What are Biomolecules?

All living organisms are made up of a fundamental unit called the cell. The cell
consists of organic and inorganic compounds and elemental analysis of the cell shows
that it is made of various elements such as carbon, hydrogen, oxygen, chlorine etc. All
carbon-containing compounds found in living organisms are termed as biomolecules.

Biomolecules are defined as any organic molecule present in a living

cell which includes carbohydrates, proteins, fats etc. Each
biomolecule is essential for body functions and manufactured within
the body. They can vary in nature, type, and structure where some
may be straight chains, some may be cyclic rings or both. Also, they
can vary in physical properties such as water solubility, melting
points.
 CARBOHYDRAT
ES

1. Role & Significance of

Carbohydrates
2. Monosacharides
3. Oligosacharides
4. Polysacharides
5. Glyconoconjugates
ROLE OF CARBOHYDRATES

• As a major energy source for living

organisms (glucose is a principal energy source in animal and plants)

• As a means of transporting energy ( exp: sucrose in

plant tissues)

• As a structural material ( cellulose in plants, chitin in insects, building

.
blocks of nucleotides)

• As a precursor for other biomolecules (purine,

pyrimide)
SIGNIFICANCE OF CARBOHYDRATES

• Carbohydrates are the most abundant

biomolecules in nature, having a direct link
between solar energy and the chemical bond
energy in living organisms.
• Source of rapid energy production
• Structural building blocks of cells
• Components of several metabolic pathways
• Recognition of cellular phenomena, such as
cell recognition and binding (e.g., by other
cells, hormones, and viruses)
 CARBOHYDRATES

Carbohydrate : compounds contains H, C & O with the comp : (CH 2O)n

(Hydrate of carbon)
Carbohydrates : Consist of sugar (saccharum)
Sugars : compound that contains alcohol & carbonyl functional group

Carbonyl func.group : >C=o

Adehyde  aldose
Ketone  ketose
Examples:
 Classification

Carbohydrate

Mono Oligo Poly

Glyconoconjugates
saccharide saccharide saccharide

Glucose, fructose cellulose, chitin, glycoproteins

Ribose (aldopentose) disaccharides
starch, glycogen, and
Deoxy ribose Glycoproteins
glucoaminoglycans proteoglycans
(bacterial cell
walls
MONOSACHARIDES
Monosaccharides

Sub sections :
• 2.1 Properties & classification
• 2.2 Stereoisomers
• 2.3 Cyclic structure
• 2.4 Important Reactions
• 2.5 Important monosach
• 2.6 glycoproteins and proteoglycans
• 2.7 Monosaccharide derivatives
2.1 Monosach Properties& classification
• Colorless, crystalline solids
• Soluble in water but insoluble in nonpolar
solvents
• One of the carbon atoms is double-bonded to
an oxygen atom to form a carbonyl group;
each of the other carbon atoms has a hydroxyl
group.
• Carbohydrates with an aldehyde (-CHO) functional
group are called aldoses
e.g. glyceraldehyde (CH2OH-CHOH-CHO)

Those with a keto group (-C=O) are ketoses

(CH2OH-C=O-CH2OH)
e.g.dihydroxyacetone

• Classified according to the number of carbon

atoms they contain
Monosacharides : Exp. aldoses & ketoses

Aldotriose Aldotetrose Aldopentoses Aldohexose

Ketotriose Ketotetrose Ketopentose Ketohexose

2.2. MONOSACCHARIDES STEREOISOMERS
• Isomers: same chemical formulas, different structures
• Conformation : the spatial arrangement of substituent groups
• chiral centers: asymmetric carbons, i.e carbon atom with four different
substituents
• Enantiomers : mirror images Stereoisomers
• The simplest aldose, glyceraldehyde, contains one chiral center (the middle
carbon atom) and has two different optical isomers, or enantiomers

the projection in which the carbohydrate backbone is

drawn vertically with the carbonyl shown on the top.
D- and L- enantiomers
 2.3 Cyclic structure of monosacharides
In aqueous solution, monosaccharides with five or more carbon
atoms in the backbone occur predominantly as cyclic (ring)
structures in which the carbonyl group has formed a covalent
bond with the oxygen of a hydroxyl group along the chain.

The new chiral center in cyclic (c1) is called anomeric carbon

 Pyranoses& Furanoses

Pyranoses: six-membered ring compounds ( resemble

pyran )
Furanoses : fivemembered rings, (resemble furan)

The structure systematic names glucose & fructose

become
HAWORTH STRUCTURES
An English chemist
W.N. Haworth gave a
more accurate picture
of carbohydrate
structure. (Ref. P.205 of
textbook)
FISHER AND HAWORTH FORMS OF SUGAR
SUMMARY OF SUGAR STRUCTURES
• ISOMERS- compounds that have the same chemical formula e.g. fructose,
glucose, mannose, and galactose are isomers of each other having
formula C6H12O6.
• EPIMERS- refer to sugars whose configuration differ around one specific
carbon atom e.g. glucose and galactose are C-4 epimers and glucose and
mannose are C-2 epimers.
• ENANTIOMERS- a special type of isomerism found in pairs of structures
that are mirror images of each other. The mirror images are termed as
enantiomers and the two members are designated as D- and L- sugar. The
vast majority of sugars in humans are D-sugars.
• CYCLIZATION OF SUGARS- most monosaccharides with 5 or more carbon
atoms are predominately found in a ring form, where the aldehyde or
ketone group has reacted with an alcoholic group on the same sugar
group to form a hemiacetal or hemiketal ring.
Pyranose ring- if the ring has 5 carbons and 1 oxygen.
Furanose ring- if the ring is 5-membered (4 carbons and 1 oxygen
 2.4.IMPORTANT REACTIONS IN MONOSACCHARIDES

Monosaccharides undergo the following reactions :

1. Mutarotation
2. Oxidation
3. Reduction
4. Isomerization
5. Esterification
6. Glycoside formation
IMPORTANT REACTIONS IN MONOSACCHARIDES
Details
1. Mutarotation –
alfa and beta forms of sugars are readily interconverted when dissolved in water
2 Oxidation and reduction
in presence of oxidising agents, metal ions (Cu2+) and enzymes, monosacchs undergo several
oxidation reactions e.g. Oxidation of aldehyde group (R-CHO) yields aldonic acid; of terminal
CH2OH (alcohol) yields uronic acid; and of both the aldehyde and CH2OH gives aldaric acid.
The carbonyl groups in both aldonic and uronic can react with an OH group in the sam
3 REDUCTION
reduction of the aldehyde and ketone groups of monosacchs yield sugar alcohols (alditols)
Sugar alcohols e.g.sorbitol.
 IMPORTANT REACTIONS (Cont)

4. ISOMERIZATION
Monosaccharides undergo several types of isomerization e.g. D-glucose in alkaline solution for several hours
containn D-mannose and D-fructose. The conversion of glucose to mannose is termed s epimerization.

5 ESTERIFICATION
Free OH groups of carbohydrates react with acids to form esters. This reaction Can change the physical and
chemical propteries of sugar.

6. GLYCOSIDE FORMATION-
Hemiacetals and hemiketals reaction with alcohols to form the corressponding aceta or ketal (p.210 of
Text).On the contrary when a cyclic hemiacetal or hemiketal form of monosaccharide reacts with alcohol, the
new linkage is called glycosidic linkage and the compound glycoside.
Glycosides are formed when the anomeric (hemiac-etal or hemiketal)
hydroxyl group of a monosaccharide undergoes condensation with the
hydroxyl group of a second molecule, with the elimination of water. ... The
linkage resulting from such a reaction is known as a glycosidic bond.
https://youtu.be/fUKUwADHZt8
Isomerism: Classification # 1. D and L:
The designation of an isomer as D- or L-
form is determined by its spatial
configuration to the parent compound.
When the OH group around the carbon
atom adjacent to the terminal primary alco­
hol carbon (carbon atom 5 in glucose) is on
the right, the sugar is a member of the D
series.

When it is on the left, it is a member of the

L series. The majority of the
monosaccharides occurring in mam­malian
metabolism are of the D configuration.
Optical Isomer
When a beam of polarized light is passed
through a solution exhibiting optical
activity, it will be rotated to the right or to
the left in accord­ance with the type of
compound, i.e. the optical isomer, which is
present. A compound which causes
rotation of polarized light to the right is
said to be dextrorotatory and a plus (+)
sign is used to desig­nate the fact.
Rotation of the beam to the left
(levorotatory action) is designated by a
minus (-) sign.
Isomerism: Classification # 2. α- and β-
anomers:
The cyclic structure of glucose is retained
in solution, but isomerism takes place
about position 1. This is accomplished by
optical rotation (mutarotation) by which the
positions of -H and -OH groups are
changed around carbon.
Isomerism: Classification
# 3. Epimers:
Isomers formed as a result of interchange
of the -OH and -H on carbon atoms 2, 3
and 4 of glucose are known as epimers.
Biologically, the most important epimers of
glucose are mannose and galactose formed
by epimerization at carbons 2 and 4,
respectively. In the body, epimerization
takes place by the enzyme epimerase.
Isomerism: Classification # 4. Pyranose
and Furanose Ring Structures:
Haworth, in 1929, proposed a scheme in
which all sugars forming six-membered
rings are called pyranoses from their
relation to pyrane and those forming five-
membered rings furanoses after furane.

The amylene oxide form of glucose would

be called glucopyranose and the butylene
oxide form glucofuranose.

If a sugar is referred to by its ordi­nary

name only, the pyranose form is to be
inferred. The pyranose and furanose forms
of some sugars are set out below in
straight chain fonnulae as well as in ring
formulae.
REDUCING SUGARS

• All monosacchs are reducing sugars.

• They can be oxidised by weak oxidising agent such
as Benedict’s reagent
• Benedict's reagent is a solution of copper sulfate,
sodium hydroxide, and tartaric acid.
Aqueous glucose is mixed with Benedict's reagent and heated. The reaction reduces the
blue copper (II) ion to form a brick red precipitate of copper (I) oxide. Because of this,
glucose is classified as a reducing sugar .
 Isomerism: Classification # 5. Aldose-
ketose Isomerism:

Fructose has the same molecular formula as glucose but differs

in its structural formula since carbon 2 is a part of a > Co group,
which makes fructose a ketose rather than an aldose. Generally,
there is a free -H on carbon 1, the sugar is an al­dose, but if a –
CH2OH group is substituted, the sugar is a ketose
Alfa & beta GLYCOCIDIC BOND
2.5 IMPORTANT MONOSACCHARIDES
• GLUCOSE
• FRUCTOSE
• GALACTOSE
D-Glucose:
D-glucose (dextrose) is the primary fuel
in living cells especially in brain cells that
have few or no mitochondria.

Cells such as eyeballs have limited

oxygen supply and use large amount of
glucose to generate energy

Dietary sources include plant starch,

and the disaccharides lactose, maltose,
and sucrose
DIABETES (diabetes
mellitus)
• Characterized by high blood glucose levels that splills over
into the urine
• These high glucose levels impairs the insulin-stimulated
glucose entry into cells and starve the cells of insulin.
• This leads to ketosis or high levels of ketone bodies (acids)
that hinders the buffering capacity of the blood in the kidney,
which controls blood pH (by excreting excess H+ ions into the
urine).
• The H+ excretion is accompanied by the excretion ammonia,
sodium,potassium, and phosphate ions causing severe
dehydration
• This leads to excessive thirst symptom of diabetes and life-
threatening decrease in blood volume.
 Important monosaccharides. Cont

• FRUCTOSE
• D-fructose (levulose) is often referred as fruit sugar and
is found in some vegetables and honey
• This molecule is an important member of ketose
member of sugars
• It is twice as sweet as sucrose (per gram basis) and is
used as sweeting agent in processed food products
• It is present in large amounts in male reproductive tract
and is synthesised in the seminal vesicles.
Important monosaccharides. Cont....
• GALACTOSE
• is necessary to synthesize a variety of
biomolecules (lactose-in mammalary glands,
glycolipids, certain phospholipids,
proteoglycans, and glycoproteins)
• Galactose and glucose are epimers at carbon 4
and interconversion is catalysed by enzyme
epimerase.
• Medical problems – galactosemia (genetic
disorder) where enzyme to metabolize
galactose is missing; accumulation of
galactose in the body can cause liver damage,
cataracts, and severe mental retardation
2.7.MONOSACCHARIDE DERVATIVES
• URONIC ACIDS – formed when terminal
CH2OH group of a mono sugar is oxidised
• Important acids in animals – D-glucuronic acid
and its epimer L-iduronic acid
• In liver cells glucuronic acid combines with
steroids, certain drugs, and bilirubin to
improve water solubility therby helping the
removal of waste products from the body
• These acids are abundant in the connective
tissue carbohydrate components.
Mono sugar derivatives

• AMINO SUGARS –
• Sugars in which a hydroxyl group
(common on carbon 2) is replaced by an
amino group e.g. D-glucosamine and D-
galactosamine
• common constituents of complex
carbohydrate molecule found attached to
cellular proteins and lipids
• Amino acids are often acetylated e.g. N-
acetyl-glucosamine.
Mono sugar derivatives
• DEOXYSUGARS
• monosaccharides in which an - H has replaced
an – OH group
• Important sugars: L-fucose (formed from D-
mannose by reduction reactions) and 2-deoxy-
D-ribose
• L-fucose – found among carbohydrate
components of glycoproteins, such as those of
the ABO blood group determinates on the
surface of red blood cells
• 2-deoxyribose is the pentose sugar
component of DNA.
GLYCOSIDES
• Monosaccharides can be linked by glycosidic bonds (joining
of 2 hydroxyl groups of sugars by splitting out water
molecule) to create larger structures.
• Disaccharides contain 2 monosaccharides e.g. lactose
(galactose+glucose); maltose (glucose+glucose);
sucrose (glucose+fructose)
• Oligosaccharides – 3 to 12 monosaccharides units e.g.
glycoproteins
• Polysaccharides – more than 12 monosaccharides units e.g.
glycogen (homopolysaccharide) having hundreds of sugar
units; glycosaminoglycans (heteropolysaccharides) containing
a number of different monosaccharides species .
 DISACCHARIDES
AND
OLIGOSACCHARIDES
DISACCHARIDES AND
OLIGOSACCHARIDES
• Cnfigurations: alfa or beta ( 1,4, glycosidic
bonds or linkages; other linkages 1,1; 1,2;
1,3; 1,6)
• Digestion aided by enzymes. Defficiency of
any one enzyme causes unpleasant
symptoms (fermentation) in colon
produces gas [bloating of cramps].
• Most common defficiency, an ancestoral
disorder, lactose intolerance caused by
reduced synthesis of lactase
 Important sugars of Disaccharides
• LACTOSE
(milk sugar) disaccharide found in milk; composed of one
molecule of galactose and glucose linked through beta(1,4)
glycosidic linkage; because of the hemiacetal group of the
glucose component, lactose is a reducing sugar
Lactose intolerance
• Lactose (milk sugar) in infants is hydrolyzed by
intestinal enzyme lactase to its component
monosacch for absorption into the bloodstream
(galactose epimerized to glucose).
• Most adult mammals have low levels of beta-
galactosidase. Hence, much of the lactose they
ingest moves to the colon, where bacterial
fermentation generates large quantities of CO2, H2
and irritating organic acids.
• These products cause painful digestive upset
known as lactose intolerance and is common in the
African and Asian decent.
MALTOSE ( malt sugar)
An intermediate product of starch hydrolysis; it is a
disaccharide with an alfa(1,4) glycosidic linkage between
two D-glucose molecules; in solution the free anomeric
carbon undergoes mutarotation resulting in an equilibrium
mixture of alfa and beta – maltoses; it does not occur freely
in nature
• SUCROSE
common table sugar: cane sugar or beet sugar produced in
the leaves and stems of plants; it is a disaccharide containing
both alfa-glucose and beta-fructose residues linked by
alfa,beta(1,2)glycosidic bond.
• CELLOBIOSE
degradation product of cellulose containing two
molecules of glucose linked by a beta (1,4)
glycosidic bond; it does not occur freely in nature
OLIGOSACCHARIDE SUGARS
• Oligosaccharides are small polymers
often found attached to polypeptides in
glycoproteins and some glycolipids.
• They are attached to membrane and
secretory proteins found in
endoplasmic reticulum and Golgi
complex of various cells
• Two classes: N-linked and O-linked
 Section 4
POLYSACCHARIDES
4.1. Intro to Polysaccharides
4.2. Classification of Polisacharides
4.2.1. Homosacharides
4.2.2. Heteropolysacharides
Polysaccharides

• Composed of large number of monosaccharide units

connected by glycosidic linkages
• Classified on the basis of their main monosaccharide
components and the sequences and linkages between them,
as well as the anomeric configuration of linkages, the ring size
(furanose or pyranose), the absolute configuration (D- or L-)
and any other substituents present.
(http://www.lsbu.ac.uk/water/hypol.html)

• Polysaccharides are more hydrophobic if they have a greater

number of internal hydrogen bonds, and as their
hydrophobicity increases there is less direct interaction with
water
• Divided into homopolysaccharides (e.g.Starch, glycogen,
cellulose, and chitin) & heteropolysaccharides
(glycoaminoglycans or GAGs, murein).
4.2. Classification of Polisacharides
4.2.1.HOMOSACCHARIDES

• Found in abundance in nature

• Important examples: starch, glycogen, cellulose,
and chitin
• Starch, glycogen, and cellulose all yield D-glucose
when they are hydrolyzed
• Cellulose - primary component of plant cells
• Chitin – principal structural component of
exoskeletons of arthropods and cell walls of many
fungi; yield glucose derivative N-acetyl glucosamine
when it is hydrolyzed.
STARCH (Homosaccharide)
• A naturally abundant nutrient carbohydrate, (C 6H10O5)n, found chiefly in
the seeds, fruits, tubers, roots, and stem pith of plants, notably in corn,
potatoes, wheat, and rice, and varying widely in appearance according to
source but commonly prepared as a white amorphous tasteless powder.
• Any of various substances, such as natural starch, used to stiffen cloth, as
in laundering.
• Two polysaccharides occur together in starch: amylose and amylopectin
• Amylose – unbranched chains of D-glucose residues linked with
alfa(1,4,)glycosidic bonds
• Amylopectin – a branched polymer containing both alfa(1,4,) and alfa(1,6)
glcosidic linkages; the alfa(1,6) branch points may occur every 20-25
glucose residues to prevent helix formation
• Starch digestion begins in the mouth; alfa-amylase in the saliva initiates
hydrolysis of the gycosidic linkages
GLYCOGEN (Homosaccharide)
• Glycogen is the storage form of glucose in animals and humans which is
analogous to the starch in plants.
• Glycogen is synthesized and stored mainly in the liver and the muscles.
• Structurally, glycogen is very similar to amylopectin with alpha acetal
linkages, however, it has even more branching and more glucose units are
present than in amylopectin.
• Various samples of glycogen have been measured at 1,700-600,000 units
of glucose.
• The structure of glycogen consists of long polymer chains of glucose units
connected by an alpha acetal linkage.
• The branches are formed by linking C # 1 to a C # 6 through an acetal
linkages.
• In glycogen, the branches occur at intervals of 8-10 glucose units, while in
amylopectin the branches are separated by 12-20 glucose units.
STRUCTURE OF GLYCOGEN
CELLULOSE (Homosaccharide)
• Cellulose is found in plants as microfibrils (2-20 nm diameter and 100 - 40 000 nm long). These
form the structurally strong framework in the cell walls.
• Cellulose is mostly prepared from wood pulp
• Cellulose is a linear polymer of β-(1 4)-D-glucopyranose units in 4C1 conformation. The fully
equatorial conformation of β-linked glucopyranose residues stabilizes the chair structure,
minimizing its flexibility
• Cellulose has many uses as an anticake agent, emulsifier, stabilizer, dispersing agent, thickener,
and gelling agent but these are generally subsidiary to its most important use of holding on to
water.
• Water cannot penetrate crystalline cellulose but dry amorphous cellulose absorbs water
becoming soft and flexible.
• Purified cellulose is used as the base material for a number of water-soluble derivatives e.g.
Methyl cellulose, carbomethycellulose
CELLULOSE
CHITIN (Homosaccharide)
• Chitin is a polymer that can be found in anything from the shells
of beetlesto webs of spiders. It is present all around us, in plant
and animal creatures.
• It is sometimes considered to be a spinoff of cellulose, because
the two are very molecularly similar.
• Cellulose contains a hydroxy group, and chitin contains
acetamide.
• Chitin is unusual because it is a "natural polymer," or a
combination of elements that exists naturally on earth.
• Usually, polymers are man-made. Crabs, beetles, worms and
mushrooms contain large amount of chitin.
• Chitin is a very firm material, and it help protect an insect against
harm and pressure
Structure of the chitin molecule, showing two of the N-acetylglucosamine units that
repeat to form long chains in beta-1,4 linkage.
CHITOSAN
• A spinoff of chitin that has been discovered by the market is
chitosan. This is a man-made molecule that is often used to
dye shirts and jeans in the clothing industry.
• Chitosan can be used within the human body to regulate diet
programs, and researchers are looking into ways in which it
can sure diseases.
• Chitin, the polysaccharide polymer from which chitosan is
derived, is a cellulose-like polymer consisting mainly of
unbranched chains of N-acetyl-D-glucosamine. Deacetylated
chitin, or chitosan, is comprised of chains of D-glucosamine.
When ingested, chitosan can be considered a dietary fiber.
HETEROPOLYSACCHARIDES

• Are high-molecular-weight carbohydrate polymers

more than one kind of monosaccharide
• Important examples include glycosaminoglycans
(GAGs) – the principle components of
proteoglycans and murein, a major component of
bacterial cell walls.
GAGs - high-molecular-weight carbohydrate
polymers
• Glycosaminoglycans forming the
proteoglycans are the most abundant
heteropolysaccharides in the body. They
are long unbranched molecules containing
a repeating disaccharide unit. Usually one
sugar is an uronic acid (either D-glucuronic
or L-iduronic) and the other is either
GlcNAc or GalNAc. One or both sugars
contain sulfate groups (the only exception
is hyaluronic acid).
• GAGs are highly negatively charged what
is essential for their function.
 THE SPECIFIC GAGs OF PHYSIOLOGICAL
SIGNIFICANCE

Hyaluronic acid
Occurence : synovial fluid, ECM of loose connective
tissue
Hyaluronic acid is unique among the GAGs because
it does not contain any sulfate and is not found
covalently attached to proteins. It forms non-
covalently linked complexes with proteoglycans in
the ECM.
Hyaluronic acid polymers are very large (100 -
10,000 kD) and can displace a large volume of
water.
Hyaluronic acid (D-glucuronate + GlcNAc)
Dermatan sulfate (L-iduronate + GlcNAc sulfate)

Occurence : skin, blood vessels, heart

valves
Chondroitin sulfate (D-glucuronate + GalNAc sulfate)

Occurence : cartilage, bone, heart

valves ;
It is the most abundant GAG.
Heparin and heparan sulfate (D-glucuronate sulfate + N-sulfo-D-
glucosamine)

Heparans have less sulfate groups than heparins

Occurence :
Heparin :component of intracellular granules of mast cells lining the arteries of the lungs, liver
and skin Heparan sulfate : basement membranes, component of cell surfaces
Keratan sulfate ( Gal + GlcNAc sulfate)

Occurence : cornea, bone, cartilage ;

• Keratan sulfates are often aggregated with chondroitin sulfates.
MUREIN (Peptidoglycan)

• Peptidoglycan, also known as murein, is a polymer consisting of sugars and

amino acids that forms a mesh-like layer outside the plasma membrane of
eubacteria.

• The sugar component consists of alternating residues of β-(1,4) linked N-

acetylglucosamine and N-acetylmuramic acid residues.

• Attached to the N-acetylmuramic acid is a peptide chain of three to five

amino acids.

• The peptide chain can be cross-linked to the peptide chain of another strand
forming the 3D mesh-like layer.

• Some Archaea have a similar layer of pseudopeptidoglycan.

• Peptidoglycan serves a structural role in the bacterial cell
wall, giving the wall shape and structural strength, as well as
counteracting the osmotic pressure of the cytoplasm.

• Peptidoglycan is also involved in binary fission during

bacterial cell reproduction.

• The peptidoglycan layer is substantially thicker in Gram-

positive bacteria (20 to 80 nm) than in Gram-negative
bacteria (7 to 8 nm), with the attachment of the S-layer.

• Peptidoglycan forms around 90% of the dry weight of Gram-

positive bacteria but only 10% of Gram-negative strains.

• In Gram-positive strains, it is important in attachment roles

and serotyping purposes.
 SECTION 5
GLYCOCONJUGATES
5.1. Intro to
glycoconjugates
5.2. glycoproteins
5.3. glycosylation
5.4. proteoglycans
5.1. Intro to glycoconjugates
• They are compounds that result from covalent
linkages of carbohydrate molecules to both
proteins and lipids.
• They have a profound effects on the functions
of individual cells as weell as cell-cell
interactions of multicellular organisms.
• Two classes of carbohydrate-protein
conjugate: glycoproteins and proteoglycans.
• The glycolipids (oligosaccharide-containing
lipid molecules) are found predominately on
the outer surface of plasma membrane.
5.2.glycoproteins
• Glycoprotein carbohydrate chains are highly diverse. They are
formed by glycosylation and classified into two groups:
1. N-linked oligosaccharides
2. O-linked oligosaccharides
• The N-linked oligosaccharides have a minimum of 5 sugar
residues
• N-linked attached to polypeptides by an N-glycosidic bond
with a chain amide group of amino acid and asparagine
• O-linked oligosaccharides are generally short (1-4 sugar
residues)
• O-linked are attached to polypeptides by the side chain
hydroxyl group of amino acids serine or threonine in
polypeptide chains or hydroxyl groups of membrane lipids
5.3.glycosylation
• Glycosylation is the process or result of addition of
saccharides to proteins and lipids
• The process plays an important role in the synthesis of
membrane and secreted proteins
• Majority of proteins synthesized in the rough ER undergo
glycosylation
• It is an enzyme -directed site-specific process.
• Two types of glycosylation exist: N-linked glycosylation to the
amide nitrogen of asparagine side chains and O-linked
glycosylation to the hydroxy oxygen of serine and threonine
side chains.
• Glycosylation may play a role in cell-cell adhesion (a
mechanism employed by cells of the immune system), as
well.
GLYCOPROTEIN FUNCTIONS
• Types of glycoproteins: asparagine-linked carbohydrate;
mucin-type cabohydrate
• Examples: glycophorin (membrane protein, source – human
RBC, % carbohydrate - 60); potato lectin (lectin, carbohydrate
binding proteins, source – potato, % carbohydrate – 50)
• Functions: Many glycoproteins have structural functions:
constituent of the cell wall; form connective tissues such as
collagen; found in gastrointestinal mucus secretions; used as
protective agents and lubricants ;found abundantly in the
blood plasma.
• The human blood groups A, B, AB, and O depend on the
oligosaccharide part of the glycoprotein on the surface of
erythrocyte cells. The terminal monosaccharide of the
glycoprotein at the nonreducing end determines blood group.
BLOOD GROUPS
TYPE TERMINAL SUGAR
A N-acetylgalactosamine
B -D-galactose
AB both the above
O neither of the above
O is the “universal donor”
AB is the “universal
acceptor”
Oligosaccharides are antigeneic determinants

• Carbohydrates on cell surfaces are

immunochemical markers.
• ABO blood group antigens are oligosaccharide
components of glycoproteins and glycolipids on
the surfaces of individual cells, besides blood cells.
• Individuals with type A cells have A antigens on
their cell surfaces and carry anti-B antibodies
• Those with type B cells which bear B antigens, carry
anti-A antibodies
• Those with type AB cells, which have both
A and B antigens, carry neither anti-A nor
anti-B antibodies
• Type O individuals whose cells bear
neither antigen, carry both anti-A and
anti-B antibodies.
• Transfusion of type A blood group into a
type B individual, results in an anti-A
antibody- A antigen reaction.
• This reaction clumps together
(agglutinates) the transfused erythrocytes,
resulting in an often fatal blockage of
blood vessels
Functions of glycoproteins (elaborated)
http://www.cs.stedwards.edu/chem/Chemistry/CHEM43/CHEM43/Glycoproteins/Glycoproteins.HTML

Carbohydrates and proteins by themselves serve in a vast

number of biological functions,linking the two together
results in a macromolecule with an extremely large number
of functions.
• Structural: Glycoproteins are found throughout matrices.
They act as receptors on cell surfaces that bring other cells
and proteins (collagen) together giving strength and support
to a matrix.
• In nerve tissue glycoproteins are abundant in gray matter
and appear to be associated with synaptosomes, axons, and
microsomes.
• Protection: Human lacrimal glands produce a glycoprotein
which protects the corneal epithelium from desiccation and
foreign particles. Human sweat glands secrete glycoproteins
which protect the skin from the other excretory products that
could harm the skin
Functions of glycoproteins (further elaborated-1)

• Prothrombin, thrombin, and fibrinogen are all glycoproteins

that play an intricate role in the blood clotting mechanism
• In certain bacteria the slime layer that surrounds the
outermost components of cell walls are made up of
glycoproteins of high molecular weight. In addition to forming
these s-layers, glycoproteins also function as bacterial
flagella. These are made up of bundles of glycoproteins
protruding from the cell's surface. Their rotation provides
propulsion.
• In plants, glycoproteins have roles in cell wall formation,
tissue differentiation, & embryogenesis.
• Reproduction: Glycoproteins found on the surface of
spermatozoa appear to increase a sperm cell's attraction for
the egg by altering the electrophoretic mobility of the plasma
membrane.
Functions of glycoproteins (further elaborated-2)

• Adhesion: Glycoproteins serve to adhere

cells to cells and cells to substratum.
• Hormones: There are many glycoproteins
that function as hormones such as human
chorionic gonadotropin (HCG) which is
present in human pregnancy urine.
Another example is erythropoietin which
regulates erythrocyte production
• Enzymes: Glycoprotein enzymes are of
three types. These are oxidoreductases,
transferases, and hydrolases.
 Functions of glycoproteins (further elaborated-3)

• Carriers: Glycoproteins can bind to certain molecules and

serve as vehicles of transport. They can bind to vitamins,
hormones, cations, and other substances.
• Inhibitors: Many glycoproteins in blood plasma have shown
antiproteolytic activity. For example, the glycoprotein a1-
antichymotrypsin inhibits chymotrypsin.
• Immunological: The interaction of blood group substances
with antibodies is determined by the glycoproteins on
erythrocytes. Many immunoglobulins are actually
glycoproteins.
B and T cells contain surface glycoproteins that attract
bacteria to these sites and bind them. In much the same
manner, glycoproteins can direct phagocytosis. Because the
HIV virus recognizes the receptor protein CD4, it binds to
helper T cells which contain it.
CELL MEMBRANE
• The cell membrane is a fluid mosaic of lipids, proteins, and
carbohydrates.
• Membrane carbohydrates are usually branched
oligosaccharides with fewer than 15 sugar units.
• Some of these oligosaccharides are covalently bonded to
lipids, forming molecules called glycolipids.
• Most are covalently bonded to proteins, which are thereby
glycoproteins.
• Plants produce pectin, major component of cell wall.
• The oligosaccharides on the external side of the plasma
membrane vary from species to species
• The diversity of the molecules and their location on the cell's
surface enable oligosaccharides to function as markers that
distinguish one cell from another.
THE MOSAIC OF CELL’S MEMBRANE
CELL MEMBRANE MATRIX
• The biological membrane is a collage of
many different proteins embedded in the
fluid matrix of the lipid bilayer.

• The lipid bilayer is the main fabric of the

membrane, and its structure creates a semi-
permeable membrane.

• The hydrophobic core impedes the

transport of hydrophilic structures, such as
ions and polar molecules but enable
hydrophobic molecules, which can dissolve
in the membrane, cross it with ease.
Protein layer of cell membrane
• Proteins determine most of the
membrane's specific functions.

• The plasma membrane and the

membranes of the various organelles each
have unique collections of proteins.

• For example, to date more than 50 kinds

of proteins have been found in the plasma
membrane of red blood cells.
5.4. PROTEOGLYCANS
• Proteoglycans represent a special class of glycoproteins that
are heavily glycosylated.
• They consist of a core protein with one or more covalently
attached glycosaminoglycan chain(s).
• These glycosaminoglycan (GAG) chains are long, linear
carbohydrate polymers that are negatively charged under
physiological conditions, due to the occurrence of sulphate
and uronic acid groups.
• Proteoglycans can be categorised depending upon the
nature of their glycosaminoglycan chains. These chains may
be:
1. chondroitin sulfate and dematan sulfate
2. heparin and heparin sulfate
3. keratan sulfate
• Proteoglycans can also be categorised
by size.
• Example of large proteoglycan is
aggrecan.
• Aggrecan, is the major proteoglycan in
cartilage, present in many adult tissues
including blood vessels and skin.
• The small leucine rich repeat
proteoglycans (SLRPs) include decorin,
biglycan, fibromodulin and lumican.
SYNTHESIS OF PROTEOGLYCANS
• The protein component of proteoglycans is
synthesized by ribosomes and translocated into
the lumen of the rough endoplasmic reticulum.
• Glycosylation of the proteoglycan occurs in the
Golgi apparatus in multiple enzymatic steps.
• First a special link tetrasaccharide is attached to a
serine side chain on the core protein to serve as a
primer for polysaccharide growth.
• Then sugars are added one at the time by glycosyl
transferase.
• The completed proteoglycan is then exported in
secretory vesicles to the extracellular matrix of the
cell.
Structure of proteoglycans
• The GAGs extend perpendicular from the core protein in a bottlebrush-
like structure.
• The linkage of GAGs such as (heparan sulfates and chondroitin sulfates) to
the protein core involves a specific trisaccharide linker
• Some forms of keratan sulfates are linked to the protein core through an
N-asparaginyl bond.
• The protein cores of proteoglycans are rich in Ser and Thr residues which
allows multiple GAG attachment.
FUNCTION OF PROTEOGLYCANS

• Proteoglycans are a major component of the animal extracellular matrix, the

'filler' substance existing between cells in an organism.
• Individual functions of proteoglycans can be attributed to either the protein
core or the attached GAG chain.
• In extracellular matrix, they form large complexes, with other proteoglycans, to
hyaluronan and to fibrous matrix proteins (such as collagen).
• They are also involved in binding cations (such as sodium, potassium and
calcium) and water, and also regulating the movement of molecules through the
matrix.
• They can affect the activity and stability of proteins and signalling molecules
within the matrix.
ROLE OF PROTEOGLYCANS
http://www.cryst.bbk.ac.uk/pps97/assignments/projects/emilia/Proteoglycans.HTM

• GAG dependent functions can be divided into two classes:

the biophysical and the biochemical.

• The biophysical functions depend on the unique properties

of GAGs : the ability to fill the space, bind and organize water
molecules and repel negatively charged molecules. Because
of high viscosity and low compressibility they are ideal for a
lubricating fluid in the joints. On the other hand their rigidity
provides structural integrity to the cells and allows the cell
migration due to providing the passageways between cells.

For example the large quantities of chondroitin sulfate and

keratan sulfate found on aggrecan play an important role in
the hydration of cartilage. They give the cartilage its gel-like
properties and resistance to deformation.
Role of proteoglycans contd.
• The other, more biochemical functions of
GAGs are mediated by specific binding of
GAGs to other macromolecules, mostly
proteins. Proteoglycans participate in cell
and tissue development and physiology.

• Hurler’s syndrome: (refer Text) disease

related with proteoglycan metabolism
where excessive accumulation of dermatin
sulfate due to deficiency of a specific
enzyme may cause mental retardation,
skeletal deformity ansd death in early
childhood.
SUMMARY
• Monosaccharides, the simplest carbohydrates, are classified
as aldoses or ketoses.
• The cyclic hemiacetal and hemiketal forms of monosacchs
have either alfa or beta configuration at their anomeric
carbon.
• Monosacch derivatives include aldonic acids, uronic acids,
deoxy sugars, amino sugars, alfa & beta glycosides.
• Disaccharides simplest polysaccharides occuring as hydrolysis
products of larger molecules e.g. Lactose,sucrose
• Oligosaccharides play important roles in determining protein
structure and in cell-surface recognition phenomena.
Oligosacchs with 3 or more sugar residues are mostly found
in plants.
Summary contd. -1
• POLOYSACCHARIDES consist of
monosacchs linked by glycosidic bonds.
• Cellulose and chitin are structural
polysacchs with beta(1-4) linkages that
adopt rigid and extended structures.
• The storage polysacchs starch and
glycogen consist of alfa-glycosidically
linked glucose residues
• Glycosaminoglycans are unbranched
polysacchs containing uronic acids and
amino sugars that are often sulfated
Summary contd.-2
• GLYCOCONJUGATES: Proteoglycans &
glycoproteins play important roles in
information transfer in living organisms.

• Proteoglycans are enormous molecules

consisting of hyaluronate with attached
core proteins that bear numerous
glycosaminoglycans and oligosaccharides.
Found in the extracellular matrix of tissues

• Bacterial cell walls are made up of

peptidoglycan, a network of
polysaccharide and poypeptide chains.
Summary contd.-3
• Glycoproteins or Glycosylated proteins
may contain N-linked oligosacchs attached
to Asn (asparagine) or O-linked
oligosacchs attached to Ser or Thr (serine
or threonine) or both
• Different molecules of glycoproteins may
contain different sequences and locations
of oligosaccharides.
• Occur in cells in both soluble and
membrane bound forms, and in
extracellular fluids
END NOTES
• The destiny of a nation depends on the manner in
which it feeds itself.

• We eat to live, NOT, live to eat.

• Lower your carbohydrate consumption, but balance

it with the right amount of protein and fat.
• Describe, Discuss, and compare the classification,
structure and function of carbohydrates and its
derivatives.