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Chem of Carbohydrates 3
Chem of Carbohydrates 3
• Introduction:
• Carbohydrates are widely distributed in nature. They are found
abundantly in plants and in animals. In plants carbohydrates may be
found as sucrose, cellulose, starch and the like. In animals, they are
very important sources of food. They may be transformed to simpler
forms in the animal digestive tract. In the liver they are transformed
into glycogen also known as animal starch. When broken down to
glucose, they provide the main source of energy for living organisms.
Carbohydrates are likewise found in the connective tissues of animals
where they serve as lubricants in joints.
• The simplest form of carbohydrates are the monosaccharides. When 2
of these are linked together the resulting carbohydrate is called a
disaccharide. Both monosaccharides and disaccharides are called
sugars .Linking together of many thousands of monosaccharides lead to
the formation of larger carbohydrates known as polysaccharides.
OBJECTIVES:
At the end of unit, you should be able to.
• define the term ”carbohydrates”
• classify carbohydrates into monosaccharides ,disaccharides, and
polysaccharides.
• give examples of each class
• draw the linear structure of sugar
• draw the ring structure of sugar
• predict the possible stereoisomers, given the structure of a simple
sugar
• explain the properties of carbohydrates as related to their structure.
CHEMISTRY OF CARBOHYDRATES
1. Definition
Carbohydrates – also known as saccharides, are polyhydroxy aldehydes or
ketones and their derivatives with at least three carbon atoms that possess a
carbonyl group.
- most abundant organic molecules
- represented by the simple stoichiometric formula (CH2O)n hence
used to be known as “hydrated carbon”.
- functions: provide significant fraction of the energy in the diet
of most organisms
storage form of energy in the body; used as a primary cellular
fuel
serve as cell membrane components that mediate some forms of
intercellular communication
serve as structural components of many organisms
2. CLASSIFICATION
Classification of carbohydrates is based on their ability to be hydrolyzed
to smaller compounds, by the number of carbon atoms, by the direction
of rotation of polarized light, and by the structural relationships to the
three-carbon sugar glyceraldehyde.
2.1 Monosaccharides are simple, monomeric sugars that can no longer
Glyceraldehyde Dihydroxyacetone
H-C=O H-C=O
H-C-OH HO-C-H
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde
3.3.2 Epimers. These are isomers that differ only in the configuration
around one specific carbon atom. Glucose and mannose are
epimers with respect to carbon atom 2, while glucose and
galactose are epimers with respect to carbon 4.
3.3.3 Optical activity. When a beam of polarized light is allowed to pass
through a solution of an optical isomer, it will be
rotated either to the right, dextrorotatory (+), or to the left, leverotatory
(-), D and L- sugars are not necessarily d-or l-, respectively.
HO-C-H H O OH
H-C-OH H
HO H H
HO-C-H O OH
H-C-OH H OH
H-C
CH2OH
ß-D-Glucopyranose ß-D-Glucopyranose
CH2OH CH2OH
HO-CH2-C-OH O
HO-C-H
O H H HO OH
H-C-OH
OH H
H-C
CH2OH
ɑ-Fructofuranose ɑ-D-Fructofuranose
In the Haworth projection, the alpha (ɑ) designation is used if the
OH group of the anomeric carbon is below the plane of the ring and ß if
the OH group is above the plane of the ring.
O equatorial
Boat form
4. BIOLOGICALLY IMPORTANT SUGARS (Derivatives of Monosaccharides)
4.1 Glycosides- asymmetric mixed acetals formed by the reaction of the
anomeric carbon atom of the intermolecular hemiacetal or pyranose form of
the aldohexose with a hydroxyl group furnished by an alcohol. The anomeric
carbon in glycosides do not interconvert by mutarotation in the absence of
an acid catalyst.
The glycosidic linkage is also formed by the reaction of the anomeric
carbon of the monosaccharide with a hydroxyl group of another
monosaccharide to yield a disaccharide.
They are also hydrolyzed by enzymes called glycosidase which differ
in their specificity according to the type of glycosidases which differ in their
specificity according to the type of glycosidic bond (ɑ or ß ), structure of the
monosaccharide unit (s); and the structure of the alcohol.
4.2 Neutral Sugars
CH2OH
H O H HOCH 2 O
H CH2OH
OH H H HO
HO OH H OH
H OH HO H
ɑ-D-Galactopyranose ɑ-D-Mannopyranose
CH2OH CH 2OH
HO O H H O H
H
OH H OH HO
H OH HO OH
H OH H H
ɑ-D-Galactopyranose ɑ-D-Mannopyranose
4.3 Sugar Acids
The oxidation of the terminal group/s (either the aldehyde group or the
alcohol group, or both) to carboxylic group /s produces three different acid
derivatives of the aldoses.
4.3.1 Aldonic acid is formed from the oxidation of the aldehyde group.
4.3.2 Uronic acid is produced by oxidation of the terminal carbon
(primary alcohol group) to a carboxyl group.
4.3.3 Aldaric acid results from the oxidation of both aldehyde group and
the terminal carbon (primary hydroxyl group) to carbonyl group,
also called saccharic acids.
COOH CHO COOH
(CHOH)n (CHOH)n (CHOH)n
CH2OH COOH COOH
Aldonic acid Uronic acid Aldaric acid
HO H
N-acetyl-Neuraminic acid
(sialic acid)
4.5 Pentoses
The major pentoses are D- ribose, L-arabinose, D-xylose and
L-xylulose.
O CHO
HOCH2 OH HO-C-H
H-C-OH
H H N H-C-OH
H CH 2OH
OH OH
ß-D-Ribofuranose D-Arabinose
4.6 Deoxysugars
These are formed thru selective reduction, when a hydroxyl group
attached to the ring structure has beebn replaced by a hydrogen atom.
The most important is 2-deoxy-D-ribofuranose.
O
HOCH2 OH
H H N
H
CH H
2-deoxy ß-D-Ribofuranose
4.7 Phosphoric Acid Esters of Monosaccharides
These are formed by the reaction of the sugar with a phosphate group which usually comes from a
high-energy compound such as adenosine triphosphate (ATP).
O
CH2OH CH2-C-P-OH
O
O O
H H H H
O
HO OH H O-P-OH HO OH H OH
O
H OH H OH
Glucose-1-phosphate D Glucose-6-phosphate
4.8 Sugar Alcohols
Polyols result from the reduction of the carbonyl group of the sugar
to alcohol.
glyceraldehyde – glycerol
glucose – sorbitol or glucitol
mannose- mannitol
galactose – dulcitol or galactitol
ribose – ribitol
CH2OH CH2OH
H-C-OH HO-C-H
HO-C-H HO-C-H
H-C-OH H-C-OH
H-C-OH H-C-OH
CH2OH CH2OH
D-Sorbitol D-Mannitol
5. OLIIGOSACCHARIDES
5.1 Homo-oligosaccharides yield only one kind of sugar upon
hydrolysis.
Maltose (D-glucopyranosyl-ɑ-1,4-ɑ-D-glucopyranose)
CH2OH CH2OH
H O H H O H -formed as an intermediate
OH H O OH product of the action of amy-
HO OH lass on starch
H OH H OH - contains 2-D- glucose
residues
Isomaltose (D-glucopyranosyl-ɑ-1,6-ɑ-D-glucopyranose)
CH2OH
O
HO OH
O CH2
OH O
OH
HO OH
OH
Cellobiose (D-glucopyranosyl-ß-1, 4-ß-D- glucopyranose
CH2OH CH2OH
O O
OH
O
OH OH
HO
OH OH
5.2 Hetero-oligosaccharides yield more than one kind of sugar units
upon hydrolysis.
5.2.1 Lactose (D-galactopyranosyl-ß-1, 4-ɑ-D-glucopyranose)
CH2OH CH2OH
HO O O -has a free anomeric carbon
on the glucose residue
O hence in redicing sugar
OH OH OH
OH OH
5.2.2 Sucrose (D-glucopyranosyl-ɑ-1, 2- D –fructofuranose)
H O HOCH2 O H
OH H
HO O CH2OH
H OH 1, 2 OH
N-acetylglucosamine-asparagine linkage
CH2OH O
H O H N NH
N - C - CH2 - CH
C=O N-linked
OH
HO
O
NH - C - CH3
N-acetylgalactosamine-serine linkage
CH2OH
HO O
H
C=O O-linked
OH H
O – CH-CH-NH-
N NH-C-CH3
O
Galactose - hydroxylysine linkage
CH2OH NH2
HO O CH2
OH H O CH
H H CH2 O-linked
H OH CH2
CH-NH2
C=O
Xylose-serine linkage