Biochemistry

Dr. Usman Saleem

Pharm.D, R.Ph
Carbohydrates
CHEMISTRY, CLASSIFICATION & IMPORTANCE
Carbohydrates
Functions of Carbohydrates

 Carbohydrates have four important functions in living organisms:

 To provide energy through their oxidation.
 To supply carbon for the synthesis of cell components.
 To serve as a stored form of chemical energy.
 To form a part of the structural elements of some cells and tissues.
Definition

 A carbohydrates is a polyhydroxy aldehyde or polyhydroxy ketone or

compound that yield such derivatives upon hydrolysis.
Classification of Carbohydrates

 Carbohydrates are classified on the basis of molecular size as:

1. Monosaccharides
2. Disaccharides
3. Oligosaccharides
4. Polysaccharides
Monosaccharides
“mon-oh-SACKuh-ride”

 A monosaccharide is a carbohydrate that contains a single

polyhydroxy aldehyde or polyhydroxy ketone unit.
 Monosaccharides cannot be hydrolyzed further into simpler sugars.
 Naturally occurring monosaccharides have from three to seven carbon
atoms; five- and six-carbon species are especially common.
Nomenclature & Classification of
Monosaccharides

 Monosaccharides with an aldehydic

carbonyl or potential aldehydic carbonyl
group are called aldoses.

 Monosaccharides with a ketonic carbonyl

or potential ketonic carbonyl group are
called ketoses.
Nomenclature & Classification of
Monosaccharides

 Monosaccharides are further classified according to the number of

carbon atoms they contain:
Nomenclature & Classification of
Monosaccharides

Examples
No. of Type of Sugar Aldoses Ketoses
Carbon
3 Trioses (C3H6O3) Glyceraldehyde (Aldotriose) Dihydroxyacetone (Ketotriose)
4 Tetroses (C4H8O4) Erythrose (Aldotetrose) Erythrulose (Ketotetrose)
5 Pentoses (C5H10O5) Ribose (Aldopentose) Ribulose (Ketopentose)
6 Hexoses (C6H12O6) Glucose, Galactose Fructose (Ketohexose)
(Aldohexose)
7 Heptoses (C7H14O7) Glucoheptose Sedoheptulose
“
Stereochemistry of Carbohydrates

”
 Optical isomers, also called stereoisomers, are compounds that have the same
molecular and structural formula but differ in the orientation of the atoms in space.
D & L Isomerism

 D & L designations are based on the configuration about the single

asymmetric carbon in glyceraldehyde.
D & L Isomerism

 For sugars with more than one chiral

center, D or L refers to the asymmetric
carbon farthest from the aldehyde or
keto group.
 Most naturally occurring sugars are D
isomers.
Enantiomers
“en-AN-tee-o-mer”

 Enantiomers are stereoisomers that

are non-superimposable mirror
images of each other.
 D and L sugars are referred to as
enantiomers.
Diastereomer
“dye-a-STEER-ee-o-mer”

 Stereoisomers that are not mirror images of each other are described as
diastereomers .
 Molecules that contain more than one chiral center can also exist in
diastereomeric as well as enantiomeric forms.
Van’t Hoff’s Rule of ‘n’

 In general, a compound that has n chiral centers may exist in a maximum of 2n

stereoisomeric forms.
 For example, when two chiral centers are present, at most four stereoisomers (2 2 = 4) are
possible (two pairs of enantiomers).
D Aldoses
D Ketoses
Optical Activity

 Enantiomers are said to be optically active because of the way they

interact with plane-polarized light.
 An enantiomer that rotates plane-polarized light in a clockwise direction
(to the right) is said to be dextrorotatory (+) enantiomer.
 An enantiomer that rotates plane-polarized light in a counterclockwise
direction (to the left) is said to be levorotatory (-) enantiomer.
Optical Activity

 Not all D enantiomers rotate plane-polarized light in the same direction,

nor do all L enantiomers rotate plane-polarized light in the same
direction.
 Some D enantiomers are dextrorotatory (+); others are levorotatory (-).
 There is no way of knowing which way an enantiomer will rotate light
until it is examined with a polarimeter.
Optical Activity
Epimers

 Diastereomers that differ from each other in the configuration at only one
chiral carbon are called Epimers.
 Examples
 D-glucose and D-mannose are epimers with respect to C2.
 D-glucose and D-galactose are epimers with respect to C4.
Epimers
Cyclization of Monosaccharides

 Alcohols react readily with aldehydes to form hemiacetals:

 Likewise, alcohols react with ketones to produce hemiketals:

Cyclization of Monosaccharides

 Monosaccharides have hydroxyl and carbonyl groups in the same molecule.

 Therefore, they can undergo intermolecular reaction to form cyclic hemiacetals (from aldoses)
and hemiketals (from ketoses).
 Cyclic forms with a:
 three-membered ring are called oxiroses,
 four-membered ring oxetoses,
 five-membered ring furanoses,
 six-membered ring pyranoses,
 seven-membered ring septanoses,
 eight-membered ring octanoses, and so on. 
Cyclization of Monosaccharides

 Five- and six-membered cyclic hemiacetals are relatively strain-free and

particularly stable.
 Glucose, for instance, exists in aqueous solution primarily in the six-
membered, pyranose form resulting from intermolecular nucleophilic
addition of the –OH group at C5 to the C1 carbonyl group.
 Some monosaccharides also exist in a five-membered cyclic hemiacetal
form, called a furanose form.
Anomers

 Regardless of whether hemiacetal or hemiketal is formed, the carbonyl carbon

(of open-chain form) becomes chiral in this process, and is referred to as
anomeric carbon.
 The two stereoisomers are referred to as anomers, designated a or β according
to the configurational relationship between the anomeric centre and a specified
anomeric reference atom.
 For example, Glucose forms a six-membered ring with two anomeric forms:
 a-D-Glucoyranose
 b-D-Glucopyranose
Anomers
(Fischer Projection Formula)

 The Fischer projection of the a-anomer of a D sugar (e.g D-Glucose)

has the anomeric hydroxyl group to the right of the anomeric carbon,
and the β-anomer of a D Sugar has the anomeric hydroxyl group to
the left of the anomeric carbon.
Anomers
(Fischer Projection Formula)
Anomers
(Haworth Projection Formula)

 In glucose, the a-anomers has the —OH group of C-1 trans to the CH2OH
group attached to carbon 5.
 In glucose, the b-anomers has the —OH group of C-1 cis to the CH2OH group
attached to carbon 5.
Mutarotation

 Mutarotation is the change in specific rotation that accompanies the equilibration of a

and b anomers in aqueous solution.
 For example, a solution prepared by dissolving crystalline a-D-glucopyranose in water
has a specific rotation of +112°, which gradually decreases to an equilibrium value of
+52.7° as a-D-glucopyranose reaches equilibrium with b-D-glucopyranose.
 A solution of b-D-glucopyranose also undergoes mutarotation, during which the specific
rotation changes from +18.7° to the same equilibrium value of +52.7°.
Mutarotation

 The equilibrium mixture of glucose consists of:

 64% (two-third) b-D-glucopyranose ,
 36% (one-third) a-D-glucopyranose and
 only a trace (0.003%) of the open-chain form.
 Mutarotation is common to all carbohydrates that exist in hemiacetal
forms.
 Some cells contains mutarotases that acceletrate the interconversion of
anomeric sugars.
a-D-glucofuranose b-D-glucofuranose
~0.5% ~0.5%
Open
chain
Form
~0.003%

a-D-glucopyranose b-D-glucopyranose
36% 64%

Observed rotation = 52.7o

BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

D-Ribose and Deoxyribose

 Two pentoses, ribose and deoxyribose, are extremely important because they are
used in the synthesis of nucleic acids (DNA and RNA).
 D-Ribose is a component of a variety of complex molecules, including
ribonucleic acids (RNAs) and energy-rich compounds such as adenosine
triphosphate (ATP).
 2-Deoxy-D-ribose (along with phosphate groups) forms the long chains of
deoxyribonucleic acid (DNA).
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

 2-deoxyribose differs from ribose by the absence of one oxygen atom, that
in the –OH group at C2.
 Both ribose and 2-deoxyribose exist in the usual mixture of open-chain
and cyclic hemiacetal forms.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

D-Glucose
 Of the monosaccharides, the hexose glucose is the most important
nutritionally and the most abundant in nature.
 Glucose is present in honey and fruits such as grapes, figs, and dates.
 Ripe fruits, particularly ripe grapes (20%–30% glucose by mass), are a
good source of glucose, which is often referred to as grape sugar.
 Glucose is also known as blood sugar because it is the sugar transported
by the blood to body tissues to satisfy energy requirements.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

 The normal concentration of glucose in human blood is in the range of 70

–100 mg/dL.
 All tissues use glucose as a primary source of energy.
 Erythrocytes and brains cells utilize glucose solely for energy.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

D-Galactose
 D-Galactose is seldom encountered as a free monosaccharide.
 In the human body, galactose is synthesized from glucose in the
mammary glands to produce lactose (milk sugar).
 D-Galactose is sometimes called brain sugar because it is a component
of glycoproteins (protein–carbohydrate compounds) found in brain and
nerve tissue.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

 Like glucose, galactose is an aldohexose; it differs from glucose

only in the spatial orientation of the – OH group at carbon 4.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

D-Fructose
 D-Fructose, often called levulose or fruit
sugar, occurs in honey and many fruits.
 Aqueous solutions of naturally occurring
D-fructose rotate plane-polarized light to
the left; hence the name levulose.
 D-fructose is present in honey in equal
amounts with glucose.
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

 Like glucose and galactose, fructose is a 6-carbon sugar.

 However, it is a ketohexose rather than an aldohexose.
 In solution, fructose forms five-membered rings:
BIOCHEMICALLY IMPORTANT
MONOSACCHARIDES

 Fructose is sweeter than sucrose and is an ingredient in many sweetened

beverages and prepared foods.
 As a phosphate, it is an intermediate in glucose metabolism.
 Seminal fluid is rich in fructose and sperms utilize fructose for
energy.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

1. Oxidation to Produce Acidic Sugars

 Monosaccharide oxidation can yield three different types of acidic
sugars.
a) Aldonic acids
b) Aldaric acids
c) Alduronic acid
 The oxidizing agent used determines the product.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 Oxidation of the aldehyde end of an

aldose with mild oxidizing agent such
as bromine gives an aldonic acid.

 For example, the oxidation of the

aldehyde end of D-glucose with
bromine produces D-gluconic acid.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 Oxidation of both ends of an aldose (the

aldehyde and the terminal primary alcohol
group) with Strong oxidizing agent such as
nitric acid produces a dicarboxylic acid.
 Such polyhydroxy dicarboxylic acids are
known as aldaric or saccharic acid.
 For glucose, this oxidation produces
glucaric acid.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 In biochemical systems, enzymes can

oxidize the primary alcohol end of an
aldose such as glucose, without oxidation
of the aldehyde group, to produce an
alduronic acid.

 For D-glucose, such an oxidation

produces D-glucuronic acid.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 Oxidation reactions are often used as a test for the presence of an

aldehyde group in a carbohydrate.
 Benedict’s test and Fehling’s test both employ a solution of Cu 2+ ions in
aqueous base.
 When the carbohydrate is oxidized, the blue Cu2+ ion is reduced to Cu2O,
which forms a brick red precipitate.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

2. Reduction to Produce Sugar Alcohols

 The carbonyl group present in a monosaccharide (either an aldose or a
ketose) can be reduced to a hydroxyl group, using hydrogen as the
reducing agent.

 The resulting compound is one of the polyhydroxy alcohols known as

alditols or sugar alcohols.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 For example, the reduction of D-

glucose gives D-glucitol.
 D-Glucitol, also known by the
common name D-sorbitol, is used as
the sweetener.
 D-Sorbitol accumulation in the eye is
a major factor in the formation of
cataracts due to diabetes.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 The sugar alcohols formed from mannose, fructose and galactose are:
 D-Mannose D-Mannitol
 D-Fructose D-Mannitol + D-Sorbitol
 D-Galactose D-Dulcitol
 D-Xylose D-Xylitol
 Mannitol is frequently used medically as an osmotic diuretic to reduce
cerebral edema.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

3. Glycoside Formation
 Cyclic monosaccharides (hemiacetals and hemiketals) readily react with
alcohols in the presence of acid solution to form acetals and ketals, which
are called glycosides.
 A glycoside produced from glucose is called a glucoside, that from
galactose is called a galactoside, and so on.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 For example, glucose reacts with methanol to produce methyl glucoside.

IMPORTANT REACTIONS OF
MONOSACCHARIDES

 The bond between the anomeric carbon atom of the monosaccharide and
the oxygen atom of the –OR group is called a glycosidic bond.

 Disaccharides and polysaccharides form as a result of glycosidic bonds

between monosaccharide units.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

4. Phosphate Ester Formation

 The hydroxyl groups of a monosaccharide can react with acids and
derivatives of acids to form esters.
 The phosphate esters are particularly important because they are the usual
intermediates in the breakdown of carbohydrates to provide energy.
 Phosphate esters are frequently formed by transfer of a phosphate group
from ATP to give the phosphorylated sugar and ADP.
IMPORTANT REACTIONS OF
MONOSACCHARIDES

 For example, specific enzymes in the

human body catalyze the esterification of
the hemiacetal group (carbon 1) and the
primary alcohol group (carbon 6) in
glucose to produce the compounds
glucose 1-phosphate and glucose 6-
phosphate, respectively.
Lesson No: 2 LEARNING OBJECTIVES
Biochemistry  Draw the structures and list sources
and properties for important
Dr. Usman Saleem disaccharides.
Pharm.D, R.Ph  Write reactions for the hydrolysis
of disaccharides.
Disaccharides

 Disaccharides are sugars composed of two monosaccharide units linked

together by the acetal or ketal linkages.
 They can be hydrolyzed to yield their monosaccharide building blocks by
boiling with dilute acid or reacting them with appropriate enzymes.
 In disaccharide formation, one of the monosaccharide reactants functions
as a hemiacetal, and the other functions as an alcohol.
Disaccharides
Disaccharides

 Three important naturally occurring disaccharides are:

1. Maltose
2. Lactose
3. Sucrose
 They illustrate the three different ways monosaccharides are linked:
 By a glycosidic bond in the a orientation (maltose),
 A glycosidic bond in the b orientation (lactose), or
 a bond that connects two anomeric carbon atoms (sucrose).
Maltose
(Malt Sugar)

Occurrence
 Maltose, often called malt sugar, is present in fermenting grains and
can be prepared by enzyme-catalyzed degradation of starch.

 In the body, it is produced during starch digestion by a-amylase in the

small intestine and then hydrolyzed to glucose by a second enzyme,
maltase.
Maltose
(Malt Sugar)

Chemistry
 Chemically, maltose consists of two
D-glucose units, one of which must
be a-D-glucose.

 The glycosidic linkage between the

two glucose units is called an (1 → 4)
linkage.
Maltose
(Malt Sugar)

 Maltose has one free hemiacetal group. Consequently, maltose exists in

three forms:
 a-maltose,
 b-maltose, and
 open-chain form.
 In solution, maltose exists as an equilibrium mixture of all the three
forms.
 In the solid state, the b form is dominant.
Maltose
(Malt Sugar)

Properties
 Maltose is a white crystalline solid, with a melting point 160–165 °C.
 It is soluble in water and is dextrorotatory.
 Maltose is a reducing sugar because the hemiacetal group on the right
unit of D-glucose is in equilibrium with the free aldehyde and can be
oxidized to a carboxylic acid.
 It is also capable of exhibiting mutarotation.
Maltose
(Malt Sugar)

 Hydrolysis of D-maltose produces two molecules of D-glucose.

 Acidic conditions or the enzyme maltase is needed for the hydrolysis to
occur.
Lactose
(Milk Sugar)

 Lactose, or milk sugar, is the principal

carbohydrate in milk.
 Human mother’s milk obtained by
nursing infants contains 7%–8% lactose,
almost double the 4%–5% lactose found
in cow’s milk.
 Lactose is an important ingredient in
commercially produced infant formulas
that are designed to simulate mother’s
milk. Cow’s milk is about 5% lactose.
Lactose
(Milk Sugar)

Chemistry
 Chemically, lactose is made up of b-
D-galactose unit and a D-glucose.
 The linkage between two sugar units
is b (1→4) glycosidic linkage.
Lactose
(Milk Sugar)

Properties
 Lactose is a white, crystalline solid with a melting point 203°C and is also
dextrorotatory.
 The equilibrium mixture has a specific rotation +52.5°.
 It is less soluble in water and much less sweet than sucrose.
 The presence of a hemiacetal group in the glucose unit makes lactose a
reducing sugar.
Lactose
(Milk Sugar)

 Lactose can be hydrolyzed by acid or by the enzyme lactase, forming an

equimolar mixture of galactose and glucose.

 In the human body, the galactose so produced is then converted to glucose

by other enzymes.
Lactose
(Milk Sugar)

Lactose Intolerance
 The genetic condition lactose intolerance is an
inability of the human digestive system to
hydrolyze lactose.
 In lactose-intolerant individuals, lactose
remains in the intestines undigested rather than
being absorbed, causing fullness, discomfort,
cramping, nausea, and diarrhea.
Sucrose or Saccharose
(Table sugar, Cane sugar, Beet sugar)

Occurrence
 Sucrose is common table sugar,
which is principally extracted from
sugarcane and sugar beets.
 Sugar cane contains up to 20% by
mass sucrose, and sugar beets
contain up to 17% by mass sucrose. Hummingbirds depend on the
sucrose and other carbohydrates
of nectar for their energy.
Sucrose or Saccharose
(Table sugar, Cane sugar, Beet sugar)

Chemistry
 The monosaccharide units that make up
sucrose are a-D-glucose and b-D-
fructose.
 The a C-1 carbon of the glucose is linked
to the β C-2 carbon of the fructose in a
glycosidic linkage that has the notation
α,β(1 → 2).
Sucrose or Saccharose
(Table sugar, Cane sugar, Beet sugar)

Properties:
 Sucrose is a white crystalline solid, soluble in water and with a melting
point 180°C.
 When heated above its melting point, it forms a brown substance known
as caramel.
 It is dextrorotatory and has a specific rotation of + 66.7°.
 Sucrose does not exhibit mutarotation.
Sucrose or Saccharose
(Table sugar, Cane sugar, Beet sugar)

 Sucrose is not a reducing sugar because both anomeric groups are involved
in the glycosidic linkage.
 Sucrase, the enzyme needed to break the a, b (1 → 2) linkage in sucrose,
is present in the human body. Hence sucrose is an easily digested substance.
 Sucrose hydrolysis (digestion) produces an equimolar mixture of D-glucose
and D-fructose called invert sugar.
Sucrose or Saccharose
(Table sugar, Cane sugar, Beet sugar)

 Honeybees and many other insects possess

an enzyme called invertase that hydrolyzes
sucrose to invert sugar.
 Thus honey is predominantly a mixture of
D-glucose and D-fructose with some
unhydrolyzed sucrose.
Invert Sugar

 The term invert sugar comes from the observation that the direction of
rotation of plane-polarized light changes from positive (clockwise) to
negative (counterclockwise) when sucrose is hydrolyzed to invert sugar.
 The rotation is +66o for sucrose. The net rotation for the invert sugar
mixture of fructose (-92o) and glucose (+52 o)is -40o.
Summery of Important Disaccharides

 Following table summarizes some features of the three disaccharides we have

discussed.

Monosaccharide Glycoside
Name Constituents Linkage Source
Maltose Two glucose units a(1 → 4) Hydrolysis of starch

Lactose Galactose and glucose b(1 → 4) Mammalian milk

Sucrose Glucose and fructose a-1 → b-2 Sugar cane and sugar
beet juices
Lesson No: 3
Biochemistry LEARNING OBJECTIVES
 Describe the structures and list
Dr. Usman Saleem sources and uses for important
Pharm.D, R.Ph polysaccharides.
Polysaccharides

 A polysaccharide is a polymer that contains many

monosaccharide units bonded to each other by glycosidic linkages.

 Polysaccharides are often also called glycans.

 Glycan is an alternate name for a polysaccharide.

Polysaccharides

 The important parameters that distinguish various polysaccharides (or

glycans) from each other are:
1. The identity of the monosaccharide repeating unit(s) in the polymer
chain.
 The more abundant polysaccharides in nature contain only one type of
monosaccharide repeating unit.
 Such polysaccharides, including starch, glycogen, cellulose, and chitin,
are examples of homopolysaccharides.
Polysaccharides

 Polysaccharides whose structures contain two or more types of

monosaccharide monomers, including hyaluronic acid and heparin, are
called heteropolysaccharides.
2. The length of the polymer chain.
 Polysaccharide chain length can vary from less than a hundred monomer
units to up to a million monomer units.
3. The type of glycosidic linkage between monomer units.
 As with disaccharides, several different types of glycosidic linkages are
encountered in polysaccharide structures.
Polysaccharides

4. The degree of branching of the polymer chain.

 The ability to form branched-chain structures distinguishes
polysaccharides from the other two major types of biochemical
polymers: proteins and nucleic acids, which occur only as linear
(unbranched) polymers.
Homopolysaccharides

 A homopolysaccharide is a polysaccharide in which only one type of

monosaccharide monomer is present.
 The most important Homopolysaccharides are:
 Starch
 Glycogen
 Cellulose
 Starch and glycogen are examples of storage polysaccharides, cellulose
and chitin are structural polysaccharides.
Starch

Over View
 Starch is energy-storage polysaccharide in plants.
 It occur in plant cells usually as starch granules in the cytosol.
 Starch is fully digestible and is an essential part of the human diet.
 The major sources of starch are beans, the grains wheat and rice, and
potatoes.
Starch

Chemistry
 Starch is a homopolysaccharide containing only a-D-glucose
monosaccharide units.
 Two different polyglucose polysaccharides can be isolated from most
starches:
a. Amylose
b. Amylopectin.
Starch

a. Amylose
 Amylose, a linear glucose polymer, usually accounts for 15%–20%
of the starch.
 In amylose’s non-branched structure, the glucose units are connected
by (a1→4) glycosidic linkages.
 The number of glucose units present in an amylose chain depends on
the source of the starch; 300–500 monomer units are usually present.
Fig: Structure of Starch
Amylose
Starch

b. Amylopectin
 Amylopectin, a branched glucose polymer, accounts for the
remaining 80%–85% of the starch.
 Amylopectin has a high degree of branching in its polyglucose
structure.
 The branch points involve a(1→6) glycosidic linkages.
 There are usually 24 to 30 D-glucose units, all connected by a(1→4)
linkages, between each branch point of amylopectin.
Fig: Structure of Starch
Amylopectin
Starch

Amylopectin
 Because of the branching,
amylopectin has a larger average
molecular mass than the linear
amylose.
 Up to 100,000 glucose units may be
present in an amylopectin polymer
chain.  An a(1→ 6) linkage is present in
the amylopectin structure at each
branch point.
Starch

 All of the glycosidic linkages in starch (both amylose and amylopectin) are
of the a type.
 In amylose, they are all a(1→4); in amylopectin, both a(1→4) and a(1→6)
linkages are present.
 Because starch molecules are digested mainly in the small intestine by a-
amylase, which catalyzes hydrolysis of the a(1→4) linkages, starch has
nutritional value for humans.
 Complete hydrolysis of both amylose and amylopectin yields only D-
glucose.
Starch

 The most usual conformation of amylose is a

helix with six residues per turn.
 Iodine molecules can fit inside the helix to
form a starch–iodine complex, which has a
characteristic dark-blue color.
 The formation of this complex is a well-
known test for the presence of starch.
 Activity No. 1
An individual starch molecule contains
thousands of glucose units but has only a single
hemiacetal group at the end of the long polymer
chain. Would you expect starch to be a reducing
carbohydrate? Explain.
Glycogen

Over-View
 Glycogen is the glucose storage polysaccharide in humans and animals.
 Glycogen, sometimes called animal starch, serves the same energy
storage role in animals that starch serves in plants.
 The largest amounts of glycogen are stored in the liver and muscles.
 The total amount of glycogen in the body of a well-nourished adult human is
about 350 g.
Glycogen

Chemistry
 Glycogen is a branched-chain polymer of a-D-glucose, and in this
respect it is similar to the amylopectin fraction of starch.
 Like amylopectin, glycogen consists of a chain of a(1→4) linkages
with a(1→6) linkages at the branch points.
 Branch points occur about every 8-12 residues in glycogen.
Glycogen

 Glycogen is about three times more highly branched than amylopectin,

and is much larger—up to one million glucose units per molecule.
Cellulose

Over-View
 Cellulose is the major structural
component of plants, especially of wood
and plant fibers.
 Cotton is almost pure cellulose(95%),
and wood is about 50% cellulose.
Cellulose

Chemistry
 It is a linear homopolysaccharide of β-D-glucose, and all residues are
linked in β(1→4) glycosidic bonds.
 Typically, cellulose chains contain about 5000 glucose units.
 Click
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Fig: Structure of Cellulose

Repeating disaccharide in cellulose is β-cellobiose
Cellulose

 Humans and other animals lack the enzymes

capable of catalyzing the hydrolysis of β-
linkages in cellulose.
 However, the intestinal tracts of grazing animals
such as horses, cows, and sheep contain bacteria
that produce cellulase, an enzyme that can
hydrolyze b(1→4) linkages and produce free
glucose from cellulose.
Cellulose

 Despite its nondigestibility, cellulose is

still an important component of a balanced
diet.
 It serves as dietary fiber.
 Dietary fiber provides the digestive tract
with “bulk” that helps move food through
the intestinal tract and facilitates the
excretion of solid wastes.
 Common Polysaccharides

Glycosidic
Type Made From Function Digestible by Humans
Linkage
Amylose Glucose a(1→4) Fuel storage in plant Yes, requires amylase
a(1→4)
Fuel storage in plant Yes, requires amylase and
Amylopectin Glucose a(1→6) at debranching enzyme
branch points
a(1→4) Fuel storage in plant
Yes, requires amylase and
Glycogen Glucose a(1→6) at (Sometimes, called
debranching enzyme
branch points “animal starch”).
Structural material in
Cellulose Glucose β(1→4) No, requires cellulase
plant
Heteropolysaccharides

 A heteropolysaccharideis a polysaccharide in which more

than one (usually two) type of monosaccharide monomer
is present.
 They are also called heteroglycans.
Glycosaminoglycans (GAGs) or
Mucopolysaccharides

 A GAG is an unbranched heteropolysaccharide, made up of

repeating disaccharides.
 The repeating disaccharide unit is generally composed of:
 An amino sugar which is almost always either an N-
acetylglucosamine or N-acetylgalactosamine.
 A uronic acid residue which usually is D-glucuronic acid
or in some cases it may be L-Iduronic acid.
Glycosaminoglycans (GAGs) or
Mucopolysaccharides

 In some glycosaminoglycans, one or more of the hydroxyls of

amino sugar are esterified with sulphate, hence they are called
sulphur-containing mucopolysaccharides.
 Glycosaminoglycans whose sugar units are not sulphated are called
sulphur-free mucopolysaccharides.
 They are also called mucopolysacchride because they were first
extracted from mucus.
Glycosaminoglycans (GAGs) or
Mucopolysaccharides

 The presence of sulphate and carboxyl groups contributes to acidity of

molecules, making them acidic mucopolysaccharides.
 The important mucopolysaccharides or GAGs include:
 Hyaluronic acid
 Chondroitin sulfate
 Dermatan sulfate
 Heparin
 Keratan sulfate
Hyaluronic Acid

Occurrence:
 Hyaluronic acid is an important GAG found in the ground substance of
synovial fluid of joints, and vitreous humour of eyes.
 It is also present in the umbilical cord and forms the gel around ovum.
Composition:
 Hyaluronic acid is composed of repeating units of D-glucuronic acid and
N-acetylglucosamine linked together by b(1→3) glycosidic linkages.
Hyaluronic Acid

 It contains up to 25,000 repeats of basic disaccharide units held by

b(1→4) linkages.
Hyaluronic Acid

Hydrolysis
 It yields equimolecular quantities of D-glucosamine, D-glucuronic acid, and
acetic acid.
 Hyaluronidase, an enzyme secreted by some pathogenic bacteria, can
hydrolyze the glycosidic linkage of hyaluronic acid, rendering tissues more
susceptible to bacterial invasion.
 Hyaluronidase of semen hydrolyzes the outer polysaccharides coat of the
ovum allowing a better penetration of sperm into the ovum.
Hyaluronic Acid

Function:
 Hyaluronic acid forms clear, highly viscous solution that serves as
lubricants in the synovial fluid of joints and give the vitreous humour of
eye its jelly-like consistency.
Chondroitin Sulphate

Occurrence:
 It is present in ground substance of connective tissues widely distributed in
cartilage, bone, tendons, cornea and skin.
Composition:
 Chondroitin sulphate contains repeating units of D-glucuronic acid and N-
acetylgalactosamine linked together by b(1→3) glycosidic linkages.
 The repeating units in turn are joined together by b(1→4) linkages.
Chondroitin Sulphate

Types
 There are two types, one sulphated on the
C-4 of the N-acetylgalactosamine residue
and other at C-6.
1) Chondroitin A is Chondroitin-4-
Sulphate.
2) Chondroitin C is Chondroitin-6-
Sulphate.
Chondroitin Sulphate

Function:
 They are required for the synthesis of osteocytes and cartilage.
 It is required for the transparency of cornea.
Dermatan Sulphate

Occurrence
 Dermatan sulphate is found in skin, blood vessels, heart valves and
tendons.
 The dermatan sulphate is also known as chondroitin sulphate B.
Composition
 It is structurally related to chondroitin 4-sulphate.
 The only difference is that there is an inversion in the configuration
around C5 of D-glucuronic acid to form L-Iduronic acid.
Keratan Sulphate

Occurrence:
 It is present in cornea, cartilage and intervertebral disc.
Composition:
 Keratan sulphate is composed of repeating units of D-galactose and N-
acetylglucosamine-6-sulphate linked by b(1→4)linkages.
 The repeating units are in turn joined together by b(1→3) linkages.
 It is the only GAG, which doesn’t contain any uronic acid.
Heparin

Occurrence:
 Heparin is present in liver, lungs, spleen and monocytes.
Chemistry:
 It contains repeating units of sulphated glucosamine and D-glucuronic
acid joined together by a(1→4) glycosidic linkages.
 Heparin is a small polysaccharide with only 15–90 disaccharide residues
per chain.
Heparin

Function:
 The best known of heparin’s biochemical
functions is that of an anticoagulant; it
helps prevent blood clots.
 It binds strongly to a protein involved in
terminating the process of blood clotting,
thus inhibiting blood clotting.
Glycoconjugates
Proteoglycans and Glycoproteins

 Glycoproteins are conjugated proteins to which carbohydrates are

covalently attached.
 Glycoproteins have short oligosaccharide chains (1-20 sugars), which are
highly branched and generally don't have a repeating sequence.
 On the other hand, sugar chains of proteoglycans are longer (100 or more
sugars), linear and unbranched, with disaccharide repeats.
Glycoconjugates
Proteoglycans and Glycoproteins

 Many simple heteropolysaccharides are, in fact, are proteoglycans in

which a terminal unit is covalently attached through an O-glycosidic
linkage to –OH group of serine residue of a protein.
 The amount of carbohydrate in a proteoglycan is usually much greater
than glycoproteins and may comprise 95 percent of its weight, e.g.
aggrecan found cartilage.
 Glycoproteins are found on the outer surface of the plasma membrane,
serving as receptors and forming highly specific sites for cell-cell
recognition.