BIOCHEMISTRY OF

CARBOHYDRATE

Dr. Shabbir Hussain

MPhil. Ph.D.(Biochemistry)
Assistant Professor
University of Health Sciences Lahore
 Carbohydrate

General characteristics

• The term carbohydrate is derived from the french: hydrate de carbone

• Compounds composed of C, H, and O

• Empirical formula: (CH2O)n

Greek “sakcharon” = sugar

Carbohydrates

• Definition:
• Poly hydroxy aldehydes or poly hydroxy-ketones or substances which
yield such substances on hydrolysis are known as carbohydrates .
• Aldose – polyhydroxyaldehyde, eg glucose
• Ketose – polyhydroxyketone, eg fructose
 General Biological functions
• sources of energy
• intermediates in the biosynthesis of other basic biochemical entities
(fats and proteins)
• associated with other entities such as glycosides, vitamins and
antibiotics)
• form structural tissues in plants and in microorganisms (cellulose, lignin,
murein)
• participate in biological transport, cell-cell recognition, activation of
growth factors, modulation of the immune system
 Biomedical importance
• Glucose is the sugar of the body
• Glucose is the precursor of other sugars formed in the body e.g.
glycogen, ribose, galactose etc
• Ribose and deoxyribose sugars forms part of the structural frame
works of DNA & RNA
• Diseases associated with carbohydrate metabolism are diabetes
mellitus, lactose intolerance, glycogen storage diseases and
galactosemia
• Types of carbohydrates:
• Monosaccharides – carbohydrates
that cannot be hydrolyzed to simpler
carbohydrates; eg. Glucose or fructose.

• 3Carbons: trioses Glyceraldehyde

• 4 Carbons: tetroses Erythrose

• 5 Carbons: pentoses Ribose

• 6 Carbons: hexoses Glucose

• 7 Carbons: heptoses sedoheptulose

Disaccharides –
carbohydrates that can be hydrolyzed into two monosaccharide units; eg. Sucrose, which is
hydrolyzed into glucose and fructose.

Maltose: 2 glucose residues

Lacotse: glucose and galactose

Oligosaccharides – carbohydrates that can be hydrolyzed into a few

monosaccharide units. (From 3 to 10 units)
Maltotriose

Polysaccharides – carbohydrates that are polymeric sugars; eg Starch or

cellulose.
1. Homopolysaccharides
Starch, Glycogn, Cellolose
2. Heteropolysaccharides:
Hemicellulose, Heparin, Chondroitin sulfate
 Derived carbohydrates
• Compounds which are derived from other carbohydrates
• Suger acids
• Suger alcohols
• Amino sugers
• Deoxy sugers
 Monosaccharides
• The most important monosaccharides are pentoses and hexoses ….
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 Monosaccharides
Glucose:
 The most important of the monosaccharides. It is an aldohexose and is found in
The free state in plant and animal tissue.
 Glucose is also known as dextrose and grape sugar.
 Glucose is a component of the disaccharides sucrose, maltose, and lactose and is the
monomer in the polysaccharides amylose, amylopectin, cellulose, and glycogen.
 Glucose is the key sugar of the body and is carried by the bloodstream to all body parts.
Galactose
• It is an aldohexose like glucose and occurs, along with glucose, in lactose and in many
oligo- and polysaccharides.
• Galactose is synthesized in the mammary glands to make the disaccharide lactose
(milk sugar).
• It is also a constituent of glycolipids and glycoproteins in many cell membranes.

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 Monosaccharides
Fructose,
• It is also known as levulose
• it is a ketohexose that occurs in fruit juices, honey, and, along with glucose, is a
constituent of the disaccharide sucrose.
• Fructose is the major constituent of the polysaccharide inulin.
• Fructose is the sweetest of all the common sugars, being about twice as sweet a
glucose.
This accounts for the sweetness of high-fructose corn syrup and honey.

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Sugars show many kinds of isomerism
Isomers:
The compounds which have the same empirical formulae but having different
molecular structure is said to be Isomers.

• Aldo and keto isomers

• D and L isomers
• Enantiomers
• Diasteriomers

Epimers
Rearrangement of OH- around a specific chiral carbon may result into epimerism. e.g
Mannose and galactose are C-2 and C-4 epimers of glucose.
Stereochemistry in Monosaccharides
Multiple chiral centers
• Recall that a chiral center is a carbon atom that has four different atoms
or groups of atoms attached to it.
• Glucose, a ketohexose, contains four different chiral centers, each with a
tetrahedral geometry.
Multiple chiral centers
• Carbons 2 through 5 of glucose are tetrahedral and have four different
atoms or groups of atoms attached. Carbons 1 and 6 are not chiral
centers.
Multiple chiral centers
• Groups bonded to each chiral center have two different
arrangements or mirror images, which result in
stereoisomers.
• The number of stereoisomers for a molecule increases with
the number of chiral centers in the molecule.
• The general formula for determining the number of
stereoisomers is 2n, where n is the number of chiral centers
present in the molecule.
• Glucose has 4 chiral centers, so there are 16 stereoisomers,
24 = 16.
Representing stereoisomers—the Fischer projection
• Fischer projection is a simple way of indicating chiral
molecules by showing their three-dimensional structure in
two dimensions, without showing all the wedges and
dashes on all the chiral centers.
• In the Fischer projection, horizontal lines on a chiral center
represent wedges, and vertical lines on a chiral center
represent dashes.
Representing stereoisomers—the Fischer projection
• D and L designations of sugars are based on the
Fischer projection positioning in glyceraldehyde.
• All D-sugars have the –OH on the chiral carbon
farthest from the carbonyl group on the right side of
the molecule.
• All L-sugars have the –OH on the chiral carbon
farthest from the carbonyl group on the left side of
the molecule.
• Most sugars in nature have the D designation.
 Monosaccharides
The Fischer projections of D-glucose, D-galactose and D-fructose are shown here.

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 Monosaccharides
The Fischer projections of the pentoses D-ribose and D-2-deoxyribose are shown here.

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Ring Formation—The Truth about Monosaccharide Structure
• Carbonyl groups can also react with a hydroxyl functional group (–OH).
• When this happens, a hemiacetal functional group is formed as shown:
A hemiacetal can form within a monosaccharide
since it contains both a carbonyl and several hydroxyl
functional groups.
• The carbonyl carbon that reacts to form the
hemiacetal is referred to as the anomeric carbon.
• Two ring arrangements can be produced. These are
termed anomers, and are referred to as the alpha ()
and beta (β) anomer.
• The position of the –OH group on the anomeric
carbon relative to the position of the carbon outside
the ring determines the type of anomer present
• In the six-member ring (five carbons and an oxygen)
form of D-isomers, called a pyranose, carbon 6 is
always drawn on the top side of the ring.
• In the  anomer, the –OH on the anomeric carbon is
trans to the carbon outside the ring.
• In the β anomer, the –OH on the anomeric carbon is
cis to the carbon outside the ring.
• D-Fructose contains both a ketone group and several
hydroxyl groups.
• The ring structure of D-fructose contains four carbons
and an oxygen to form a five-membered ring called a
furanose.
• In a furanose, carbons 1 and 6 remain outside the ring.
• In a five-membered and six-membered ring, the
anomers are distinguished similarly.
• In the alpha anomer, the –OH on the anomeric carbon
is trans to the carbon outside the ring.
• In the beta anomer, the –OH on the anomeric carbon
is cis to the carbon outside the ring.
 Cyclic Structure of Glucose; Mutatoration
Straight open-chain D-glucose is so reactive that almost all molecules quickly rearrange
their bonds to form two new structures. These structures are six-membered rings called
pyranose sugars.

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 Cyclic Structure of Glucose; Mutatoration
An interesting phenomenon occurs when the α- and β-forms of glucose are put into
separate solutions and allowed to stand for several hours. The phenomena that occurs
is called mutarotation.

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 Cyclic Structure of Glucose; Mutatoration
During mutarotation the two cylic forms convert into each other through the open-chain
form. The resulting equilibrium solution contains about 36% α and 64% β molecules
with a trace of open-chain molecules.

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 Pentoses
D-Ribose and its derivative D-2-deoxyribose are
the most important pentoses because they
are found in the nucleic acids RNA and DNA.

The 2-deoxy in D-2-deoxyribose means an

oxygen is omitted from the D-ribose
molecule at carbon #2.

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 Pentoses
Ribulose is a ketose that is related to ribose. It is a
biological intermediate used by cells to make other
monosaccharides.

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Disaccharides

Maltose:
• Maltose contains 2 glucose residues joined by a glycosidic linkage C-
1 of one glucose residue and C-4 of the other.
• It’s a reducing sugar.
• Digested by maltase enzyme.
• Linkage α (1→4)
• Digestion of starch by amylase, germinating cereals and malt.
• Relative sweetness:32
Lactose:
Lactose contains D-Galactose and D- glucose joined by β (1→4)
Glycosidic linkage.
It’s a reducing suger.
It is digested by lactase enzyme.
Source:
It occurs naturally only in milk, also called as milk sugar.
Lactose intolerance:
Sucrose:
• it contains D-glucose and D-fructose residues joined by α-
β(1→2) Glycosidic linkage.
• Relative sweetness: 100
Sources:
• Cane and beet sugar, pine apple, carrot roots.
• In sucrase deficiency, Malabsorption of sucrose leads to diarrhea
and flatulence.
Other disaccharides

1. Trehalose α (1→1) glucose-glucose

2. Cellobiose β (1→4) glucose-glucose
3. Isomaltose α (1→6) glucose-glucose
Chemical properties of monosaccharides

Carbonyl reactions
1. Osazone formation
2. Oxidation
3. Reduction
4. Action of acid
5. Action of base
6. Ring chain tautomerism
Continuous……………….

Alcohol reactions:
1. Glycosidic formation
2. Ether formation
3. Ester formation
Formation of Osazones:
Reaction of monosaccharides with phenyl hydrazine.
e.g.,
glucose→glucozasone
Oxidation reactions:
Aldoses may be oxidized to 3 types of acids:
e.g.
Glucose ------ gluconic acid
glucaric acid
glucoronic acid→ conjuga on reac ons
Reduction reactions:
On reduction, monosaccharides are converted into sugar ALCOHOLS.
e.g.
Glucose ---------- sorbitol (cataract)
Mannose ---------- mannitol
(osmotic diuretic)
Glyceraldehyde ------- -- glycerol
• Action of strong acids on monosaccharides:
5 carbon monosaccharides-------- furfural compounds
6 carbon monosaccharides-------- hydroxy methyl furfural compounds.
• Action of strong bases:
Sugars can form salts at high pH.
Enediols salts are formed
• Tautomerism :
Rearrangement in sugar molecules in alkaline medium is known as
tautomerism.
e.g. formation of endioles.
Alcohol reactions

• Glycoside formation:
Glycosidic bond is formed by a reaction between the –OH group of the
anomeric carbon of a monosaccharide and a second compound that
may or may not be another monosaccharide, typically an alcohol,
purines, Pyrimidine or sugar)
If second group is –OH the O-glycosidic bond is formed------glycosides
If second group is an amine ,an N-glycosidic bond is formed e.g.
between adenine and ribose in nucleotides such as ATP.
Cardiac glycosides: steroids are aglycone part.
• Ester formation:
Sugar OH groups react with acids to form sugar esters.
e.g. glucose 6-phosphate

• Reducing property of monosaccharides:

Certain sugars have reducing property ( can reduce other substances)
Its Free anomeric carbon which causes reduction of other substances. .
e.g.
Glucose ,galactose,mannose,maltose,lactose.
What about sucrose??????
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