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Manoj Sigdel

Carbohydrates
Polyhydroxy aldehydes or ketones, or
substances that yield such compounds on
hydrolysis
Many, but not all, carbohydrates have the
empirical formula (CH2O)n; some also contain
nitrogen, phosphorus, or sulfur
Most abundant organic molecule in nature
Photosynthesis converts CO2 and H2O into

The term carbohydrate was originally coined


for this class of compounds as most of them
were hydrates of carbon or could be
represented by the general formula,
Cx(H2O)y.
Later, it was found that some of them, such
as deoxyribose (C5H10O4) and rhamnose
(C6H12O5) do not have the required ratio of
hydrogen to oxygen.
In addition, certain other carbohydrates are
now known to possess nitrogen (e.g.,
glucosamine, C6H13O5N), phosphorus or sulfur

Furthermore, formaldehyde (H.CHO or CH2O),


acetic acid (CH3.COOH or C2H4O2) and lactic
acid (CH3.CHOH.COOH or C3H6O3) which have
C, H and O and the ratio of H : O is also the
same as in water, but are not a
carbohydrates. Hence, the continued usage
of the term carbohydrate is for convenience
rather than exactness.
To accommodate a wide variety of
compounds, the carbohydrates are nowadays
broadly defined as polyhydroxy aldehydes or
ketones and their derivatives or as
substances that yield one of these
compounds on hydrolysis

Functions of
carbohydates
1) Are the major source of energy for man as
the oxidation of carbohydrates is the central
energy-yielding pathway in most
nonphotosynthetic cells. For example,
glucose is used in the human body for
energy production.
2) Some carbohydrates serve as reserve food
material in humans and in plants. For
example, glycogen in animal tissue and
starch in plants serves as reserve food
materials.

3) Carbohydrates are components of several


animal structure and plant structures.
In animals, carbohydrates are
components of skin (dermatan sulfate) ,
connective tissue (chondroitin sulfate)
tendons, cartilage and bone.
In plants, cellulose is a component of
wood and fiber.
Also serve as structural and protective
elements in the cell walls of bacteria (eg;
muerin)
4) Some carbohydrates are components of cell

5) Carbohydrates are components of nucleic


acids and blood group substances.
6) carbohydrate polymers (eg; hyaluronic acid)
lubricate skeletal joints and participate in
recognition and adhesion between cells.
7) Derivative of carbohydrates are drugs. For
example, a glycoside ouabain is used in
clinical medicine. Streptomycin an antibiotic
is a glycoside.

8) Aminosugars, derivatives of carbohydrates


are components of antibiotics like
erythromycin and carbomycin.
9) Ascorbic acid, a derivative of carbohydrate is
a water-soluble vitamin.
10) Survival of Antarctic fish in icy environment
is due to presence of anti-freeze
glycoproteins in their blood.

Classification of
carbohydrates
Are often referred to as saccharides
( Greek: sakcharon- sugar)
Carbohydrates are usually classified in 3
groups
Monosaccharides
Oligosaccharides
Polysaccharides

Monosaccharides (Greek, mono = one;


sakcharon= sugar)
Are compounds which possess a free
aldehyde (CHO) or ketone (C=O) group and
2 or more hydroxyl (OH) groups.
H

O
CH2OH

OH

HO

HO

OH

OH

OH

OH

CH2OH

D-glucose

CH2OH

D-fructose

Often called simple sugars. They are,


in fact, the simplest sugars and
cannot be hydrolyzed into smaller
units.
General formula: Cn(H2O)n or
CnH2nOn.

The monosaccharides may be subdivided into


trioses, tetroses, pentoses, hexoses, heptoses
etc., depending upon the number of carbon
atoms they possess; and as aldoses or ketoses,
depending upon whether they contain aldehyde
or ketone group
The suffix -oses is kept reserved for the aldoses
and the suffix - uloses is used for ketoses.
Thus, glucose is a hexose and fructose, a
hexulose. However, a few ketoses are named
otherwise, such as fructose (Latin; fructus =
fruit) as fruits are a good source of this sugar

Oligosaccharides (Greek: oligo = few)


Are compound sugars that yield 2 to 10
molecules of the same or different
monosaccharides on hydrolysis.
Accordingly, an oligosaccharide yielding 2
molecules of monosaccharide on hydrolysis is
designated as a dissaccharide, and the one
yielding 3 molecules of monosaccharide as a
trisaccharide and so on.
General formula of disaccharides is Cn(H2O)n
1 and that of trisaccharides is Cn(H2O)n 2 and so
on.

Eg;
Disaccharides Sucrose, Lactose, Maltose,
Cellobiose, Trehalose, Gentiobiose, Melibiose
Trisaccharides Rhamninose, Gentianose,
Raffinose
Rabinose, Melezitose
Tetrasaccharides Stachyose, Scorodose
Pentasaccharide Verbascose

Polysaccharides (Greek: poly = many)


Called as compound sugars and yield >10
molecules of monosaccharide units on
hydrolysis.
These may be further classified depending on
whether the monosaccharide molecules
produced as a result of the hydrolysis of
polysaccharides are of the same type
(homopolysaccharides) or of different type
(heteropolysaccharides).
Their general formula is (C6H10O5)x.

Homopolysaccharides Starch,
Glycogen, Inulin,
Cellulose,
Pectin, Chitin
Heteropolysaccharides Hyaluronic
acid,
Chondrotin sulfate,
dermatan sulfate,
keratan sulfate,
heparin

The Structure of
Glucose Can Be
Represented in
Three Ways

D-Glucose
A: straight chain form.
B: -D-glucose; Haworth
projection.
C: -D-glucose; chair form.

The straight-chain structural formula can


account for some of the properties of
glucose, but a cyclic structure is favored on
thermodynamic grounds and accounts for the
remainder of its chemical properties.
For most purposes, the structural formula is
represented as a simple ring in perspective
as proposed by Haworth
In this representation, the molecule is viewed
from the side and above the plane of the
ring.
By convention, the bonds nearest to the
viewer are bold and thickened.

PROPERTIES OF MONOSACCHARIDES
1) Optical Isomerism
) All the monosaccharides except
dihydroxyacetone contain at least one
asymmetric carbon atom and hence they
exhibit optical isomerism.
(The smallest monosaccharides, for which n =
3, are dihydroxyacetone and D and Lglyceraldehyde)

The two optical isomers of glyceraldehyde


containing one asymmetric carbon atom
are
D-glyceraldehyde and
L-glyceraldehyde

D vs L Designation
D&L
designations are
based on the
configuration
about the single
asymmetric C in
glyceraldehyde.

OH

HO

D-glyceraldehyde

OH

CH2OH

D-glyceraldehyde

L-glyceraldehyde

CHO
C

CH2OH

CH2OH

The lower
representations
are Fischer

CHO

CHO

CHO
HO

CH2OH

L-glyceraldehyde

Such mirror image isomers


are also called as

Sugar Nomenclature
For sugars with
more than one
chiral center, D or
L refers to the
asymmetric C
farthest from the
aldehyde or keto
group.

C
H C OH
HO C H
H C OH
H C OH
CH2OH
D-glucose

Most naturally
occurring sugars

C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose

D & L sugars are mirror


images of one another.

C
They have the same H C OH
name, e.g., D-glucoseHO C H
& L-glucose.
H C OH
H C OH
Other stereoisomers
CH2OH

have unique names,


D-glucose
e.g., glucose, mannose,
galactose, etc.

C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose

The number of stereoisomers is 2n, where


n is the number of asymmetric centers.

The 6-C aldoses have 4 asymmetric


centers. Thus there are 16 stereoisomers
(8 D-sugars and 8 L-sugars).

Though both forms of sugars are present in


nature D-isomer is abundant and sugars
present in the body are all D-isomers

2) Optical Activity
Monosaccharides except dihydroxy acetone
exhibit optical activity because of the
presence of asymmetric carbon atom.
If a sugar rotates plane polarized light to
right then it is called as dextrorotatory and
if a sugar rotates the plane polarized light
to the left then it is called as levorotatory.

Usually + sign or d indicates dextrorotation


and
sign or l indicates levorotation of a sugar.
Eg; D-glucose which is dextrorotatory is
designated as D(+) glucose and
D-fructose, which is levorotatory is
designated as D() fructose.
(The letter D does not indicate whether a
given sugar is dextro or levorotatory)

3) Epimers
Are those monosaccharides that differ in the
configuration of single specific carbonOH
group on carbons other than the 1st carbon
(anomeric carbon)

Glucose and Galactose are C4 epimers, while


Glucose and Mannose are C2 epimers
Ribulose and xylulose are also epimers. They
differ in the configuration of OH group on
third carbon atom ( C3 epimers)

4) Functional Isomerism
Functional isomers have same molecular formulae
but differ in their functional groups.
Eg; Glucose and Fructose have same molecular
formulae C6H12O6, but glucose contains aldehyde as
functional group and fructose contains keto group.
Hence, glucose and fructose are functional isomers.
This type of functional isomerism is also called as
aldose-ketose isomerism because aldose is an
isomer of ketose and vice versa.

O
CH2OH
C

HO

OH

OH

OH

OH

OH

HO

CH2OH

CH2OH

D-glucose

D-fructose

Both have the same formula: C6H12O6

5) Ring Structures
In solution, the functional aldehyde group of
glucose combines with hydroxyl group of 5th
carbon atom. As a result a 6 numbered
heterocyclic pyranose ring structure containing
5 carbons and one oxygen is formed.
The linkage between aldehyde group and
alcohol is called as hemiacetal linkage

Similarly, a 5 numbered furanose ring structure


is formed from fructose when keto group
combines with hydroxyl group on 5 carbon
atom.
The linkage between keto and alcohol group is
called hemi ketal linkage.

Both hemi acetal and hemi ketal are internal or

However,
Fructose forms either
a 6-member pyranose ring, by reaction
of the C2 keto group with the OH on
C6, or
a 5-member furanose ring, by reaction
of the C2 keto group with the OH on
C5.

Hemiacetal & hemiketal


formation
An aldehyde
can react
with an
alcohol to
form a
hemiacetal.
A ketone can
react with an
alcohol to

H
C

H
O

R'

OH

R'

OH

aldehyde

alcohol

hemiacetal

R
C

R
O

"R

OH

R'

ketone

"R

C
R'

alcohol

hemiketal

OH

6) Anomers
Those monosaccharides that differ in
configuration of OH groups on carbonyl
carbon (anomeric carbon) are called as
anomers.
Formation of ring structure of glucose
generates anomers of glucose, which are
designated as and forms.
These two forms of glucose differ in the
configuration of OH on carbonyl carbon or 1st
carbon atom.

H
HO
H
H

2
3
4
5
6

CHO
C

OH

D-glucose

OH

(linear form)

OH

CH2OH
6 CH2OH

6 CH2OH
5

H
4

OH

H
OH
3

OH

-D-glucose

OH

H
4

OH

H
OH
3

OH

OH

-D-glucose

Haworth projections represent the cyclic sugars as


having essentially planar rings, with the OH at the
anomeric C1:
(OH below the ring)
(OH above the ring).

H OH
4

HO
HO

H OH

H O
5

OH 1
OH

-D-glucopyranose

H O

HO
H
HO

H
H

OH

OH

-D-glucopyranose

Because of the tetrahedral nature of carbon


bonds, pyranose sugars actually assume a
"chair" or "boat" configuration, depending on
the sugar.
The representation above reflects the chair
configuration of the glucopyranose ring more
accurately than the Haworth projection.

7) Mutarotation
Mutatrotation is defined as the change
in specific optical rotation
representating the interconversion of
alpha and beta forms to form an
equilibrium mixture
and anomers of Glucose have different
optical rotations.
The specific rotation of a freshly prepared
glucose (anomer) solution in water is +
112.2 which gradually changes and attains
equilibrium with a constant value of +52.7.

The optical rotation of glucose is + 18.7


The equilbrium mixture contains 63%
anomer , 36% anomer withless than 1%
open and as well as form of Glucofuranose
In aqueous solution, theform is more
predominant due to its stable conformation
The and forms of glucose are
interconvertible which occurs through a linear
form

Mutarotation of fructose
Fructose also exhibit mutarotation
The pyranose ring is converted to furanose
ring, till an equilibrium is attained
Fructose has specific rotation of -92

Configuration of D- Aldoses
The representation of the configuration of
D-Aldoses by increasing the chain length
of an aldose by one carbon at a time is
known as Killiani Fischer synthesis
Among the D-aldoses, D-Glucose is the
only aldose monosaccharide that
predominantly occur in nature

Structural relationship between D-aldoses shown in Fischer


projection.

REACTIONS OF
MONOSACCHARIDES
1) Tautomerization or enolization
The process of shifting hydrogen atom from
one carbon atom to another to produce
enediols is known as tautomerism
Sugars possessing anomeric carbon undergo
tautomerism in alkaline solution
When glucose is kept in alkaline solution for
several hours, it undergoes isomerization to
form D-fructose and D-mannose

This reaction results in the formation of


common intermediate namely enediol for all
the three sugars
The enediols are highly reactive, hence sugars
in alkaline solution are powerful reducing
agents

2) Reducing properties
Sugars are classified as reducing and nonreducing based on the presence of free
aldehyde or keto group on anomeric carbon
In lab many tests are employed to identify the
reducing action of sugars. These include
Benedicts test
Fehlings test
Barfoeds test
The reduction is much more efficient in
alkaline medium due to the formation of
enediols

3) Oxidation
Depending on the oxidizing agent
used, the aldehyde or the ketone group
or the terminal alcohol or both may be
oxidised

4) Reduction
When treated with reducing agents such as
sodium amalgum, the aldehyde or the ketone
froup of monosaccharide is reduced to
corresponding alcohol

D-Glucose : D- Sorbitol
D-Galactose: D-Dulcitol
D-Mannose:
D-Mannitol
D-Fructose: D-Mannito
D-Sorbitol
D-Ribose:
D-ribitol

5) Dehydration
When treated with conc sulfuric acid,
monosaccharides undergo dehydration with an
elimination of 3 water molecules
Hexoses form hydroxy methyl furfural and
pentoses form furfural
These furfurals can condense with phenolic
compounds (alpha naphtol) to give coloured
product (purple ring)
This is the chemical basis of Molischs test
( characteristic test for carbohydrates)

6) Osazone formation
Phenylhydrazine in acetic acid, when
boiled with reducing sugars forms osazone

Glucosazone/ Fructosazone
Needle shaped

Lactosazone:
Puff ball shaped

Maltosazone:
Sunflower shaped

7) Formation of esters
Esterification of carbohydrate with
phosphoric acid is a common
reaction in metabolism
Eg; Glucose 6-phosphate and
Glucose 1-phosphate

8) Glycosides formation
Glycosides are formed when the hemiacetal
or hemiketal hydroxy group (of anomeric
carbon) of a carbohydrate reacts with hydroxy
group/ amino group of another carbohydrate
or non-carbohydrate
The bond formed is known as glycosidic bond
Are of two types:

A) O-glycosides
When hydroxyl group on anomeric
carbon of a sugar reacts with an alcohol
(sugar) O-glycoside is formed
) O-glycosidic linkage is present in
disaccharides, oligosaccharides and
polysaccharides. So, disaccharides,
oligosaccharides and polysaccharides are Oglycosides.

B) N-glycosides
N-Glycoside is formed when hydroxyl group
on anomeric carbon of sugar reacts with an
amine
N-glycosidic linkage is present in nucleotides,
RNA and DNA. So, nucleotides, RNA and DNA are
examples for N-glycosides.

9) Fermentation
Monosaccharides such as glucose,
fructose and mannose are readily
fermented by yeast.
The process of yeast fermentation is very
complex.
During this process, sugar phosphate and
sugar acid phosphate are formed.
Ordinarily, this process results in the formation
of alcohol and carbon dioxide.

Important monosaccharides in the


metabolic point of view are glucose,
fructose, galactose, ribose, erythrose and
glyceraldehyde.
Glucose is found in several fruit juice blood
of humans and in honey.
Galactose is a part of lactose.
Fructose is found in several fruit juices and
honey.
Commonly glucose is referred as dextrose.

Sugar Derivatives

1) Sugar acids
) Oxidation of aldo group of sugars produces aldonic
acids. Eg; oxidation of glucose produces gluconic and
) oxidation of terminal alcohol group (OH sixth carbon
atom) of glucose produces glucuronic acid or uronic
acid
) Uronic acids are components of mucopolysaccharides
and required for detoxification.
) Ketoses are not easily oxidized.
) Vitamin C or ascorbic acid is also sugar acid.

CHO

COOH
H

OH

HO

OH

OH

OH

OH

OH

HO

CH2OH

D-gluconic acid

COOH

D-glucuronic acid

2) Sugar alcohols
Reduction of aldose and keto groups of
sugar produces sugar alcohols or polyols
These polyols are intermediates of
metabolic reactions.

The alcohols formed from


glucose, galactose and fructose are
sorbitol, galactitol and mannitol/sorbitol,
respectively

3) Alditols (polyhydroxy alcohols)

Ribitol is a constituent of flavin coenzymes

Glycerol and myoinositol are components of lipids


Xylitol is sweetner used in sugarless gums and candies

CH2OH
H

OH

OH

OH

CH2OH

D-ribitol

4) Deoxy sugars
Sugars in which oxygen of a hydroxyl
group is removed leaving hydrogen.
Deoxyribose is an example
It is present in nucleic acids.
Fucose is a deoxy sugar present in
blood group substances.

5) Sugar phosphates
Breakdown of sugar in animals
involves formation of sugar
phosphates. Eg; Glucose-6phosphate

6) Amino sugars
CH2OH

CH2OH
H

O
H
OH

H
OH

OH
H

NH2

-D-glucosamine

O
H
OH

H
O OH

OH
H

CH3

-D-N-acetylglucosamine

amino sugar - an amino group substitutes for a


hydroxyl.
Eg; D-glucosamine, D-galactosamine
Amino group may be acetylated, as in N-

O
H3C

NH
R
H

COO

R=
OH

H
OH

HC

OH

HC

OH

CH2OH

N-acetylneuraminate
(sialic acid)
N-acetylneuraminate
(N-acetylneuraminic
acid,
also called sialic acid) is often found as a
terminal residue of oligosaccharide chains of
glycoproteins.

It is a derivative of N-acetylmannose and


pyruvic acid
Sialic acid imparts negative charge to
glycoproteins, because its carboxyl group tends
to dissociate a proton at physiological pH, as

DISACCHARIDES

1) Maltose
Contains two glucose units.
Anomeric carbon atom of first glucose and
carbon atom 4 of the second glucose are
involved in glycosidic linkage.
Glycosidic linkage of maltose is symbolized as
(14)

In the symbol, letter -indicates the


configuration of anomeric carbon atoms of
both glucose units and numbers indicates
carbon atoms involved in glycosidic linkage.
Systematic name: O--D glucopyranosyl-(14)-D glucopyranose.
Maltose is a reducing sugar because anomeric
carbon of second glucose is free.
Source:
Present in germinating cereals and in
barley
Commercial malt sugar contains
maltose

2) Lactose
It contains one glucose and one galactose.
The anomeric carbon atom of galactose and
carbon atom 4 of glucose are involved in
glycosidic linkage. It is symbolized as (14)
The systematic name: O--D galactopyranosyl(14)--D-glucopyranose. Lactose is a reducing
sugar because anomeric carbon of glucose is
free.
Source: Lactose is synthesized in
mammary gland and hence it
occurs in milk

3) Sucrose
It contains glucose and fructose. The
anomeric carbon of glucose and anomeric
carbon of fructose are involved in glycosidic
linkage.
Further, glucose is in -form whereas fructose
is in -form in sucrose. Hence the glycosidic
linkage of sucrose is designated as , (12).

Systematic name: O--D-glucopyranosyl-(12)-D-fructofuranose.


Sucrose is a non reducing sugar because both the
functional groups of glucose and fructose are
involved in glycosidic linkage.
Sources:

Ripe fruit juices like pineapple, sugar


cane
Honey
Sugar beets
Carrot roots

4) Isomaltose
It contains two glucose units.
Glycosidic linkage is (16)
Disaccharide unit present in glycogen,
amylopectin and dextran.
5)Cellobiose
Contains two glucose units but they are
joined in (14) linkage. It is formed from
cellulose.
6) Trehalose
It also contains two glucose units. The
glycosidic linkage is (11). So, it is a nonreducing
Disaccharide. It is a major sugar of insect

Invert sugar
Sucrose has specific optical rotation of
+66.5.
On hydrolysis, it changes to 19.8.
This change in optical rotation from dextro to
levo when sucrose is hydrolysed is called as
inversion.
The hydrolysis mixture containing glucose and
fructose is called as invert sugar.
The change in optical rotation on hydrolysis is
because of fructose which is more levo
rotatory than dextro rotatory glucose.

Polysaccharides

Polysaccharides (glycans)
consist of repeat units of
monosaccharides or their
derivatives held together
by glycosidic bonds.
Polysaccharides are linear
or branched polymers

Functions of polysaccharides

Provide mechanical stability


to cells, organs and microorganisms (structural
polysaccharides)
Eg; Cellulose is found in the cell walls of
plants,
Peptidoglycan in bacterial cell wall
Chitin in exoskeleton of arthropods

Serve as carbohydrate

Polysaccharide

omopolysaccharide

On hydrolysis,
yield only one
type
of
monosacchari
des. Eg;
Starch
Glycogen

Heteropolysaccharid

On hydrolysis,
give 2 or more
monsaccharides
or their
derivatives. Eg;
Hyaluronic acid
Chondroitin
sulfate

Based on their functional aspect, the


polysaccharides may be grouped under two
heads :
1) Nutrient (or digestible) polysaccharides
These act as metabolic reserve of
monosaccharides in plants and animals, e.g.,
starch, glycogen and inulin.
2) Structural (or indigestible) polysaccharides
These serve as rigid mechanical structures in
plants and animals, e.g.,cellulose, pectin,
chitin, hyaluronic acid and chondroitin.

Starch
Carbohydrate reserve of pants
Most imp dietary source for higher
animals, including man
Consists of D-glucose units held by glycosidic bond (glucosan or glucan)
Consists of two polysaccharide units
Amylose and Amylopectin

Amylose: (15-20%), water soluble, long


unbranched chain with 200-1000 DGlucose units held by (1 4) glycosidic
linkages

Amylopectin: (80-85%), water


insoluble, branched chain with (1 6)
glycosidic bonds at the branching
points and (1 4) bonds elsewhere,
looks like a branched tree

Dextrins
Breakdown products of starch by enzyme
amylase or dilute acids
Starch is sequentially hydrolysed through
different dextrins and finally to maltose
and glucose
Various intermediates are identified by
iodine colouration;

Blue (starch)
Violet (amylodextrin)
Red (erythrodextrin)
Colourless (archodextrin)

Inulin

Polymer of fructose i.e; fructosan


Soluble in water
Low molecular wt
Source: Dahlia bulbs, garlic, onion
Not utilised by our body so used for
assessing kidney function through
measuring GFR

Glycogen
carbohydrate reserve of animals (animal
starch)
stored in liver, muscle, brain
found in plants that do not contain chlorophyll
(eg; yeast, fungi)
structure is similar to amylopectin with more
no. of branches
ie; Glucose with (1 6) glycosidic bonds at the
branching points and (1 4) bonds elsewhere
Glycogen: Glucose has (1 6) branches every
8- 12 residues whereas amylopectin has (1 6)
branches in every 12-30 residues

no of glucose units vary in glycogen ( up to

g: General structure of glycogenFig: Enlargement of


glycogen

Cellulose
totally absent in animal body
occurs extensively in plants and is the most
abundant organic substance in plant kingdom
cannot be digested by mammals including
humans due to the lack of enzyme that breaks
glycosidic bonds. However, certain
hervivores contain microorganisms in the gut
which produce enzyme that cleave
glycosidic bonds
It is a major constituent of fiber, the non
digestible carbohydrate. So decrease the
absorption of glucose and cholesterol from the

composed of -D glucose units linked


by (1 4) glycosidic bonds
hydrolysis of cellulose yields a
disaccharide cellobiose followed by
-D-Glucose

Fig: Structure of cellulose

Chitin
Composed of N-acetyl DGlucosamine units held together by
(1 4) glycosidic bonds
Structural polysaccharide found in
exoskeleton of some invertibrates
e.g; insects, crustaceans

Mucopolysaccharides
are heteroglycans made up of repeating units
of sugar derivatives namely amino sugars
and uronic acids

(A single exception is keratan sulfate, in which


galactose

comonly known as
glycosaminoglycans (GAG)
acetylated amino groups, sulfate and
carboxyl groups are generally
present
presence of sulphate and carboxyl
groups contributes to acidity of the
molecules

Function
essential components of tissue structure
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
the extracellular spaces of tissue (esp.
connective tissue- cartilage, tendons, blood
vessels, skin) consist of collagen and elastin
fibres embedded in the matrix of ground
substance (predominantly composed of

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

Hyaluronic acid

consists of alternate units of DGlucuronic acid and N-acetyl


Glucosamine
(1 3 ) glycosidic bond
consists of 250-25,000 disaccharide
units held by (1 4 ) bonds

Hyaluronic acid is found in the ground substance of


synovial fluid of joints and vitreous humor of eyes
Forms a gel around the ovum
Hyaluronidase ( an enzyme) breaks 1 4 linkages of
hyaluronic acid and other GAG
present in testes, seminal fluid, snake venom
hyaluronidase of semen clears the gel around the
ovum allowing better penetration of sperm into the
ovum
hyaluronidase of bacteria helps their invasion into
the animal tissue

Medical importance
1) As the age advances hyaluronic acid is
replaced by-dermatan sulfate in synovial
fluid. Dermatan sulfate is not a good
lubricant, hence age related pains develop in
old people.
2) In young people, vitreous is clear elastic gel
in which hyaluronic acid is associated with
collagen. As the age advances the elasticity
of vitreous is reduced due to decreased
association between collagen and hyaluronic
acid. As a result, vision is affected in older
people.

4) Hyaluronic acid is involved in wound healing


(repair). In the initial phase of wound healing
(repair), hyaluronic acid concentration increases
many fold at the wound site.It allows rapid
migration of the cells to the site of connective
tissue development.
5) Hyaluronic acid helps in scarless repair. If suitable
levels of HA are maintained during would healing
scar formation is reduced or even prevented.
6) HA content of skin decreases as age advances this
is the reason for increased susceptibility of aged
people for scar formation.
7) Pneumonia, meningitis and bacteremia causing

Different from other GAGs:


Unsulfated
Not covalently bound to proteins
Not limited to animal tissue but also
found in bacteria

Chondroitin sulfates
chondroitin 4 sulphate is a major constituent of
various mammalian tissues (bone, cartilage,
tendons, heart valves, skin cornea etc)
structurally comparable to hyaluronic acid
consists of repeating disaccharide units
composed of D-glucoronic acid and N-acetyl Dglucosamine 4-sulfate

Heparin
composed of alternating units of N-sulfo Dglucosamine 6-sufate and glucoranate 2sulfate
acts as an anticoagulant
helps to release lipoprotein lipase which
helps in clearing the turbidity of lipemic
plasma

Unlike other GAGs that are extracellular, heparin


is intracellular component of mast cells that line

Dermatan sulfate
mostly occurs in skin
structurally related to chondroitin 4sulfate except for the inversion in the
configuration around C5 of Dglucuronic acid to form L-iduronic
acid

Keratan sulfate
Essentially consists of alternating
units of D-galactose and Nacetylglucosamine 6-sulfate

Proteoglycans
Some mucopolysaccharides are found in
combination with proteins to form
mucoproteins or mucoids or
proteoglycans.
Mucoprotein may contain upto 95%
carbohydrate and 5% protein

Fig: Proteoglycan complex

Glycoproteins
proteins covalently bound to carbohydrates
carbohydrate content of glycoprotein varies
from 1 to 90% by weight
They are found in mucous fluids, tissues, blood
and in cell membrane.
They are proteins containing short chains of
carbohydrates.
The carbohydrate chains are usually
oligosaccharides.
These oligosaccharide chains are attached to
proteins by O-glycosidic and N-glycosidic bonds

Carbohydrates found in glycoproteins


include
Mannose
Galactose
N acetyl glucosamine
N acetyl galactosamine
Xylose
L-fucose
N acetylneuraminic acid (NANA)

Glycoproteins and their major


functions
Glycoproteins
Collagen
Immunoglobulins
Synovial glycoproteins
Thyrotropin
Blood group antigens
Fibrinogen
Intrinsic factor
Fibronectin, laminin

Major functions
Structure
Defence against infection
Lubrication
Hormone
Antigens
Blood clotting
Absorption of vit B12
Cell-cell adhesion and
recognition

Antifreeze glycoproteins
Antarctic fish are able to live below
-2 C, due to the presence of
antifreeze glycoproteins which lower
the freezing point of water and
interfere with the crystal formation of
ice

Blood group antigens


Contain carbohydrate as
glycoproteins or glycolipids
N acetylglucosamine, galactose,
fucose and sialic acid are found in
blood group substances

Sialic Acid
Sialic acids are acyl derivatives of neuraminic
acid.
Neuraminic acid is a 9 carbon sugar consisting
of mannosamine and pyruvate.
Usually amino group of mannosamine of
neuraminic acid is acetylated.
Hence, N-acetyl neuraminic acid (NANA) is an
example for sialic acid.
Functions
Oligosaccharides of some membrane
glycoproteins contains a terminal sialic acid.
Sialic acid is an important constituent of
glycolipids present in cell membrane and

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