl pectin solutions gel only in the presence of calcium ions, which
provide cross bridges.
 Food Carbohydrates
Carbohydrate Digesting Enzymes
Degradation of polysaccharides is now largely replaced by enzymatic
processes as acid hydrolysis requires the use of corrosion resistant
materials which gives rise to high color, salt and ash content (after
neutralization), needs more energy for heating and is relatively difficult
to control.
Amylases
Enzymes involved in degradation of starch belong to hydrolases
(Glycosidases). Amylases are the most important starch degrading
enzymes. They hydrolyze the starch to oligosaccharides and simple
sugars. Of the two components of starch, amylopectin presents the
great challenge to hydrolytic enzyme systems. This is due to the
residues involved in α-1,6-glycosidic branch points which constitute
about 4 - 6% of the glucose present. Most hydrolytic enzymes are
specific for α-1,4-glucosidic links yet the α-1,6-glucosidic links must
also be cleaved for complete hydrolysis of amylopectin to glucose. The
following are the most important enzymes.
 Food Carbohydrates
Carbohydrate Digesting Enzymes
α-amylase
α-amylase is an endoenzyme. It hydrolyzes the α-1,4 glycosidic bonds randomly along the chain. Amylopectin is
hydrolyzed to oligosaccharides that contain two to six glucose units. The branch points are over jumped. A
mixture of amylose and amylopectin is hydrolyzed into a mixture of dextrins, maltose and glucose. Amylose is
completely hydrolyzed to maltose. Calcium ions are required for its activation. α-amylase cleaves both amylose
and amylopectin molecules producing oligosaccharides. Oligosaccharides of 6-7 glucose units are released from
amylose. α-amylase activity leads to a rapid decrease in viscosity of starch solution.
Enzymatic hydrolysis is increased by the gelatinization of starch. α-amylase hydrolyzes the α-1,4-bonds of
amylose and amylopectin in a random manner, liberating small units with free non-reducing end groups. Low
molecular weight dextrins are formed.
β-amylase
β-amylase also hydrolyzes the α-1,4-bonds of amylose and amylopectin, removing maltose units from the non-
reducing end of starch in an orderly fashion. The α-amylase and β-amylase do not cleave the α-1,6-linkagees in
amylopectin.
Glucoamylase
Glucoamylase is used in combination with an α-amylase to produce D-glucose syrups and crystalline D-glucose.
The enzyme acts upon fully gelatinized starch sequentially releasing single D-glucosyl units from the
nonreducing ends of amylose and amylopectin molecules.
Pullulanase
Pullulanase hydrolyzes α-1,6 glucosidic bonds in polysaccharides, e.g. in amylopectin, glycogen, and pullulan.
Linear amylose fragments are formed from amylopectin.