Carbohydrates

Polysaccharides

Dr. Nikhat Siddiqi 1

 Contents
• Polysaccharides – Classification
• Homoglycans
• Heteroglycans

Dr. Nikhat Siddiqi 2

 Joining of monosaccharides
• Monosaccharides can be joined to form disaccharides,
oligosaccharides, and polysaccharides.
• Important disaccharides include lactose (galactose +
glucose), sucrose (glucose + fructose), and maltose (glucose
+ glucose).
• Important polysaccharides include branched glycogen (from
animal sources) and starch (plant sources) and unbranched
cellulose (plant sources); each is a polymer of glucose.
• The bonds that link sugars are called glycosidic bonds. These
are formed by enzymes known as glycosyltransferases.

Dr. Nikhat Siddiqi 3

 Naming glycosidic bonds
• Glycosidic bonds between sugars are named
according to the numbers of the connected
carbons, and also with regard to the position
of the anomeric hydroxyl group of the sugar
involved in the bond.

Dr. Nikhat Siddiqi 4

 Naming glycosidic bonds
• If this anomeric hydroxyl is in
the α configuration, the
linkage is an α-bond.
• If it is in the β configuration,
the linkage is a β-bond.
• Lactose, for example, is
synthesized by forming a
glycosidic bond between
carbon 1 of β-galactose and
carbon 4 of glucose. The
linkage is, therefore, a
β(1→4) glycosidic bond.

Dr. Nikhat Siddiqi 5

 Polysaccharides
• Polysaccharides are also called as glycans.
• Made up of large number of monosaccharides
linked by glycosidic linkages.
• Smaller glycans are called as oligosaccharides
(10-15 monomers) found attached to
popypeptides in glycoproteins and some
glycolipids.
• Found in membrane and secretary proteins.

Dr. Nikhat Siddiqi 6

Polysaccharides - Classification

Homoglycans
Polysaccharides

Heteroglycans

Dr. Nikhat Siddiqi 7

Polysaccharides - Classification

Structural
Polysaccharides
Polysaccharides

Storage
Polysaccharides

Dr. Nikhat Siddiqi 8

 Homoglycans
• Found in starch, glycogen, cellulose and chitin.
• Starch, glycogen, cellulose give D-glucose when
hydrolysed.
• Starch –energy storage molecule in plants.
• Glycogen –energy storage molecule in animals.
• Chitin – component of exoskeleton of insects,
cell wall of fungi, yields glucose derivative N-
acetylglucosamine when hydrolyzed.

Dr. Nikhat Siddiqi 9

 Starch (Storage Polysacchardes)
• Significant source of carbohydrate in human
diet.
• Source- potatoes, rice, wheat, corn.

Amylose
Starch
Amylopetin
Dr. Nikhat Siddiqi 10
 Amylose
• Composed of long,
unbranched chains of S-
glucose residues that
are linked by (1,4)
glycosidic bonds.
• Have one reducing end
in which the ring can
open to form free
aldehyde group with
reducing properties.
Dr. Nikhat Siddiqi 11
 Amylose
• Contains several thousand glucose residues
has molecular weight 150,000 to 600,000.
• Linear amylose molecule forms tight helices.
• Gives blue colour with iodine due to
interaction between iodine molecules and the
helically arranged glucose rsidues.

Dr. Nikhat Siddiqi 12

 Amylopectin
• is branched polymer
containing (1,4) and
(1,6)glycosidic
linkages.
• The (1,6) points may
occur every 20 to 35
residues and prevent
helix formation.

Dr. Nikhat Siddiqi 13

• Starch digestion begins in the mouth where the
salivary enzyme - amylase initiates hydrolysis
of glycosidic bonds.
• Digestion continues in the small intestine where
pancreatic -amylase hydrolyzes all the (1,4)
glycosidic bonds except the branch points.
• The products of - amylase maltose,
trisaccharide maltotriose and  limit dextrin.

Dr. Nikhat Siddiqi 14

Starch - Structure

Dr. Nikhat Siddiqi 15

Glycogen (Storage Polysaccharides)
• Storage carbohydrate in vertebrates.
• Found in liver and skeletal muscle.
• Structure similar to amylopectin except that it
has more branch point possibly at every fourth
glucose residue.

Dr. Nikhat Siddiqi 16

Glycogen-Structure

Dr. Nikhat Siddiqi 17

Glycogen- Structure

Dr. Nikhat Siddiqi 18

 Cellulose (Structural Polysaccharides)
• Polymer of D-glucopyranose residues linked by
(1,4) glycosidic bonds. Unbranched
• Structural polysaccharide in plants.
• Pairs of unbranched cellulose molecules may
contain as many as 12,000 glucose units each
held together by hydrogen bonding to form
sheet like strips called microfibrils. These
structures are found in primary and secondary
cell walls of plants.
Dr. Nikhat Siddiqi 19
• The ability to digest cellulose is found in
microorganism which contain the enzyme
cellulase.
• Cellulose can be hydrolyzed to its constituent
glucose units by microorganisms that inhabit the
digestive tract of termites and ruminants.
• Cellulose makes up dietary fiber.
• Paper, wood, textiles are some of cellulose
containing products.
Dr. Nikhat Siddiqi 20
Cellulose - Structure

Dr. Nikhat Siddiqi 21

 Chitin (Structural Polysaccharide)
• Chitin is an unbranched polymer of N-Acetyl-D-
glucosamine.
• It is found in fungi and is the principal component
of arthropod and lower animal exoskeletons, e.g.,
insect, crab, and shrimp shells.
• It may be regarded as a derivative of cellulose, in
which the hydroxyl groups of the second carbon
of each glucose unit have been replaced with
acetamido (-NH(C=O)CH3) groups.
Dr. Nikhat Siddiqi 22
Chitin - Structure

Dr. Nikhat Siddiqi 23

Polysaccharides

Heteroglycans

Dr. Nikhat Siddiqi 24

 Heteroglycans
• High molecular weight carbohydrate polymers
that contain more than one kind of
monosaccharides.
• Major classes found in animals are N and O-
linked glycans attached to proteins.

Dr. Nikhat Siddiqi 25

 Glycosaminoglycans (GAGs)
• Glycosaminoglycans (GAGs) are large
complexes of negatively charged
heteropolysaccharide chains.
• They are generally associated with a small
amount of protein, forming proteoglycans,
which typically consist of over 95%
carbohydrate.

Dr. Nikhat Siddiqi 26

 Glycosaminoglycans (GAGs)
• Glycosaminoglycans have the special ability to bind
large amounts of water, thereby producing the gel-
like matrix that forms the basis of the body's ground
substance, which, along with fibrous components
such as collagen, make up the extracellular matrix.
• The viscous, lubricating properties of mucous
secretions also result from the presence of
glycosaminoglycans, which led to the original
naming of these compounds as
mucopolysaccharides.
Dr. Nikhat Siddiqi 27
 Structure of Glycosaminoglycans
• Glycosaminoglycans are
long, unbranched,
heteropolysaccharide
chains generally
composed of a
repeating disaccharide
unit [acidic sugar–
amino sugar]n.

Dr. Nikhat Siddiqi 28

 Structure of Glycosaminoglycans
• The amino sugar is either D-
glucosamine or D-
galactosamine, in which the
amino group is usually
acetylated, thus eliminating
its positive charge.
• The amino sugar may also be
sulfated on carbon 4 or 6 or
on a nonacetylated nitrogen.
• The acidic sugar is either D-
glucuronic acid or its carbon-
5 epimer, L-iduronic acid.

Dr. Nikhat Siddiqi 29

 Structure of Glycosaminoglycans
• A single exception is keratan sulfate, in which
galactose rather than an acidic sugar is
present.
• These acidic sugars contain carboxyl groups
that are negatively charged at physiologic pH
and, together with the sulfate groups, give
glycosaminoglycans their strongly negative
nature.

Dr. Nikhat Siddiqi 30

Some monosaccharide units found in
glycosaminoglycans.

Dr. Nikhat Siddiqi 31

 Functions of GAGs
• Because of their large number of negative charges,
these heteropolysaccharide chains tend to be
extended in solution.
• They repel each other, and are surrounded by a shell
of water molecules.
• When brought together, they “slip” past each other,
much as two magnets with the same polarity seem to
slip past each other.
• This produces the “slippery” consistency of mucous
secretions and synovial fluid.
Dr. Nikhat Siddiqi 32
 Functions of GAGs---cont
• When a solution of glycosaminoglycans is
compressed, the water is “squeezed out” and the
glycosaminoglycans are forced to occupy a smaller
volume.
• When the compression is released, the
glycosaminoglycans spring back to their original,
hydrated volume because of the repulsion of their
negative charges.
• This property contributes to the resilience of synovial
fluid and the vitreous humor of the eye.
Dr. Nikhat Siddiqi 33
Classification of the glycosaminoglycans

• The six major classes of glycosaminoglycans

are divided according to monomeric
composition, type of glycosidic linkages, and
degree and location of sulfate units.

Dr. Nikhat Siddiqi 34

Structure and distribution of
glycosaminoglycans (GAGs).

Dr. Nikhat Siddiqi 35

 Hyaluronic Acid
• Hyaluronate molecules may consist of as
many as 25,000 disaccharide units, with
molecular weights of up to 107.
• Hyaluronates are important components of
the vitreous humor in the eye and of synovial
fluid, the lubricant fluid of joints in the body.

Dr. Nikhat Siddiqi 36

• The chondroitins and keratan sulfate are
found in tendons, cartilage, and other
connective tissue, whereas dermatan sulfate,
as its name implies, is a component of the
extracellular matrix of skin.
• Heparin, with the highest net negative charge
of the disaccharides shown, is a natural
anticoagulant substance.

Dr. Nikhat Siddiqi 37

 Proteoglycans
• High carbohydrate content (about 95%).
• Occur on cell surfaces or are secreted into
extracellular matrix.

Dr. Nikhat Siddiqi 38

 Structure of proteoglycans
• All of the glycosaminoglycans, except
hyaluronic acid, are found covalently attached
to protein, forming proteoglycan monomers.

Dr. Nikhat Siddiqi 39

 Structure of proteoglycan monomers
• A proteoglycan monomer found in cartilage consists of a
core protein to which the linear glycosaminoglycan chains
are covalently attached.
• These chains, which may each be composed of more than
100 monosaccharides, extend out from the core protein,
and remain separated from each other because of charge
repulsion.
• The resulting structure resembles a “bottle brush”. In
cartilage proteoglycan, the species of glycosaminoglycans
include chondroitin sulfate and keratan sulfate.

Dr. Nikhat Siddiqi 40

“Bottle-brush” model of a cartilage
proteoglycan monomer.
• A proteoglycan
monomer found in
cartilage consists of a
core protein to which
the linear
glycosaminoglycan
chains are covalently
attached.

Dr. Nikhat Siddiqi 41

 Linkage region of glycosamino-glycans
• Linkage between the
carbohydrate chain and the
protein: This linkage is most
commonly through a
trihexoside (galactose-
galactose-xylose) and a
serine residue, respectively.
• An O-glycosidic bond is
formed between the xylose
and the hydroxyl group of
the serine.

Dr. Nikhat Siddiqi 42

 Proteoglycan aggregates
• The proteoglycan monomers
associate with a molecule of
hyaluronic acid to form
proteoglycan aggregates. The
association is not covalent,
but occurs primarily through
ionic interactions between
the core protein and the
hyaluronic acid. The
association is stabilized by
additional small proteins
called link proteins .

Dr. Nikhat Siddiqi 43

 Proteoglycans
• Proteoglycans consist of
a protein core (brown)
and one or more
covalently attached
glycosaminoglycan
chains ([blue].

Dr. Nikhat Siddiqi 44

Dr. Nikhat Siddiqi 45
 Examples of proteoglycans
• Examples include syndecans, glycipcans and
affrecans
• The syndecans are a class of heparan sulfate
and chondroitin sulfate containing
proteoglycans in which the core protein is a
transmembrane protein.
• Aggregans is found in cartilage.

Dr. Nikhat Siddiqi 46

 Mucopolysaccharidoses
• The mucopolysaccharidoses are hereditary disorders
(1:25,000 births) that are clinically progressive.
• They are characterized by accumulation of
glycosaminoglycans in various tissues, causing varied
symptoms, such as skeletal and extracellular matrix
deformities, and mental retardation.
• Mucopolysaccharidoses are caused by a deficiency of
any one of the lysosomal hydrolases normally
involved in the degradation of heparan sulfate
and/or dermatan sulfate .
Dr. Nikhat Siddiqi 47
 Functions of Proteoglcans
• Organizing extracellular matrix.
• Membrane bound syndecans, glycipcans bind to
specific signal molecules like growth factors
involved in cell cycle regulation.
• Because of their vast number of polyionic GAG
chains, the aggrecans trap large volume of water.
• Give strength, flexibility to cartilage and tensile
strength to collagen fibers.

Dr. Nikhat Siddiqi 48

 Glycoproteins
• Proteins that are linked covalantly to
carbohydrates through N- or 0- linkages.
• Carbohydrate content varies from 1% to more
than 85% of total weight.
• Carbohydrates include monosaccharides or
disaccharides such as those attached to
collagen or branched oligosaccharides found
on plasma glycoproteins.

Dr. Nikhat Siddiqi 49

 Polysaccharides
• Two broad classed viz., N-linked and O-linked.
• N-linked are attached to polypeptides by an N-
glycosidic bond with the side chain amide
group of amino acid asparagine.
• O-linked are attached to polypeptides by side
chain hydroxyl group of the amino acid serine
or threonine in a polypeptide chain or the
hydroxyl group of membrane lipids.

Dr. Nikhat Siddiqi 50

Polysaccharides linked to polypeptides

Dr. Nikhat Siddiqi 51

 Differences between Glycoproteins and
Protoglycans
• They differ from the proteoglycans (which
might be considered a special case of
glycoproteins) in that the length of the
glycoprotein's carbohydrate chain is relatively
short (usually 2–10 sugar residues in length,
although they can be longer).

Dr. Nikhat Siddiqi 52

 Differences between Glycoproteins and
Protoglycans ---cont
• In addition, whereas glycosaminoglycans have
diglucosyl repeat units, the carbohydrates of
glycoproteins do not have serial repeats.
• The glycoprotein carbohydrate chains are
often branched instead of linear, and may or
may not be negatively charged.

Dr. Nikhat Siddiqi 53

• Glycoproteins contain highly variable amounts
of carbohydrate.
• For example, immunoglobulin IgG, contains
less than 4% of its mass as carbohydrate,
whereas human gastric glycoprotein (mucin)
contains more than 80% carbohydrate.

Dr. Nikhat Siddiqi 54

 Functions of glycoproteins
• Membrane-bound glycoproteins participate in a broad
range of cellular phenomena, including cell surface
recognition (by other cells, hormones (insulin
receptors), and viruses),
• cell surface antigenicity (such as the blood group
antigens),
• as components of the extracellular matrix and
• of the mucins of the gastrointestinal and urogenital
tracts, where they act as protective biologic lubricants.

Dr. Nikhat Siddiqi 55

Functions of Glycoproteins

Dr. Nikhat Siddiqi 56

• Sialic acid residues are responsible for high
viscosity and luricating properties of saliva.
• Cellular adhesion eg selectins (transient cell-
cell interaction), intergins (cell attachment to
components of extracellular matrix) and
cadherins (calcium dependent binding of cells
to each other within tissue.

Dr. Nikhat Siddiqi 57

Dr. Nikhat Siddiqi 58