BIOMOLECULES
Carbohydrates
Module II (Part III)
Integrated MSc Semester II
2020-2025 batch
• Heteropolysaccharides are made up of more than one type of monosaccharide
unit.
• In general, most naturally occurring heteropolysaccharides are attached with
peptides, protein and lipids.
• Some of the common heteropolysaccharides are
1) Peptidoglycans
2) Agarose
3) Glycosaminoglycans (GAGs)
Bacterial and Algal Cell Walls Contain Structural Heteropolysaccharides
• The rigid component of bacterial cell walls (peptidoglycan) is a
heteropolymer of alternating (𝛃1→4)-linked N-
acetylglucosamine and N-acetylmuramic acid residues.
• The linear polymers lie side by side in the cell wall, cross-linked
by short peptides, the exact structure of which depends on the
bacterial species.
• The enzyme lysozyme kills bacteria by hydrolyzing the (𝛃1→4)
glycosidic
• Penicillin and related antibiotics kill bacteria by preventing
synthesis of the cross- links, leaving the cell wall too weak to
resist osmotic lysis.
Agarose
• Certain marine red algae (Gelidium, Gracilaria),
including some of the seaweeds, have cell walls that
contain agar
• Agar is a complex mixture of polysaccharides, all with
the same backbone structure but subs=tuted to
varying degrees with sulfate and pyruvate.
• Agarose is an alterna=ng copolymer 1,3-linked β-D-
galactose and 1,4-linked 3,6-anhydro-α-L-galactose,
infrequently subs=tuted with carboxylate, pyruvate
and/or sulfate residues.
Agarose
• Agarose gels are used as inert supports for the
electrophore=c separa=on of nucleic acids, an
essen=al part of the DNA-sequencing process
• Agar is also used to form a surface for the growth of 3,6-anhydro-alpha-L-galactopyranose is an
bacterial colonies. anhydrohexose obtained by formation of a ring
across the 3 and 6 positions of alpha-L-
• Another commercial use of agar is for the capsules in galactopyranose.
which some vitamins and drugs are packaged; the
dried agar material dissolves readily in the stomach
and is metabolically inert.
Glycosaminoglycans Are Heteropolysaccharides of the Extracellular Matrix
• The extracellular space in the tissues of multicellular animals is filled with a gel-like material,
the extracellular matrix (ECM), also called ground substance, which holds the cells together
and provides a porous pathway for the diffusion of nutrients and oxygen to individual cells.
• These heteropolysaccharides, the glycosaminoglycans, are a family of linear polymers
composed of repeating disaccharide units
• They are unique to animals and bacteria and are not found in plants.
• One of the two monosaccharides is always either N-acetylglucosamine or N-
acetylgalactosamine; the other is in most cases a uronic acid, usually D-glucuronic or L-iduronic
acid.
• Some of the examples of glycosaminoglycans are hyaluronic acid, chondroitin sulphate,
heparin, dermatan sulphate and keratin sulphate.
Hyaluronan (hyaluronic acid)
• The glycosaminoglycan hyaluronan (hyaluronic acid)
contains alterna=ng residues of D-glucuronic acid and N-
acetylglucosamine.
• With up to 50,000 repeats of the basic disaccharide unit,
hyaluronan has a molecular weight of several million; it
forms clear, highly viscous solu=ons that serve as
lubricants in the synovial fluid of joints and give the
vitreous humor of the vertebrate eye its jellylike
consistency (the Greek hyalos means “glass”; hyaluronan
can have a glassy or translucent appearance).
• Hyaluronan is also a component of the extracellular
matrix of car=lage and tendons, to which it contributes
tensile strength and elas=city
• Hyaluronidase, an enzyme secreted by some pathogenic
bacteria, can hydrolyze the glycosidic linkages of
hyaluronan, rendering =ssues more suscep=ble to
bacterial invasion.
• In many animal species, a similar enzyme in sperm
hydrolyzes an outer glycosaminoglycan coat around the
ovum, allowing sperm penetra=on.
Chondroi1n sulfate
• ChondroiCn sulphate or ChondroiCn-4-sulphate is a
major polysaccharide of carClage, which contains
alternaCng units of D-Glucuronic acid and N-Acetyl-
D-galactosamine.
• The linkage is similar to hyaluronic acid and the N-
acetyl galactosamine is sulphated at 4th posiCon.
• ChondroiCn-4-sulfate (chondros = carClage) is a
major consCtuent of various mammalian Cssues
(bone, carClage, tendons, heart, valves, skin,
cornea etc.).
Dermatan sulfate
• The name dermatan sulfate is derived from
the fact that this compound mostly occurs in
the skin.
• It is also present in blood vessels and heart
valves. It is structurally related to chondroitin-
4-sulfate.
• The only difference is that there is an
inversion in the configuration around C5 of D-
glucuronic acid to form L-iduronic acid.
• It is composed of alternating units of L-
iduronic acid and N- acetyl galactosamine –4
– sulphate linked by β - 1,3 linkage and
repeating disaccharide by β - 1,4 linkage.
Keratan sulfates
• Keratan sulfates (Greek keras, “horn”) have no
uronic acid and their sulfate content is
variable.
• It is made up of repeating units of
disaccharides composed of D-galactose and N-
acetylglucosamine-6-sulfate linked by β-1, 4
linkages.
• The disaccharide units are joined together by
β-1, 3 linkage
• They are present in cornea, cartilage, bone,
and a variety of horny structures formed of
dead cells: horn, hair, hoofs, nails, and claws.
Heparan sulfate
• Heparan sulfate (Greek he p ̄ ar, “liver”; it was
originally isolated from dog liver) is produced by all
animal cells and contains variable arrangements of
sulfated and nonsulfated sugars.
• The sulfated segments of the chain allow it to
interact with a large number of proteins, including
growth factors and ECM components, as well as
various enzymes and factors present in plasma.
• Heparin is a fracConated form of heparan sulfate
derived mostly from mast cells (a type of leukocyte).
• Heparin is a therapeuCc agent used to inhibit
coagulaCon through its capacity to bind the protease
inhibitor anCthrombin.
• Heparin binding causes anNthrombin to bind to and inhibit thrombin, a protease
essenNal to blood cloOng.
• The interacNon is strongly electrostaNc; heparin has the highest negaNve charge
density of any known biological macromolecule.
• Purified heparin is rouNnely added to blood samples obtained for clinical analysis,
and to blood donated for transfusion, to prevent cloOng.
Summary of the composi>on, proper>es, roles, and occurrence of the polysaccharides