Objectives

 Introduction & Definition of carbohydrates.

 Classification.

 Sources.

 Properties and functions.

 Chemically, carbohydrates contain the elements carbon, hydrogen
and oxygen.

 The empirical formula of many simple carbohydrates is [C.H2O]n.

 Hence, the name “carbohydrate”, i.e. hydrated carbon.

 Carbohydrates are also called “saccharides” (In Greek, saccharon

means sugar).

 Although many common carbohydrates confirm the empirical

formula [CH2O]n, others like deoxyribose, rhamnohexose do not.

Definition

 Carbohydrates may be defined as polyhydroxyaldehydes or

ketones or compounds which produces them on hydrolysis.
 Importance of Carbohydrates.

1. Carbohydrates are the main sources of energy in the body. Brain cells and
RBCs are almost wholly dependent on carbohydrates as the energy source.
Energy production from carbohydrates will be 4 kcal/g.

2. Storage form of energy (starch and glycogen). Excess carbohydrate is

converted to fat.

3. Glycoproteins and glycolipids are components of cell membranes and

receptors.
4. Non-digestable carbohydrates like cellulose, serve as dietary fibers.

5.Constituent of nucleic acids RNA and DNA.

6. Carbohydrates are precursors for many organic compounds (fats, amino

acids).

7. Structural basis of many organisms: Cellulose of plants; exoskeleton of

insects; cell wall of microorganisms.
8. Heparin acts as anticoagulant.
9. Inulin is used to study the renal clearance test.
10. Pectin is used as a food preservative.
11. Agar as culture media, agarose as matrix for electrophoresis.

 Sources :- Rice, grains, cereals, fruit, milk, green vegetables, potatoes ,

corn and peas, Sugars like table sugar and honey.
Monosaccharides (Simple sugar / single unit of sugar).
Classification of carbohydrates
Disaccharides (Two sugar unit).

Oligosaccharides (3 – 10 Sugar unit).

Polysaccharides (> 10 sugar unit).

 Mono, di and oligosaccharides are sweet to taste, crystalline in
character and soluble in water, hence they are commonly
known as sugars.
Monosaccharides

 Monosaccharides are the simplest group of carbohydrates and are

often referred to as simple sugars.

 They consist of a single polyhydroxy aldehyde (CHO) OR ketone

(C=O) unit, and thus cannot be hydrolyzed into a simpler form.
 They have the general formula Cn(H2O)n.
 Monosaccharides classified as follows --

I. Based on the number of carbon atom - Trioses (3C), Tetroses (4C), ,

Pentoses (5C), Hexoses (6C), Heptoses (7C) so on..,,,

II. Based on the presence of functional group - Aldehyde (CHO) – Aldoses

& ketone (C=O) – Ketoses.
 Disaccharides
 They consists of two monosaccharide units (similar or dissimilar)
held together by a link which is knownas glycosidic bond.

 The disaccharides are of two types

1. Reducing disaccharides with free aldehyde or keto group e.g.

maltose, lactose.

2. Non-reducing disaccharides with no free aldehyde or keto group e.g.

sucrose, trehalose.
 Glycoside - When the hemiacetal group (hydroxyl group of the anomeric
carbon) of a monosaccharide is condensed with an alcohol or phenol group, it
is called a glycoside bond.
 Some important Disachharides

1. Lactose – Milk sugar - β-D-galactose and β-D-glucose held

together by β(1 --> 4) glycosidic bond.

2. Maltose - two α-D-glucose units held together by α(1 --> 4)

glycosidic bond.

3. Isomaltose - two α-D-glucose units held together by α(1 --> 6)

glycosidic bond.
4. Cellobiose – identical in structure with maltose, in which sugar
units held together by β (1 --> 4) glycosidic bond.

5. Sucrose (cane/table sugar) mostly produced by sugar cane and sugar

beets.

 Sucrose is made up of α-D-glucose and β-D-fructose. The

two monosaccharides are held together by a glycosidic bond (α1 -->

β2), between C1 of α-glucose and C2 of β-fructose.

 Oligosaccharides : carbohydrates that contain 3 to10 single sugar residues
and are not relatively abundant in the diet when compared to other more
common carbohydrates.

• Trisaccharide: Raffinose
Fructose + Galactose + Glucose

• Tetrasaccharide: Stachyose
2 moles of Galactose + Glucose + Fructose

• Pentasaccharide: Verbascose
3 moles of Galactose + Glucose + Fructose
 Polysaccharides / Glycans/ complex carbohydrates
 Polysaccharides are polymers consisting of hundreds or thousands of
monosaccharide units.

 They may be either linear, (e.g. cellulose) or branched, (e.g.

glycogen) in structure.

 They have high molecular weight and are only sparingly soluble in
water.

 They are not sweetish and do not exhibit any of the properties of
aldehyde or ketone group.
 Polysaccharides/Glycans are of two types.

i. Homopolysaccharides (homoglycans)

ii. Heteropolysaccharides (heteroglycans).

 Homopolysaccharides (Homoglycans) - When a polysaccharide is made up of

several units of one and the same type of monosaccharide unit, it is called
homopolysaccharide.

 Some iportant common homoglycans are: Starch, Glycogen, Dextrins,

Dextrans, Inulin, Cellulose, Chitin.
 Heteropolysaccharides :-

 When the polysaccharides are composed of different types of sugars

or their derivatives, they are referred to as heteropolysaccharides
or heteroglycans.

 Ex - Agar,Agarose, Hyaluronic acid, Heparin, Chondroitine

sulphate, keratan sulphate, Dermatan sulphate.
 MUCOPOLYSACCHARIDES/ GLYCOSAMINOGLYCANS (GAG).

 Mucopolysaccharides are heteroglycans made up of repeating units of

sugar derivatives, namely amino sugars and uronic acids. These are
more commonly known as glycosaminoglycans (GAG).

 Some of the mucopolysaccharides are found in combination with proteins

to form proteoglycans.

 If the carbohydrate content is < 10%, it is generally named as a

glycoprotein.

 If the carbohydrate content is > 10% it is a mucoprotein.

 Reactions of carbohydrates
I. Molisch’s test - General test for carbohydrates.

Principle - Dehydration = Furfural derivatives + Phenolic compound.

Procedure - Sample (ex- glucose) + Phenolic compound (α-naphthol) + Conc

Sulphuric Acid

Observation - Reddish violet/Purple ring at the junction of 2 layers.

II. Iodine test - General test for polysaccharides.

principle - Adsorption/Adhesion.

procedure - sample (ex- starch) + iodine reagent

observation - deep blue - positive.

III. Benedict’s test - Qualitative & semi quantitativi - To detect the presence
of sugar in a sample.

Principle - Carbohydrates with free functional group have reducing property

(in hot alkalione medium they form enediols), in hot alkaline medium they
reduce copper sulphate to Cuprous oxide.

procedure - Benedict’s reagent + sample + 2 Min boil

Observation - Depend on the concentration of sugar - Blue, green, yellow,

orange, Brick red.
IV. Barfoed’s test - General test to distinguish reducing mono saccharides
from reducing di saccharides.

Principle - In weak acidic medium Copper acetate to copper oxide (Cu2O)

which forms a brick - red precipitate.

Procedure - Barfoed’s reagent + sample + 30 sec boil.

Observation - Red scum.

V.Seliwanoff’s test - To distinguish between aldoses / ketoses (Genral test for
ketoses).

Principle - Dehydration.

Procedure - Seliwanoff’s reagent + sample + 30 sec boil.

Observation - Cherry red.

Osazone test - To identify reducing sugar by the characteristic shape of
osazone crystals.
Chemistry

Triose

Pentose

Tetrose
Hexose
 Chiral carbon : The carbon that is attached to four different atoms or
groups.

 Isomers - compounds having same molecular formula but differ in their

structure.

 Sterioisomers - compounds having same structural formula but differ in

spatial arrangement.

 Enatiomers - are type of stereoisomers which are mirror images.

 Diastereomer - are type of stereoisomers which are non mirror image,

non-identical.
 The five types of isomerism exhibited by sugar are as follows:

1. Ketose-aldose isomerism.

2. D and L isomerism

3. Optical isomerism

4. Epimerism

5. Anomerism.
 Ketose-aldose isomerism

 Glucose and fructose are isomers of each other having the same molecular

formula C6H12O6, but they differ in structural formula with respect to their
functional groups.

 There is a keto group in position two of fructose and an aldehyde group in

position one of glucose. This type of isomerism is known as ketose-aldose
isomerism.
 D and L isomers: It indicate the orientation of OH group around the
penultimate Carbon atom.They are also mirror images of each other

 D-sugars are predominant in human body.

 Optical isomerism

 When a plane polarized light is passed through a carbohydrate solution, it

will rotate the light either to left or right.

 If the rotation is towards right then it is called as Dextrorotatory (d) (+).

 If the rotation is towards left then it is called as Levorotatory (l) (-).

 D- glucose is dextrorotatory , D- fructose is levorotatory.

 Racemic mixture : If d- and l-isomers are present in equal
concentration, it is known as racemic mixture or dl mixture.

 Racemic mixture does not exhibit any optical activity, since the dextro-
and levorotatory activities cancel each other.
 Epimers: Two monosaccharides differing in the configuration around only
one specific Carbon atom (except the carbonyl carbon)

 For example: Glucose and galactose are C4 epimers, Glucose and mannose
are C2 epimers, Mannose and galactose are not epimers (differ in
configuration around two carbons C2, C4).
 Anomerism

 In the solutions carbohydrates exists in cyclic form.

 Depending on the orientation of the H and OH group around the

anomeric carbon atom, they give two forms namely α and β forms

 There are many cyclic forms of sugars e.g. Fischer projection (straight
chain) & Haworth projection (simple ring)

 Six-membered ring is called pyranose e.g. glucopyranose

 Five-membered ring is called furanose e.g. fructofuranose

Fischer projection & Haworth projection


 Mutarotation
 Freshly prepared solution of a -glucose has a specific rotation +112o.
When this solution is allowed to stand the rotation falls till reach +52.7o

 Freshly prepared solution of b -glucose has a specific rotation +18.7o.

When this solution is allowed to stand the rotation rises to reach +52.7o

 At equilibrium : 36% are a –D- glucose & 64% are b –D- glucose

 Mutarotation is defined as the change in the specific optical rotation

representing the interconversion of a and b forms of D-glucose to an
equilibrium mixture.
 Reactions of carbohydrates
1. Action of acid
2. Action of alkali / Enediol formation
3. Benedicts reaction
4. Osazone formation
5. Oxidation of sugars
6. Reduction to form alcohols
7. Glycosides
8. Formation of esters
9. Amino sugars
10. Deoxy sugars
 1. Action of acid

 Molisch’s test: Any carbohydrate + Alcoholic alpha-naphthol + conc.

H2SO4 on the wall of the test tube

 A Violet ring is formed between the two layers

 2. Action of Alkali / Enediol Formation

 Benedict’s test : In alkaline condition, the carbohydrtes containing a

free aldehyde or keto group will tautomerise to form enediols

 Enediols are reducing agents, they reduce cupric ions to cuprous

ions present in benedicts solution and form cuprous hydroxide

 Cuprous hydroxide on heating form cuprous oxide which is red in

color.
Action of Alkali / Enediol Formation

CH O CHOH CH O

H OH C OH HO H

HO H HO H HO H

H OH H OH H OH

H OH H OH H OH

CH2OH CH2OH CH2OH

D-Glucose Enediol D-Mannose

44
Benedicts reagent:

 Copper sulphate - Source for copper ions

 Sodium carbonate - To provide alkaline environment

 Sodium citrate - Prevent the precipitation of cupric hydroxide

 Benedict's Reaction

 Importance - It is semi quantitative test

 Used to test reducing substances in urine in conditions like

-Diabetes mellitus (Glucose), Alkaptonuria (homogentisic acid), Phenyl

ketonuria (ketoacids) & Other interfering substances include ascorbic acid etc
4. Osazone formation

 Reducing sugars form osazones with excess of phenyl hydrazine

when kept at boiling temperature.

Glucose & Glucosazone Needle shaped crystals

Fructose &
Fructosazone

Maltose Maltosazone Sunflower shaped crystals

Lactose Lactosazone Badminton ball shaped

crystals
5. Oxidation of sugars
Mild Oxidation :
 CHO group oxidised to COOH - “onic acids”
ex : Gluconic acid and Mannonic acid
 Enzymatic oxidation : - CH2OH oxidised to COOH -“uronic
acids”
ex - Glucuronic acid
 Strong oxidation : Both CHO and CH2OH oxidised to COOH
- “accharic acid”
ex- Glucose oxidised to saccharic acid
 CHO COOH
CH OH CH OH
I2 or Fehling's
HO CH HO CH
CH OH CH OH
CH OH CH OH
CH2OH CH2OH
D-Glucose Gluconic acid
 Oxidation to Uronic Acids

CHO CHO
H OH O
H OH
enzyme OH
HO H HO H O
H OH H OH HO
HO OH
H OH H OH OH
CH2OH COOH

D-Glucose D-Glucuronic acid

6. Reduction

 This resulted in the reduction of the Glucose Sorbitol (food

additive/ cataract in
CHO to CH2OH producing “Sugar diabetes)
Alcohols”.
Mannose Mannitol (Diuretic)

Ribose Ribitol
Galactose Dulcitol (cataract in
galactosemia)
Xylose Xylitol
7. Glycosides
1. When a monosaccharide reacts with an alcohol: A glycoside is
produced
2. Glycosides do not reduce benedicts reagent
3. Acid hydrolysis bring back the free aldo group
4. Examples
 Ouabain – Na-K ATPase inhibitor
 Streptomycin – antibiotic
 Phlorizin - to cause renal damage in experimental animals
 Digitonin - Cardiac stimulant
8. Formation of esters

 Hydroxyl group of sugars can be esterfied to form acetates,

propionates, and benzoates.

 Sugar phosphates: Metabolism of sugars inside body starts with

phosphorylation. Eg: Glucose-6-phosphate
9. Amino Sugars

 An amino group substitutes for a hydroxyl group

 Examples:

 Glucosamine: hyaluronic acid, Heparin

 Galactosamine: cartilage, bone, tendon

CH 2OH CH 2OH
 Mannosamine: mucopolysaccharides
H O H H O H
H H
OH H OH H

OH OH OH O OH
H NH 2 H N C CH 3
H
-D-glucosamine -D-N-acetylglucosamine
10. Deoxysugars
Oxygen of hydroxy group is removed to form deoxy sugar.
It is required for nucleic acid synthesis.
 Disaccharides : Maltose

 Maltose, a cleavage product of starch.

 Maltose is named after malt, the juice from sprouted barley and other
cereal grains.

 Maltose consists of two molecules of α-D-glucose joined by α 1,4-

glycosidic bond between carbon 1 (the anomeric carbon) of one unit
and carbon 4 of the other unit.

 Maltose is a reducing sugar.

Maltose
 Lactose
 Lactose is a milk sugar.
 It makes up about 5-8% of human milk, 4-6% cow’s milk.
 It is composed of β - D-galactose & α -D-glucose, with β (14) linkage.
 Lactose is also a reducing sugar.
 Deficiency of the LACTASE enzyme leads to a disorder called lactose
intolerance.
 Lactose intolerance

 Due to lactase deficiency.

 Characterized by abdominal cramps and osmotic diarrhea.
 Treated by lactose free diet.
 Sucrose
Sucrose is a common table sugar.
• Commercially, it is obtained from the juice of sugar cane and sugar beets.
 Carbon 1 of α -D-glucopyranose is joined to carbon 2 of β -D-
fructofuranose by an α-β 1,2-glycosidic bond
 Sucrose is a non-reducing sugar.

Invert sugar
Also called Invert sugar – inversion of direction of rotation by the sucrose
on hydrolysis. The products will change from dextro to levo rotation.
 Starch
Present in plants, not found in animals.
 main carbohydrate in food.
 Sources: cereals, roots, tubers, vegetables
 Starch hydrolysis

 Hydrolysis with mild acid leads to formation of amylodextrin,

erythrodextrin, acrodextrin and maltose

 Salivary and pancreatic amylase act randomly at α 1-4 glycosidic

linkage to form dextrins and further to form maltose and
maltotriose.
 Consists of amylose & amylopectin

Starch (amylose)

Branch at α-1,6 bond

Starch (amylopectin): few branches

OR
Glycogen: many branches
 Amylose

 Amylose (straight chain): formed of α-glucose units linked by α-1,4

glycosidic bonds
 stained blue by iodine

Amylopectin

 Amylopectin (branched chain): formed of α-glucose units linked by α-1,4

glycosidic bonds with α-1,6 glycosidic bonds at branch points.
 stained red-brown by iodine.
 Glycogen

 Major storage form of carbohydrates in animals: in muscle and liver.

 Formed of α-glucose units linked by α-1,4 glycosidic bonds with α-1,6
glycosidic bonds at branch points.
 Cellulose

 Major structural material of plants

 Requires cellobiase enzyme for digestion which is absent in humans
and animals
 They form dietary fiber
 Inulin

 Polymer of fructose.

 Storage polysaccharide in tubers and roots of plants - garlic, onion.

 Used in assessing glomerular filtration rate (GFR)

 Dextrans

 Highly branched homopolymers of glucose units with 1-6, 1-4 and 1-

3 linkages

 Produced by various micro-organisms growing in sucrose media

 High molecular weight of 1 million to 4millon

 Used as plasma expanders for hypovolemic shock as they do not go

out of vascular compartment
 Heteropolysaccharides

 Also called Mucopolysaccharides or Glycosaminoglycans (GAGs)

 Often attached to protein, the compound is called proteoglycan

 Not used to give energy (because they are structural polysaccharides)

 Formed of repeated disaccharide units

 Disaccharide unit is formed of a uronic acid & an amino sugar

Heteropolysaccharides

Chondorotin Glucuronic acid found in

sulfate & cartilages,
N-acetylgalactosamine tendons and
sulfate ligaments
Heparin sulfated glucuronic acid anticoagulant
&
sulfated glucosamine
Dermatan L-iduronic acid found in skin
sulfate &
N acetyl
galactosamine
Keratan sulfate galactose found in cornea
&
N acetyl glucosamine

Chondorotin Glucuronic acid found in

sulfate & cartilages, tendons
N-acetylgalactosamine and ligaments
sulfate
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