Biochemistry

Programme: BBME 2
Course code: PBS-BIO-221

Carbohydrates

Facilitator: B. Phiri Mando (Mrs)

 Uses of carbohydrates
• Carbohydrates are the most abundant class of naturally occurring organic
compounds.
• Plants are the main source of commercial carbohydrates, the dry
substance is usually composed of 50 –80% of carbohydrates.
• E.g: Glucose, cellulose, starch, and glycogen are all carbohydrates.
• Carbohydrates provide us with the necessities of life:
1. Carbohydrates are source of energy and fuels.
 We eat starch-containing grain, or feed it to animals to be converted
into meat and fat which we then eat.
2. We clothe ourselves with cellulose in the form of cotton and linen,
rayon and cellulose acetate.
3. We build houses and furniture from cellulose in the form of wood.
4. Carbohydrates play a central role in a very wide range of biological
processes..
 Uses of carbohydrates cont…
• Carbohydrates play a central role in a very wide range of biological
processes.
• As a constituent of human blood
 They play a determinant role in antibody-antigen recognition and binding
and also different sequences of sugars determine the different blood group
types.
 Antibiotics production
 Many of which are natural secondary metabolites produced by fungi,
bacteria and actinomycetes often contain carbohydrates moieties in their
basic structure e.g. streptomycin which has been used widely for treatment
of tuberculosis.
 It is the major building blocks of the genetic material, RNA and DNA
 The nucleotide components contains ribose sugar which together with a
phosphate form the backbone of polynucleotide chains of both RNA and
DNA structures.
Cell-cell communication (attached to proteins and lipids in the plasma
membrane)
 Classification of carbohydrate
• All carbohydrates have a general formula Cx(H2O)y and are always
found in the ratio of 1 carbon to 2 hydrogens to 1 oxygen (1:2:1).
• Carbohydrates are classified according to their products of
hydrolysis by acid or enzymes into:
1. Monosaccharides: simple sugars that are building blocks of all larger
carbohydrate structures.
2. Disaccharides: Two monosacharides convalently bonded together
3. Oligosaccharides: A few monosacharides convalently linked
together
4. Polysachharides: A larger polymer consisting of chains of
monosacharides or disaccharide units
 Monosaccharides
• They are the simplest forms of carbohydrates and therefore the
name ‘simple sugars’.
• Monosaccharides contain three to seven carbon atoms per
molecule.
• Cannot be hydrolysed into simpler units.
• e.g. glucose, fructose, galactose, mannose, sorbose etc.
• Monosaccharides may be further classified into two groups
depending on the nature of their carbonyl function and these are
aldoses and ketoses.
 Monosaccharides
Aldoses: These are monosaccharides containing an
aldehyde group on the first carbon atom.
• Aldoses have an aldehyde group (R-CH=O)/(R-CHO)
• Example include: glucose
Ketoses: These are monosaccharides containing a keto
group on the second carbon atome.g. fructose
• Ketoses contain a ketone group (C=O)
• An example of a ketose is fructose.
 Monosaccharides cont..
• Monosaccharides are further
classified according to the length of
their carbon chain into trioses,
tetroses, pentoses etc.
• Trioses: 3 carbon sugars e.g.
glyceraldehydes (glycerose)
• Tetroses: 4 carbon sugars e.g.
erythrose, threose
• Pentoses: 5 carbon sugars e.g.
arabinose, ribose, xylose
• Hexoses: 6 carbon sugars e.g.
glucose, fructose, galactose
Monosaccharides cont..
• A monosaccharide can be named taking into account the two
classifications thus an aldose or ketose.
• An aldohexose, for example, is a six-carbon monosaccharide
containing an aldehyde group
• A ketopentose is a five-carbon monosaccharide containing a
keto group.
• Most naturally occurring monosaccharides are pentoses and
hexoses.
• Draw an example of each type of compound.
• an aldotetrose
• a ketopentose
• Ketohexose
• ketotriose
Monosaccharides cont..
Monosaccharides cont..
 Structures: Fischer projections (open-chain)
• It is a convention commonly used • Vertical lines represent bonds
for writing two-dimensional pointing away from you, while
representations of the horizontal lines represent bonds
monosaccharides. coming toward you.
• Developed by H. Emil Fischer, a • The formulas of chiral molecules
German chemist. represented in this manner are
referred to as Fischer projections.
• In these structural formulas
aldehyde group is written at the • E.g
top, and the H atoms and OH
groups are attached to each chiral
carbon, written to the right or
left.
• If it is a ketose, ketone group is the
2nd carbon atom.
 Aldose/Ketose Isomers
• Aldoses and ketoses can be
structural isomers;
• Isomers have same molecular
formula but their atoms are
bonded in a different order.
• Due to the high number of
chiral centers within the sugar
structures, they generate a lot
of potential isomers. For every • D-Glyceraldehyde D-Dihydroxyacetone
aldose structure, there exists a Are isomers
ketose with the same
molecular formula.
Enantiomers: D and L isomers/configuration
• Enantiomers are isomers that are chiral and non-
superimposable are mirror images of each other.
• Types of enantiomers :
1. D form: OH attached to the right of prelast C.
2. L form: OH attached to the left of prelast C
• Description :They differ in all carbons (mirror image) but D
& L configuration is according to H – OH orientation in the
pre-last C.
• NB: The great majority of the sugars in humans are D-sugars
 Enantiomers: D and L isomers/configuration cont..
• Examples include:
 Enantiomers: D and L isomers/configuration
• Chiral carbon is a carbon atom • Stereoisomers are
that is attached to four different isomers/molecules that have
types of atoms. identical chemical formulas and
• Chiral carbons are also called connections between atoms but
asymmetric carbon/ different 3D structures/
stereogenic carbons. arrangement in space.
• Glyceraldehyde, the simplest • D- and L-glyceraldehyde were
possible aldose, is made up of three then used to provide reference
carbons and only one these is chiral. points for designating and
• Glyceraldehyde has two drawing all other
stereoisomers, called D- monosaccharides.
glyceraldehyde and L-
glyceraldehyde
 D and L configuration cont..
• In general, sugars may be defined as
belonging to the D-series when the
asymmetric carbon atom most
remote/farthest from the reference
group, e.g. -CHO, -CO,-COOH etc.
• D and L designations of sugars are
based on the position of the -OH
on the chiral carbon farthest from
the carbonyl group in the Fischer • Glucose, shown above, has four
projection of the molecule. asymmetric carbons marked by
asterisks.
• All D-sugars have the –OH on the
right side and L-sugars have the – • The most farthest chiral carbon (see
OH on the left side. arrow) is the one from which the
configuration D and L is derived.
 Stereoisomers
• Monosacchraides can also have many • E.g glucose has four chiral
stereoisomers, depending on how many centres, therefore there are 24 =
chiral carbon centres are present. 16 stereoisomers for this class of
• Stereoisomers: the sugars have the same sugar.
molecular formula and the same bonded
order, but a different 3‐dimensional
arrangement in space.
• To determine how many stereoisomers
exist for a particular sugar, first
determine the chiral centers of the
sugar
• The number of stereoisomers = 2n
where n = the number of chiral centres.
 Epimers
• Sugars that differ only by the
stereochemistry at a single
carbon are called epimers.
• The carbon atom where they
differ is generally stated. If the
number of the carbon atom is
not specified, it is assumed to be
C2.
• For example, glucose and
mannose differ only at C2, the
first chiral carbon. Therefore
glucose and mannose are “C2
epimers” or simply “epimers”.
• The C4 epimer of glucose is
galactose, and the C2 of epimer
of erythrose is threose.
 Epimers
• Are sugars that differ only by the stereochemistry at a single carbon and the
carbon atom where they differ is generally stated.
• If the number of the carbon atom is not specified, it is assumed to be C2. For
example, glucose and mannose differ only at C2, the first chiral carbon.
• Therefore glucose and mannose are “C2 epimers”. The C4 epimer of glucose is
galactose, and the C2 of epimer of erythrose is threose.
 Cyclic Hemiacetals and hemiketals
• The aldehyde or ketone group can • Therefore, when -OH reacts
react with a hydroxyl group to form a with an aldehyde, the product is
covalent bond. called a ‘hemiacetal’
• They are formed when an alcohol • When –OH reacts with with a
atom adds to the carbonyl carbon of ketone, the product is referred
an aldehyde or a ketone. to as a ‘hemiketal’.
• This happens through the nucleophilic
attack of the hydroxyl group at the
electrophilic carbonyl group.
• Since alcohols are weak nucleophiles
(a molecule rich in electrons), the
attack on the carbonyl carbon is
usually helped by protonation of the
carbonyl oxygen.
 Drawing Cyclic hemiacetal: Haworth’s structure
• Lay the Fischer projection.
• C and O atoms of the ring are drawn in the plane of the page.
• H and OH or other side groups are written on perpendicular plane
• All groups located on the right side of fisher’s are written downwards
Except in Last C in the ring.
• All groups located on the left side of fisher’s are written upwards.
• C5 and C6 curl back away from you. The C4-C5 bond must rotate so that
the C5 hydroxyl group can form a part of the ring.. close the ring and draw
the result.
• C1 is easily identified because it is the hemiacetal carbon, the only carbon
bonded to two oxygens. The –OH group on C1 can be either down or up
as discussed before.
Drawing Cyclic hemiacetal: Haworth’s structure
Drawing Cyclic hemiacetal: Haworth’s structure
 So why doesn’t the hydroxyl attached to C-4 react with the
carbonyl group?
 Why does the carbonyl group react with the hydroxyl attached
to C-5?
 C-4 hydroxyl attacking the carbonyl group will lead to the
formation of a 5-membered ring, while the attack of C-5
hydroxyl at the carbonyl group will generate a 6-membered ring
(as shown in glucopyranose).
 In the case of glucose, a 6-membered ring is thermodynamically
more stable than a 5-membered ring, thus favoring the formation
of a 6-membered ring over a 5-membered ring.
 Chair conformation structure
• Chair conformations are also easily drawn by recognizing the
difference between the sugar in question and glucose.
• The following procedure is useful for drawing D-aldohexoses.
• 1. Draw the chair conformation, hemiacital carbon (C1) is the
footrest.
• 2. Glucose has its substituents on alternating sides of the ring.
Chair conformation structure
• Always draw the Haworth projection of chair conformation with the
oxygen at the back, right-hand corner, with c1 at the far right. C1 is
easily identified because it is the hemiacetal carbon, the only carbon
bonded to two oxygens.
• The –OH group on C1 can be either down or up.
Drawing Cyclic hemiacetal: Haworth’s structure
• In basic organic chemistry it was seen that an aldehyde reacts
with one molecule of an alcohol to give a hemiacetal, and
with a second molecule of the alcohol to give an acetal.
• The hemiacetal is not as stable as the acetal, and most
hemiacetals decompose spontaneously to the aldehyde and
the alcohol.
• Therefore, hemiacetals are rarely isolated.
 Cyclic hemiketal
• Fructose has a ketone group and
five hydroxyl groups.
• So, fructose should also be able
to cyclize to form an
intramolecular hemiketal.
• The -OH on C-5 of the fructose
structure attaches to the
carbonyl group, yielding a 5-
membered ring (furanose form).
 Cyclic hemiketal cont..

• Chair conformation of fructose

Cyclic monosaccharides
 Creation of new chiral center in cyclization
• The cyclization of a monosaccharide creates a new chiral
centre/carbonyl carbon/ asymmetric carbon (C-1)
• The resulting pair of diastereomers are known as anomers and the
hemiacetal or hemiketal carbon is referred to as the anomeric carbon.
• Anomers are cyclic monosaccharides that differ from one another by
the orientation of their C-1 or C-2 carbons.
• For aldoses, it is C-1 and C-2 for ketoses
• Two forms of anomers are -α and –β depending on whether the OH
group attached to the anomeric carbon (C-1) is on the same side as
the CH2OH group or is on the opposite side.
• -OH: on the same side as the CH2OH group (up) then it is –β
• -OH on the opposite side as the CH2OH (down/below) then it is -α
Anomeric carbons
 Cyclic sugars have two anomeric forms

Beta (β) configuration is when the OH and CH2OH groups are

on the same side of the ring.
 Tollens Test
• It is a chemical test used to differentiate reducing sugars from
non-reducing sugars.
• Aldehydes react with Tollens reagent to give carboxylate
ions/aldaric acid (COOH) and metallic silver, often in the form
of a silver mirror of the inside of the container.
• Tollens reagent can only react with an open chain form of a
sugar, which has free aldehyde or ketone.
• If the cyclic form cannot open to the free carbonyl compound,
the sugar does not react with Tollens reagent and the sugar
gives a negative Tollens test.
• All monosaccharides are reducing sugars. E.g Glucose, fructose,
galactose
Tollens Test
 Bond formation ( glycosidic bond)
 A glycosidic bond, also known as a glycosidic linkage, is a
chemical bond in the form of a covalent connection that
connects a carbohydrate (sugar) molecule to another
group, which might be another carbohydrate or not.

 The sugar group is referred to as a glycone, while the non-sugar

group is referred to as an aglycone.
 A molecule formed when a sugar is bound to another functional
group via a glycosidic bond is called a glycoside.
 Formation of Glycosides is known as Glycosidation.
Bond formation ( glycosidic bond)
 Disaccharide
 Two monosacharides units convalently bonded together.
 The anomeric carbon can react with any of the hydroxyl groups of
another sugar to form a disaccharide.
 Disaccharides can be reducing or non-reducing, depending on
the specific groups involved in the formation of the glycosidic bond.
 They can only be reducing when there is a free anomeric carbon,
not involved in the formation of the glycosidic bond, that can
undergo the oxidation reduction with Tollen's or Benedict's
reagents.
 When the anomeric carbon on both monosaccharides is involved in
the formation of the glycosidic bond, the disaccharides is non-
reducing
 glycosidic bond in disaccharides
• Previously, you learned that monosaccharides can form cyclic
structures by the reaction of the carbonyl group with an OH
group, resulting in an cyclic hemiacetal (or hemiketal).
• In the same way that hemiacetals and ketals can react with an
additional alcohol forming acetals and ketals, these cyclic
monosaccahrides can in turn react with another alcohol
molecule.
• In the case of disaccharides, one monosaccharide acts as the
hemiacetal while the other monosaccharides acts as the alcohol.
The formation of an acetal (or ketal) bond between two
monosaccharides is called a glycosidic bond or glycosidic
linkage.
• Therefore, disaccharides are sugars composed of two
monosaccharide units that are joined by a carbon–oxygen-
carbon linkage known as a glycosidic linkage.

• This linkage is formed from the reaction of the anomeric

carbon of one cyclic monosaccharide with the OH group of
a second monosaccharide.
 Disaccharide
• Examples: sucrose (glucose +fructose), lactose (galactose+
glucose), maltose (glucose +glucose)
• Disaccharides have three common glycosidic bonding
arrangements.
1. 1,4’ link: The anomeric carbon (1st sugar) is bonded to the
oxygen atom on C4 of the second sugar. The prime symbol (’) in
1,4’ indicates that C4 is on the second sugar.
2. 1,6’ link: The anomeric carbon (1st sugar) is bonded to the
oxygen atom on C6 of the second sugar. 3.
1,1’ link: The anomeric carbon of the first sugar is bonded
through an oxygen atom to the anomeric carbon of the second
sugar.
 Disaccharides
Sucrose, the most abundant disaccharide, occurs throughout the
plant kingdom and is familiar to us as common table sugar.
It is a non-reducing sugar
Questions.

1. What type of glycosidic

bond exists in sucrose?
2. Why is sucrose called a 42

non reducing sugar.

 Disaccharide
• Sucrose is a non-reducing • Sucrose structure:
sugar because the two
monosaccharide units are held
together by a glycosidic
linkage between C1 of α-glucose
and C2 of β-fructose.
• Since the reducing groups of
glucose and fructose are involved
in glycosidic bond formation,
sucrose is a non-reducing sugar.
• Sucrose: Glucose is joined to
fructose by an α-1,β-2-glycosidic
linkage
Lactose (galactose+glucose) in β-1-4 glycosidic bond) or milk
sugar occurs naturally only in milk, where its concentration
ranges from 0 to 7% depending on the species. The free
anomeric carbon of its glucose residue makes lactose a reducing
sugar.

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• The glycoside (the left ring) in lactose is galactose rather than
glucose.
• The two rings are linked by a β-glycosidic bond of the galactose acetal
to the 4-position of the glucose ring: a β-1,4’ galactosidic linkage
Infants normally express the intestinal enzyme lactase that
catalyzes the hydrolysis of lactose to its component
monosaccharides for absorption into the bloodstream.

Many adults, have a low level of this enzyme (as do most

adult mammals, since they normally do not encounter
milk). Consequently, much of the lactose in any milk they
drink moves through their digestive tract to the colon,
where its bacterial fermentation produces large quantities
of CO2, H2, and irritating organic acids.
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This condition is termed lactose intolerance.

Maltose is a disaccharide formed when starch is treated with sprouted
barley, or malt. It has a free hemiacetal ring (on the right) and is
therefore a reducing.

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Maltose contains a α1,4’ glycosidic linkage between two glucose

units
 Disaccharides in chair conformation
• Maltose: An α-1,4’ Glucosidic Linkage
Lactose: A β-1,4’ Galactosidic linkage
 POLYSACCHARIDES

Polysaccharides, which are also known as glycans, consist of

monosaccharides linked together by glycosidic bonds.
They are classified as homopolysaccharides or
heteropolysaccharides if they consist of one type or more
than one type of monosaccharide residue.
Homopolysaccharides may be further classified according to
the identity of their monomeric unit.
49

For example, glucans are polymers of glucose, whereas

galactans are polymers of galactose.
 Cellulose, the primary structural component of plant cell walls
accounts for over half of the carbon in the biosphere.

50

It is composed of D-glucose units linked by β-1,4’ glycosidic bonds.

Humans and other animals lack the β-glucosidase enzyme needed to hydrolyze
cellulose.
Although vertebrates themselves do not possess an enzyme
capable of hydrolyzing the β (1 4) linkages of cellulose, the
digestive tracts of herbivores contain symbiotic microorganisms
that secrete a series of enzymes, collectively known as cellulase,
that do so. The same is true of termites.
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Chitin is the principal structural component of the
exoskeletons of invertebrates such as crustaceans, insects, and
spiders and is also a major cell wall constituent of most fungi
and many algae.
Chitin is a homopolymer of β (1 4)-linked N-acetyl-D-glucosamine
residue

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 Storage Polysaccharides: Starch and Glycogen
Starch is a food reserve in plants and a major nutrient for
animals
Starch is a mixture of glucans that plants synthesize as their
principal food reserve. It is deposited in the cytoplasm of plant
cells as insoluble granules composed of α amylose and
amylopectin
α amylose is a linear polymer of several thousand glucose
residues linked by α (1 4) bonds
53

Note that although α amylose is an isomer of cellulose,

it has very different structural properties.
This is because cellulose’s β glycosidic linkages cause each
successive glucose residue to flip 180° with respect to the
preceding residue, so that the polymer assumes an easily packed,
fully extended conformation
In contrast, amylose’s α-glycosidic bonds cause it to adopt an
irregularly aggregating helically coiled conformation.

54
Amylopectin consists mainly of α(1 4)-linked glucose residues but is a branched
molecule with α(1 6) branch.

55
 Glycogen Is “Animal Starch”

Glycogen, the storage polysaccharide of animals, is present in all

cells but is most prevalent in skeletal muscle and liver, where it
occurs as cytoplasmic granules.

The primary structure of glycogen resembles that of

amylopectin, but glycogen is more highly branched.
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 GLYCOPROTEINS
Until about 1960, carbohydrates were thought to be rather dull compounds
that were probably some sort of inert filler.

Protein chemists therefore considered them to be a nuisance that

complicated protein “purification.”

In fact, most eukaryotic proteins are glycoproteins, that is, they are
covalently associated with carbohydrates.
57

Glycoproteins vary in carbohydrate content from 1% to 90% by weight. They

occur in all forms of life and have functions that span the entire spectrum of
protein activities, including those of enzymes, transport proteins, receptors,
hormones, and structural proteins.
The polypeptide chains of glycoproteins, like those of all proteins, are
synthesized under genetic control.

Their carbohydrate chains, in contrast, are enzymatically generated and

covalently linked to the polypeptide without the rigid guidance of nucleic
acid templates.

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