CHEMISTRY OF

CARBOHYDRATES
 DEFINITION

z Carbohydrates are polyhydroxy aldehydes or

ketones or compounds which yield these on
hydrolysis.
H O
C C H 2O H

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

C H 2O H C H 2O H

D -g lu c o s e D -fru c to s e
BIOMEDICAL IMPORTANCE
1. Most abundant dietary source of energy.
2. Also serve as storage form of energy
Glycogen.
3. Participate in the structure of cell membrane
& cellular functions (cell growth, adhesion and
fertilization).
4. Mucopolysaccharides form the ground
substance of mesenchymal tissues.
5. Certain carbohydrate derivatives are used as
drugs, like cardiac glycosides / antibiotics.
ASSOCIATED DISORDERS

Derangement in Glucose metabolism

Diabetes Mellitus.
Inherited deficiency of certain enzymes in
metabolic pathways of different carbohydrates
cause diseases.
Glycogen storage disorders
Galactosemia
Hereditary fructose intolerence
Lactose intolerance, etc.
SOURCES
 CLASSIFICATION
z Based on number of sugar units present.
z Monosaccharides.
z Cannot be hydrolyzed further into simpler forms.
z Disaccharides.
z Yield 2 molecules of same or different
monosaccharide units on hydrolysis.
z Oligosaccharides.
z Yield 3-10 molecules of monosaccharide units on
hydrolysis.
z Polysaccharides.
z Yield more than 10 molecules of same or different
monosaccharide units on hydrolysis.
z Homo- & Heteropolysaccharides.
 MONOSACCHARIDES

z Simplest group of carbohydrates, cannot be further

hydrolysed.

z General formula : Cn(H2O)n

z Categorization of monosaccharides is based on

z the Functional Group. (Aldehyde or keto)

z the Number of Carbon atoms.

MONOSACCHARIDES BASED ON
FUNCTIONAL GROUP

KETOSE
ALDOSE
COMMON MONOSACCHARIDES

No. of C Generic name Aldoses Ketoses

atoms
3 Triose Glyceraldehyde Dihydroxy acetone

4 Tetrose Erythrose Erythrulose

5 Pentose Ribose Rilulose

Xylose Xylulose
6 Hexose Glucose Fructose
Galactose

7 Heptose Glucoheptose Sedoheptulose

 STEREOISOMERS
z Compounds having same structural formula, but differ
in spatial configuration.
z Asymmetric Carbon atom: Attached to four different
atoms or groups.
z Vant Hoffs rule: The possible isomers (2n) of a given
compound is determined by the number of asymmetric
carbon atoms (n).
z Reference C atom: Penultimate C atom, around which
mirror images are formed.
GLYCERALDEHYDE STEREOISOMERS
D & L ISOMERISM OF GLUCOSE
 OPTICAL ACTIVITY

z Dextrorotatory (+) : If the sugar solution

turns the plane of polarized light to right.

z Levorotatory () : If the sugar solution

turns the plane of polarized light to left.

z Racemic mixture: Equimolar mixture of

optical isomers has no net rotation.
 EPIMERISM

z Sugars are different from one another, only in

configuration with regard to a single C atom
(other than the reference C atom).
MUTAROTATION & ANOMERISM

z When D-glucose is crystallised at room temp. and a

fresh solution is prepared, its specific rotation of
polarised light is + 112.2O;but after 12-18 hrs it changes
to + 52.50. If initial crystallisation takes place at 980 C,
initial rotation is +190, which also changes to 52.50.

z Anomers are produced by spatial configuration with

reference to 1st C atom in aldoses and 2nd C atom in
ketoses.

z So, total 32 isomers are there for glucose.

 AND ANOMERS OF D-GLUCOSE

1
CHO

H C OH
2
HO C H D -glucose
3
H C OH (linear form)
4
H C OH
5
CH 2OH
6

6 CH 2OH 6 CH 2 OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D -glucose -D -glucose
DIFFERENT REPRESENTATIONS
OF GLUCOSE STRUCTURE

OPEN CHAIN HAWORTH

PROJECTION FISCHERS FORMULA FORMULA
1
2
3
4
5

6
 GLUCOSE VS. FRUCTOSE
z D glucopyranose is the stable form of glucose and it
exhibits the dextro rotation.
z Fructose exits as D furanose & exhibits laevo rotation.

D glucopyranose D fructofuranose
 REACTIONS OF
MONOSACCHARIDES
z Tautomerization or Enolization.
z Reducing properties.
z Oxidation.
z Reduction.
z Dehydration.
z Formation of Esters
z Glycoside formation.
 ENEDIOL FORMATION
z In mild alkaline solutions, carbohydrates containing free
sugar group tautomerises to form enediols, where 2 OH
groups are attached to double-bonded carbon.
 REDUCING PROPERTIES

z Attributed to the free aldehyde or keto group of

anomeric carbon.

z Tests done to identify the reducing action of sugars

include :
z Benedicts test.
z Barfoeds test.
z Fehlings test.
z Osazone test.

z Reduction is more efficient in alkaline medium than in

acidic medium.
BENEDICTS TEST: PRINCIPLE
REAGENT: Na2CO3, CuSO4, Na citrate

SUGAR ENEDIOL Cu++ CuSO4

OXIDISED REDUCED

SUGAR ACID Cu+

Cu2O 2Cu(OH)2
BENEDICTS TEST

water 0.5-1% 1- 1.5% 1.5 2%

 BARFOEDS TEST
z Reducing monosaccharides are oxidized by the copper
ion in solution to form a carboxylic acid and a reddish
precipitate of cuprous oxide within three minutes.

Red scum at
bottom
 FEHLINGS TEST
z Fehling I:CuSO4
z Fehling II: K-Na- tartrate + NaOH
z Fehling's reagent: Equal volumes of Fehling I and
Fehling II are mixed to form a deep blue solution.
 OSAZONE FORMATION
z Phenylhydrazine in acetic acid, when boiled with
reducing sugars, forms osazones.

PHENYL
FRUCTOSE HYDRAZINE FRUCTOSAZONE
 OSAZONE CRYSTALS

GLUCOSAZONE:NEEDLE SHAPED

LACTOSAZONE: HEDGEHOG
SHAPED MALTOSAZONE: SUNFLOWER
SHAPED
 OXIDATION

Gluconic acid
H O
C

H C OH

HO C H

H C OH Glucuronic acid
H C OH

CH2OH

D-glucose

Glucosaccharic
acid
 REDUCTION

H O
C C H 2O H
H C OH C O
HO C H HO C H

H C OH H C OH

H C OH H C OH

CH 2 OH C H 2O H

D -glucose D -fru cto se

D-
 DEHYDRATION
1
2
3 Conc. H2SO4
4
5 3H2O
6
z Furfurals condense with phenolic compounds (-naphthol)
to form coloured products.
z Basis of the Molisch test.
 FORMATION OF ESTERS
z Esterification of alcoholic groups of mono-saccharides
with phosphoric acid is a common reaction in
metabolism.

z Examples :
z Glucose-6-phosphate, and

z Glucose-1-phosphate.

z ATP donates the phosphate moiety.

GLYCOSIDE FORMATION
z The hydroxyl group of anomeric carbon of a
carbohydrate can join with a hydroxyl group of another
carbohydrate or some other compound to form a
glycoside and the bond so formed is known as glycosidic
bond.
eg. R-OH + HO-R' R-O-R' + H2O

z The non-carbohydrate moiety is known as aglycone

phenol, sterol, bases, CH3OH, glycerol.

z Glycosidic bond can be N-linked or, O-linked.

N & O GLYCOSIDIC LINKAGE

N-Glycosidic linkage O- Glycosidic linkage

 BIOMEDICAL IMPORTANCE OF
GLYCOSIDES

z Cardiac Glycosides Digoxin, Digitoxin

z Used in cardiac insufficiency.

z Contain steroids as aglycone component.

z Ouabain Sodium pump inhibitor.

z Streptomycin Antibiotic
z Phloridzin cause renal damage, glycosuria.
z Obtained from root & bark of apple tree.

z Blocks the transport of sugar across the mucosal cells

of small intestine & also renal tubular epithelium.
 AMINO SUGARS
z Amino groups are substituted for hydroxy groups of
sugars.

CH2OH CH2OH O H

H O H H O H H3C C NH O COO
H H R HC OH
OH H OH H H H R=
HC OH
OH OH OH O OH H OH
CH2OH
H NH2 H N C CH3
OH H
H
-D-glucosamine -D-N-acetylglucosamine N-acetylneuraminate (sialic acid)
 DEOXY SUGARS
z Oxygen of the hydroxyl group is removed to form deoxy
sugars.
z Non reducing and non osazone forming.
z Important part of nucleic acids.
 DISACCHARIDES
z Two monosaccharides combined together by glycosidic
linkage.

z Reducing : Maltose, Lactose with free

aldehyde or keto group.

z Non-reducing : Sucrose, Trehalose no free

aldehyde or keto group.
 SUCROSE
z Cane sugar.

z -D-glucose & -D-fructose

units held together by (1 2)
glycosidic bond.

z Reducing groups in both are

involved in bond formation,
hence non reducing.
 INVERT SUGAR
z Sucrose is dextrorotatory. (+66.50)

z During hydrolysis, sucrose is first split into -D-

glucopyranose & -D-fructofuranose (both
dextrorotatory).

z -D-fructofuranose is less stable and immediately

converted to -D-fructopyranose (strongly levorotatory).
z Net rotation : 28.20.

z Sweeter than sucrose.

 TREHALOSE

1- 1 glycosidic linkage
LACTOSE

z Present in milk.

z -D-galactose & -D-

glucose units held
together by (14)
glycosidic bond.
MALTOSE
zMalt sugar.
Produced during the course of
digestion of starch by the enzyme
amylase.
zTwo -D-glucose units held together
by (14) glycosidic bond.
 POLYSACCHARIDE
z Repeat units of monosaccharides or their derivatives
held together by glycosidic bonds.
HOMOPOLYSACCHARIDES
z Starch

z Glycogen

z Cellulose

z Inulin

z Dextrans

z Chitin
STARCH

z Carbohydrate reserve of
plants. Present in
Cereals, Roots, Tuber,
Vegetables.

z Consists of Amylose
(water soluble) &
Amylopectin (water
insoluble).
 AMYLOSE

z Long unbranched chain.

z 200 20,000 D-glucose units held together by (14)

glycosidic linkages.

AMYLOSE
 AMYLOPECTIN

z Branched chain. ( 16 glycosidic bonds at branches).

z 20 30 glucose units per branch.

AMYLOPECTIN
HYDROLYSIS OF STARCH

+ve -ve

z Colour disappears with heating and reappears when

cooled.
z Starch is non reducing.
z Hydrolysis for a short time: Violet colour due to
Amylopectin (non reducing).
z Further hydrolysis: Red colour due to Erythrodextrin
(reducing).
z Later Achrodextrin & Maltose (both reducing).
 ACTION OF AMYLASE

z Starch Dextrins /-Maltose

Salivary &
pancreatic -
amylase or -
amylase

z Amylopectin -amylase
Limit dextrin

Maltoses
 GLYCOGEN
z Reserve carbohydrate in
animals. Stored in liver &
muscle.
z Forms red-brown/brown-
violet colour with iodine.
z Contains primer protein:
Glycogenin.
z More branched and
compact than amylopectin.
Every 11th sugar molecule
has a branch.
GLYCOGEN STRUCTURE
 CELLULOSE

z Chief carbohydrate in plants.

z Made up of glucose units combined with cellobiose
bridges.
z No branching point.
z Cannot be digested by human due to absence of
Cellobiase.
INULIN

z Inulin is made up of D-
fructose units with
repeating -1,2 linkages.

z It acts as a marker for

glomerular filtration since
it is not synthesized,
metabolized but filtered
completely by glomerulus.
 CHITIN
zChitin is found in crustaceans
eg.lobsters,crabs,shrimps,insects.
zComposed of N-acetyl
glucosamine units joined by -1,4
glycosidic linkages.
HETEROPOLYSACCHARIDES

z Agar

z Mucopolysaccharides:

9 Hyaluronic acid
9 Heparin
9 Chondroitin sulphate
9 Keratan sulphate
9 Dermatan sulphate
AGAR
z Prepared from sea weeds.
z Contains Galactose, Glucose
and other sugars.
z Used as supporting medium
for immunodiffusion &
immunoelectrophoresis.
z Agarose contains Galactose
combined with3,6
anhydrogalactose units.
z Agarose is used as matrix for
electrophoresis.
MUCOPOLYSACCHARIDES
z Also known as GAG.
z Made up of repeating units of sugar derivatives
(aminosugars and uronic acids).
z Acetylated amino groups, sulfates and carboxyl groups
are generally present.
 HYALURONIC ACID

z Present in connective tissues, tendons, synovial fluid and

vitreous humor.
z Composed of repeating units of N-acetyl glucosamine
-1,4 glucuronic acid -1,3 N-acetyl glucosamine.
 HEPARIN

z Anticoagulant. Bind and activate Antithrombin III,

which in turn activates Thrombin, Factor X & Factor
IX.
z Present in lung, spleen and monocytes.
z Contains repeating units of sulphated glucosamine
-1,4 L-iduronic acid.
z Sulphated: Heparan sulphate
CHONDROITIN SULPHATE

z Present in ground substances of connective tissues of

cartilages, bones & tendons.
z Composed of Glucuronic acid -1,3 N-acetyl
galactosamine sulphate -1,4 and so on.
 KERATAN SULPHATE

z Only GAG not having Uronic acid.

z Found in cornea and tendons.
z Repeating units are Galactose & N-acetyl galactosamine
in linkage.
 DERMATAN SULPHATE

z Found in skin, blood vessels & heart vessels.

z Contains L-iduronic acidand N-acetyl galactosamine in
-1,3 linkage.
MUCOPLYSACCHARIDOSIS
NAME ENZYME DEFECT URINARY
METABOLITES
MPS I : Hurlers -L-Iduronidase Dermatan sulfate
Heparan sulfate
MPS II: Hunters Iduronate sulphatase Dermatan sulfate
Heparan sulphate
MPS IIIA: San Filippo A Sulfamidase Heparan sulfate
MPS IIIB: San Filippo B -N-acetyl glucosaminidase Heparan sulfate
MPS IIIC: San Filippo C Acetyl transferase Heparan sulfate
MPS IIID: San Filippo D N-acetyl glucosamine 6 Heparan sulfate
sulfatase
MUCOPLYSACCHARIDOSIS

NAME ENZYME DEFECT URINARY

METABOLITES

MPS IVA: Morquio A Galactosamine 6 sulfatase Keratan sulfate,

MPS IVB: Morquio B -galactosidase Chondroitin 6-sulfate

MPS VI: Maroteaux- Arylsulfatase B Keratan sulfate

Lamy

MPS VII: Sly -glucuronidase Dermatanan sulphate

 PROTEOGLYCANS &
GLYCOPROTEINS
z Proteoglycans: When carbohydrate chains
are attached to a polypeptide chain.
z Glycoproteins: Carbohydrate content
10%.
z Mucoprotein: Carbohydrate content
10%

Proteoglycan