Carbohydrate

chemistry
Dr. Yasser Elghobashy
Medical Biochemistry and Molecular
Biology
 Definition and classification
• Definition: CHO are aldehyde or ketone
derivatives of polyhydric alcohols or
compounds that can be hydrolyzed to them.
• Classification: according to hydrolytic products
1. Monosaccharides: are simple sugars that can't be
hydrolyzed into smaller molecules.
2. Disaccharides: 2 monosaccharides
3. Oligosaccharides: 3 – 10 monosaccharides
4. Polysaccharides: more than 10 monosaccharides
 Monosaccharides
• Monosaccharides can be classified according to:
1) The number of carbon atoms into:
A. Trioses: 3 carbons
B. Tetroses: 4 carbons
C. Pentoses: 5 carbons
D. Hexoses: 6 carbons
E. Heptoses: 7 carbons
2) The reactive group into:
A. Aldoses: contain aldhyde group
B. Ketoses: contain ketone group
• Nomenclature can be combined e.g glucose is an
aldohexose while fructose is an ketohexose.
 Structure of monosaccarides
• Trioses:

Glyceraldhyde Dihydroxyacetone
• Tetroses:

• Pentoses:
Erthrose Erythrulose

Ribose Ribulose xylose xylulose

 Hexoses

Glucose Mannose Galactose Fructose

(Aldohexose) (Aldohexose) (Aldohexose) (Ketohexose)
 Cyclic forms of sugars
• Hexoses and pentoses are present in a cyclic structure called Hawarth
forms.
• Glucose is present in a six-numbered ring called pyran ring forming
glucopyranose.
• While fructose and ribose are present in a five-numbered ring called furan
ring forming fructofuranose and ribofuranose.

• The hemiacetal bond present in glucose and ribose is formed between an

alcohol and aldhyde group.
• While the hemiketal bond present in fructose is formed between an
alcohol and ketone group.
• In glucose the –OH group on C5 react with the carbonyl group on C1 to
form stable, cyclic hemiacetal.
• Cyclic structure of glucose:
 Isomerism
• Isomers: These are compounds having the
same molecular formula but differ in spacial
configuration.
• It is due to the presence of asymmetric carbon
atom.
• Asymmetric carbon atom: is a carbon atom
attached to 4 different groups or atoms.
 Types of isomers
1. D and L isomers: The orientation of the H and OH groups
around the carbon atom adjacent to the terminal primary
alcohol carbon (carbon 5 in glucose) determines whether
the sugar belongs to the D or L series.
– D form: when the –OH group is on the right side.
– L from: when the –OH group is on the left side.
– This in relation to the smallest monosaccharide (glyceraldhyde)
which is known as a parent carbohydrate.
– Most monosaccharides occurring in mammals are D sugars
2. Anomers: These are isomers differing in the orientation
of the –H and –OH groups around the anomeric C atom.
• Anomeric carbon atom: Is a new asymmetric carbon
atom that is created by cyclization at the carbon bound
to oxygen in hemiacetal formation e.g C1 in glucose.
– α form if the -OH
is on the right of the
anomeric C.
– β form if the -OH
is on the left of the
anomeric C.
– In solution, α and β
sugars change slowly
to an equilibrium
mixture of both, a
process kown as
mutarotation.
3. Epimers:
– These are isomers which differ in the orientation
of –H and –OH groups around C2, C3 and C4 of
glucose.
– The most important epimers of glucose are
mannose at C2 and galactose at C4.
4. aldo-keto isomers:
– Fructose has the same molecular formula as glucose
but differs in its structural formula, since there is a
keto group in position 2, which is the anomeric carbon
of fructose, whereas there is an aldehyde group in
position 1, the anomeric carbon of glucose.
5- Optical activity:
– It is the ability of sugars to rotate the plane polarized
light (PPL).
– Specific rotation:
o If the PPl is rotated to the right (clock wise) the
compound is dextrorotatory (indicated by d or +).
o If the PPl is rotated to the left (anticlock wise) the
compound is levorotatory (indicated by l or -).
o Glucose is dextrorotatory, fructose is levorotatory.
 Derived Monosaccarides
1. Sugar acids: These are acids resulting from oxidation of C1
and or C6 of aldoses
Example: acids of glucose are formed by oxidation of;
– Aldhyde carbon (C1)→ aldonic acid (gluconic)
– Hydroxyl carbon (C6)→uronic acid (glucuronic)
– Both → Aldaric acid (glucaric or saccharic)
2. Amino sugars:
– In which the hydroxyl group at C2 is replaced by an amino
group.
– Examples:
1. Glucosamine: is a constituent of hyaluronic acid.
2. Galactosamine is found in polysaccharide of cartilage,
chondroitin sulfate.
3. It may occur in acetylated form e,g glycoproteins.
3. Deoxy sugars:
– Obtained by removal of oxygen atom.
– Example: 2-deoxyribose found in DNA

4. Sugar alcohols:
– Formed by reduction of monosaccharide at the
carbonyl carbon
– Examples:
• D-glucose → D-sorbitol.
• D-mannose → D-mannitol.
• D-galactose → D-dulcitol.
• D-fructose → D-mannitol and D-sorbitol.
• D-ribose → D-ribitol.
• D-ribitol is a constituent of riboflavin (vitamin B2)
and in hydrogen carriers FAD and FMN.
 Disaccharides
A. Maltose
– Maltose is called malt sugar
– It is formed of 2 units of α-glucose linked together by α 1-4
glucosidic bond.
– It is a reducing sugar as it has a free carbonyl group
 B. Lactose
• Lactose is the milk sugar
• It is formed of β-glucose and β-galactose linked
together by β 1-4 galactosidic bond
• It is a reducing sugar as it has a free carbonyl group.
 C. Sucrose
• It is called cane sugar.
• It is formed of α-glucose and β-fructose linked by α1-β2
glycosidic bond (C1 of glucose and C2 of fructose).
• It is not reducing as it has no free aldhyde or ketone group
so it will not reduce an alkaline copper reagent such as
Fehling’s solution.
• Invert sugar:
– It is a mixture of glucose and fructose which result
from the hydrolysis of sucrose.
– It is called “invert sugar” because the strongly
levorotatory fructose changes (inverts) the previous
dextrorotatory action of sucrose.
• N.B.
– A sugar can react with an alcohol to form an acetal
known as glycoside e.g
1. Cardiac glycosides: which contain steroids (as
alcohols). These include derivatives of digitalis used
in the treatment of heart failure.
2. Ouabain: an inhibitor of the Na-K ATPase of cell
membranes.
3. Streptomycin: is an antibiotic.
 Polysaccharides
• These are sugars consisting of more than 10
monosaccharide units.
• There are 2 types: -
1. Homopolysaccharides: - Consisting only of one
type of sugar units e.g starch.
2. Heteropolysaccharides: - Consisting of more
than one type of sugar units e.g
Glycosaminoglycans and glycoproteins.
 I. Homo-polysaccharides or
homogeneous
1. Starch:
– Is a homopolymer of glucose
– It forms α-glucosidic chain called a glucosan.
– It is the storage form of glucose in plants.
– It is a mixture of amylose and amylopectin.
a. Amylose: Linear unbranched polymer of α-D-
glucose linked by α1-4 glycosidic bond.
b. Amylopectin: Branched polymer of α-D-glucose
linked by α1-4 glycosidic bond and α1-6 at the
branch point which contain 25-30 glucose unit.
2. Glycogen:
– It is the storage form of CHO in animals.
– Found mainly in liver and muscle.
– It is a highly branched form of amylopectin
(containing both α 1-4 and α 1-6 linkages). The branch
contains 8 – 10 glucose units.
3. Cellulose:
– It is formed of β-glucose units linked by β 1-4
glycosidic bond.
– It is unbranched.
– Is a structural polysaccharide in plant cells.
– It forms part of the human diet (e.g in vegetables and
fruits), but not hydrolyzed by human enzyme systems.
4. Inulin:
- It is a polysaccharide formed of fructose
(fructosan).
- Found in artichokes, tubers and roots of dahlias.
- It is used to determine the glomerular filtration
rate.
5. Dextrins:
- These are intermediates in the hydrolysis of
starch.
6. Dextrans.
 II. Glycosaminoglycans
(mucopolysaccharides)
- These are (complex) heteropolysaccharides.
- Characterized by high content of amino sugars and
uronic acids.
- It is called proteoglycan when attached to a protein
molecule.
- Proteoglycans provide the ground substance of
connective tissues.
- Examples:
1. Hyaluronic acid:
✓ It is formed of β-glucuronic acid and N-acetyl glucosamine.
✓ Found in synovial fluid, vitreous body of the eye, cartilage
and loose connective tissue.
2. Chondroitin sulfate:
✓It is formed of β-glucuronic acid and N-acetyl
galactosamine.
✓It is a prominent component of cartilage.
3. Heparin:
✓It is formed of sulfated glucosamine (few are
acetylated) and sulfated iduronic acid.
✓It is an important natural anticoagulant.
✓Secreted by the mast cells.
✓It activates lipoprotein lipase enzyme.
Glycoproteins (Mucoproteins)
• They are proteins containing oligosaccharides.
• Present in many fluids and tissues including
the cell membranes.
• It contains sialic acid.