1-Carbohydrates 1

BIOCHEMISTRY ( I ) AUTUMN 2016 CHARBOHYDRATES SALEM EL TUMI
CARBOHYDRATES
A carbohydrate is an aldehyde or a ketone that has additional hydroxyl groups or
compounds that give these on hydrolysis.
The simplest carbohydrates are called monosaccharides, which has the basic structure
(CH2O)n , where n is three or greater.
Term “CARBOHYDRATES” came from the fact that these compounds could be
written as “hydrates of carbon”
n= 6
e.g. ( CH2O )6 C6H12O6
 Importance of Carbohydrates
i. Energy production. e.g. ( Oxidation of glucose to produce ATP )
ii. Formation of structural elements in animal and plant cells.
iii. Glycolipids and glycoproteins enter in the structure of cell membrane
 Classification of Carbohydrates
(the word “saccharide” is derived from the Greek sakcharon, meaning “sugar”). All
common monosaccharides and disaccharides have names ending with the suffix
“-ose.”
i. Monosaccharides: Contain one sugar unit. ( Glucose, Fructose, Galactose )

ii. Disaccharides: Contain two sugar units. ( Sucrose, Lactose, Maltose )
iii. Oligosaccharides: Contain 3-10 sugar units. ( Raffinose )
iv. Polysaccharides: Contain more than 10 sugar units. ( Amylose, Cellulose )
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 Carbohydrates are classified according to

 Location of carbonyl group ( C=O ).
 Length of the carbon chain.
 Stereochemistry.
 Size of ring formed.
 Number of sugar units.
1. Based on location of carbonyl functional group (C=O) aldehydes or ketones.
2. Classified according to chain length.
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Aldehyde Keton
Trioses(3) Glyceraldehyde Dihydroxyacetone
(aldotriose) (ketotriose)
Tetroses(4) Erythrose Erythulose
(aldotetrose) (ketotetrose)
Pentoses(5) Ribose Ribulose
(aldopentose) (ketopento)
Hexoses(6) Glucose,Galactose,Mannose Fructose
(aldohexose) (Ketohexose)
3. Stereochemistry of carbohydrates.
The D- and L- system of stereochemistry according to the first chiral "asymmetric"

centre from the bottom is:
to the RIGHT, then ( D ) to the LEFT, then ( L )
4. Size of ring formed.
 Five-membered ring is called furanose. This name is derived from Furan.

 Six-membered ring is called Pyranose. This name is derived from Pyran.
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5. Number of sugar units.
Monosaccharides. Dissaccharides . Oligosaccharides. Polysaccharides.
Monosaccharides
Aldoses containing three, four, five, and six carbon atoms.
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-Ketoses containing three- four, five, and six carbon atoms

 Stereochemistry terms:
 Enantiomer :- Two carbohydrates are said to be enantiomers if they are

nonsuperimposable mirror images of one another.
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 Diastereomer:- Isomers contain more than one chiral center and are not mirror
images. Unlike an enantiomer, diastereomers are not mirror image.
 Epimer:- Carbohydrate isomers differ at only a single chiral center.
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 Chiral carbon atom:- An asymmetric carbon atom is a carbon atom that is

attached to four different types of atoms or four different groups of atoms.
 Optical activity:- It is the ability of substance to rotate plane-polarized light either

to the right or to the left. The sugars rotating the plane-polarized light to left are termed
as levorotatory while those which rotate the plane-polarized light to right are termed as
dextrorotatory.
The levorotation is represented by l or (–) sign while the dextrorotation is represented by d
or (+) sign.
 Optical isomerism:- it is the ability of substance to present in more than one form
(ISOMER) dependent on the chiral carbon atoms and according to
Vant Hoff’s law (the number of possible optical isomers of a substance are equal to
( 2n ) where n is the number of chiral carbon atoms).
Racemic: When equal amounts of dextrorotatory and levorotatory isomers are present,
the resulting mixture has no optical activity, since the activities of each other isomer
cancels each other. Such a mixture is said to be Racemic.
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 Mutarotation:- it is a gradual change of specific rotation of any optically active

substance having free aldehyde (-CHO) or ketone (C=O) group. When both anomers of
glucose (α +112 degrees & β +18.7 degrees) are left for sometimes, sugar slowly change
into an equilibrium mixture which has specific rotation of (+52.5).
 Physical properties of Monosaccharides:-

They are colorless, crystalline compounds, readily soluble in water. Their solutions are
optically active and exhibit the phenomenon of mutarotation. Carbohydrates
spontaneously change between the α and β configuration.
 Chemical properties of Monosaccharides:-

i. Effect of strong acid " H2SO4":- Concentrated sulphuric acid reacts with sugars
to give furfural derivatives
Pentose reacts with sulphuric acid to give furfural.
Hexose reacts with sulphuric acid to give hydroxymethyl furfural.
 "MOLISCH TEST" these furfural compounds condense with α-naphthol to form

violet colored compounds. This is basic of the general test for carbohydrates.
ii. Oxidation:- Oxidation of carbonyl carbon, hydroxyl carbon or both to produce
compounds known as Sugar acids.
 Aldonic acid:- Oxidation carbonyl carbon to carboxylic group
e.g. glucose oxidized to gluconic acid.
 Uronic acid:- Oxidation of last hydroxyl carbon to carboxylic group
e.g. glucose oxidized to glucuronic acid.
 Aldaric acid:- Oxidation carbonyl carbon and last hydroxyl carbon to carboxylic
group. e.g. glucose oxidized to glucaric acid.
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a- Oxidation by Bromine :
b- Oxidation by Tollens Reagent
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c- Oxidation by Nitric acid
iii. Reduction:- Reduction of carbonyl carbon in both Aldoses or Ketoses to the

corresponding alcohol known as Sugar alcohol.
 Glucose is reduced to Glucitol "Sorbitol"
 Mannose is reduced to Mannitol.
 Galactose is reduced to Galacticol.
 Fructose is reduced to ………………. , ……………………
iv. Reducing property:- Sugars with free anomeric carbon atoms are good reducing
agents and will reduce (Cu++). Such reactions convert the sugar to a sugar acid. For
example, addition of alkaline CuSO4 (called Fehling’s solution) to an aldose sugar
produces a red cuprous oxide (Cu2O) precipitate. Also Benedict reagent similar to
Fehling but is more stable, more specific and more sensitive.
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v-Osazone formation
Emil fischer found that when phenylhydrazine is added to an aldose or ketose, a
yellow crystalline solid that is insoluble in water is formed. He called this derivative
an osazone ("ose" for sugar; "azone" for hydrazone).
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vi-Sugar esters:- Phosphate esters of glucose, fructose, and other monosaccharides

are important metabolic intermediates, and the ribose moiety of nucleotides such as
ATP and GTP is phosphorylated at the 5ʼ position.
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vii- Deoxy sugars:- Monosaccharides with one or more hydroxyl groups replaced by
a hydrogen. 2-deoxy-D-ribose is a key component of DNA (deoxy-ribo-nucleic acids).
Viii Amino sugars:- Some saccharides have an amino (-NH2) group instead of a
hydroxyl group. Amino sugars are found in bacterial cell walls.
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CYCLIZATION OF MONOSACCHARIDES
 Alcohols react readily with aldehyde or ketone to form HEMIACETAL or
HEMIKETAL respectively.
 stereochemistry of the aldehyde and ketone carbon it goes from being achiral to
chiral.
 Since aldoses and ketoses contain alcohol groups, in addition to their aldehyde or
ketone groups, they have the potential to react to form cyclic forms.
 In cyclic structure, the carbonyl carbon becomes asymmetric and known as

(ANOMERIC CARBON) and the sugar is present in two isomeric forms (anomers)
the β form where the OH group is on the up and the α form where the OH group is
present on the down.
 The cyclic hemiacetal that has five-membered ring is called furanose. This
name is derived from Furan Ring .
 Hemiacetal with six-membered ring is called Pyranose. This name is

derived from Pyran Ring.
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CYCLIZATION OF GLUCOSE
CYCLIZATION OF FRUCTOSE
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GLYCOSIDIC BOND FORMATION

Hemiacetals and hemiketals (found in cylic forms of saccharides) can react with
alcohols (under acidic conditions) to form acetals and ketals. The alcohol can be from
another saccharide, and form a glycosidic bond between two saccharides. This is a
condensation reaction (releases H2O)
 COMMON DISACCHARIDES
Monosaccharides bind together covalently through glycosidic linkages to form
disaccharides (two sugars) or polysaccharides (large polymers of monosaccharides).
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 MALTOSE:
Maltose is composed of two glucose units linked together by a glycosidic bond between
C1 of one glucose and C4 of the other.
 LACTOSE:
Lactose is composed of two units galactose and glucose linked together by a glycosidic
bond between C1 of one galactose and C4 of the glucose.
SUCROSE:
Sucrose is composed of two units glucose and fructose linked together by a glycosidic
bond between C1 of one glucose and C2 of the fructose.
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Polysaccharides,
Polysaccharides also called glycans, consist of monosaccharides and their derivatives. If
a polysaccharide contains only one kind of monosaccharide molecule, it is a
HOMOPOLYSACCHARIDE, or homoglycan.
Whereas those containing more than one kind of monosaccharide are
HETEROPOLYSACCHARIDES.
HOMOPOLYSACCHARIDE
i. Starch:- Starch is the major form of stored carbohydrate in plants. Starch is

composed of a mixture of two substances: amylose an essentially linear polysaccharide,
and amylopectin a highly branched polysaccharide. Natural starches contain 10-20%
amylose and 80-90% amylopectin.
Amylose:- molecules consist typically of 200 to 20,000 glucose units in α (1 4)

glycosidic linkage.
Amylopectin:- Branched polysaccharide each branched is formed of 24-30 glucose

molecules within the branch, the glucose molecules in α (1 4) glycosidic linkage and
at the branching points they are in α (1 6) glycosidic linkage.
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ii. Cellulose:- The most abundant natural polymer found in the world. Found in the cell
wall of all plants, consisting of 3,000 or more glucose units the glucose units are in β (1
4) glycosidic linkages. it provides physical structure and strength.
 Cellulose is thus resistant to hydrolysis. A special enzyme (cellulase) is needed to hydrolyze the
glycosidic bond. Some bacteria make cellulase and can therefore "eat" cellulose.
 HETEROPOLYSACCHARIDES
i. Heparin:- the most abundant a highly sulfated glycosaminoglycan, is widely used as
an injectable anticoagulant, and has the highest negative charge density of any known
biological molecule. It consist of repeating disaccharide units of glucuronate-
2-sulfate and N-sulfo-glucosamine-6-sulfate.
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ii. Hyaluronate:- differs from other types of glucosamine it is unsulfated not

covalently linked with protein. It consist of repeating disaccharide units of
glucuronate and N- acetylglucosamine.
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BIOCHEMISTRY ( I ) AUTUMN 2016 CHARBOHYDRATES SALEM EL TUMI

ii. Formation of structural elements in animal and plant cells.

iii. Glycolipids and glycoproteins enter in the structure of cell membrane

i. Monosaccharides: Contain one sugar unit. ( Glucose, Fructose, Galactose )

 Carbohydrates are classified according to

2. Classified according to chain length.

The D- and L- system of stereochemistry according to the first chiral "asymmetric"

to the RIGHT, then ( D ) to the LEFT, then ( L )

4. Size of ring formed.

 Five-membered ring is called furanose. This name is derived from Furan.

5. Number of sugar units.

Monosaccharides. Dissaccharides . Oligosaccharides. Polysaccharides.

Aldoses containing three, four, five, and six carbon atoms.

-Ketoses containing three- four, five, and six carbon atoms

 Enantiomer :- Two carbohydrates are said to be enantiomers if they are

 Epimer:- Carbohydrate isomers differ at only a single chiral center.

 Chiral carbon atom:- An asymmetric carbon atom is a carbon atom that is

 Optical activity:- It is the ability of substance to rotate plane-polarized light either

 Mutarotation:- it is a gradual change of specific rotation of any optically active

 Physical properties of Monosaccharides:-

 Chemical properties of Monosaccharides:-

Pentose reacts with sulphuric acid to give furfural.

Hexose reacts with sulphuric acid to give hydroxymethyl furfural.

 "MOLISCH TEST" these furfural compounds condense with α-naphthol to form

e.g. glucose oxidized to gluconic acid.

 Uronic acid:- Oxidation of last hydroxyl carbon to carboxylic group

e.g. glucose oxidized to glucuronic acid.

b- Oxidation by Tollens Reagent

c- Oxidation by Nitric acid

iii. Reduction:- Reduction of carbonyl carbon in both Aldoses or Ketoses to the

vi-Sugar esters:- Phosphate esters of glucose, fructose, and other monosaccharides

 In cyclic structure, the carbonyl carbon becomes asymmetric and known as

 Hemiacetal with six-membered ring is called Pyranose. This name is

GLYCOSIDIC BOND FORMATION

i. Starch:- Starch is the major form of stored carbohydrate in plants. Starch is

Amylose:- molecules consist typically of 200 to 20,000 glucose units in α (1 4)

Amylopectin:- Branched polysaccharide each branched is formed of 24-30 glucose

ii. Hyaluronate:- differs from other types of glucosamine it is unsulfated not

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