COURSE:BIOCHEMISTRY

LECTURE 3 :CARBOHYDRATES

LECTURER:MR BETERA(Bsc(NUST)Msc(NUST)
ASSESSMENT
QUIZZES

TESTS

GROUP AND NON GROUP PRESENTATIONS

PRACTICALS

ASSIGNMENTS

FINAL EXAM(Paper 1 and Paper 2)

MCQ paper there is negative marking
REFERENCE TEXT BOOKS
 Biomolecules
Your body is full of large molecules called biomolecules and the first thing we have to do to understand
biochemistry is to learn about different kinds of biomolecules. The are few different classes like:

1. Carbohydrates
2. Proteins
3. Lipids
4. Nucleic acids

In this lecture we are going to discuss carbohydrates.

BIOMEDICAL IMPORTANCE OF
CARBOHYDRATES
• Carbohydrates are widely distributed in plants and animals; they have
important structural and metabolic roles.
• Glucose is the most important carbohydrate, it is the major metabolic
fuel of mammals (except ruminants) and a universal fuel of the fetus.

• Diseases associated with carbohydrate metabolism include diabetes

mellitus,galactosemia, glycogen storage diseases, and lactose
intolerance
What are Carbohydrates?
• They are hydrates of carbon, molecules with several carbon atoms
that each bear a hydrogen and a hydroxyl group.
Carbohydrates
• Their name end with ‘’-ose’’,like glucose, sucrose which is the sugar
we commonly refer to as simply sugar.
 Carbohydrates
Let us learn about monosacharrides first
• These are monomeric units that polymerise to form polysaccharides

• They have the general formula of

• Although, it must be remembered that this is just a general formula
 Monosaccharides
• We name them according to number of which carbon atoms they
have which will be between three and six, so a three carbon
monosaccharide will be a triose.
Triose
 Monosaccharides
If it has 4 carbons it is a tetrose

Tetrose
If it has 5 carbons it is a pentose If it has 6 carbons it is a hexose

Pentose Hexose
Monosaccharides
• In addition all carbohydrates will either have an aldehyde or ketone
functional group in the molecule, so we would refer to those as an
aldose or ketose respectively.
Monosaccharides
• Combining these conversions we could refer to these
monosaccharides as aldohexose and ketopentose respectively

aldohexose ketopentose
Monosaccharides
• Each of these carbons the ones that bear both hydrogen and hydroxyl
will be a chiral centre

These carbons are chiral centres

Monosaccharides
• The convection for drawing linear monosaccharides is to use Fischer projections.
• When we look at these it is important to understand that each vertex is a stereogenic carbon

• We show the hydrogens and hydroxyls on either side

• With Fischer Projections horizontal lines are implied to be wedge bonds and
vertical lines are implied to be dash bonds.
.

• Fischer projections are just a different way of visualising a molecule, which

we can see if we draw this molecule in line notation and view it from this
side.

• The Fischer projection is what we would see if we were in the plane of the
screen looking directly at the chiral centre
.
• However we choose to view it is important to realise that Fischer
Projections do not imply a flat molecule with 90 degrees bond
angles ,these carbons are still tetrahedral we just save time by drawing
sugars this way.
• When we draw a linear monosaccharide we always put the aldehyde or
ketone group at the top and draw the rest of the molecule downwards
and we report the stereochemistry of the molecule by looking at the
chiral centre at the bottom farthest away from the carbonyl
• If on this carbon the hydroxyl points in the right it’s a D-sugar if it points
left it is an L-sugar.
.

• This is how we differentiate entatiomers of sugar molecules

• For some reason nature has selected to work with D sugars ,so unless
otherwise state we can assume that we are working with D sugars
.
• Lets also know that a molecule with n chiral centres has

There are 2 aldotrioses since there is only one chiral centre.

• There are 16 aldohexoses since there are four chiral centres

.
• Lastly with Fischer projections lets be sure to understand that
swapping the position of two groups on a chiral centre results in the
inversion of that stereo centre.
Anomers
• We know that carbonyl compounds are sp2 hybridised and therefore
exhibit planar geometry so when hydroxyl group attacks the carbonyl
it can do so from either side thus generating two different isomers
which are called anomers.
Epimers
• Now, diastereomers that differ in the configuration of only one chiral
center are called epimers.

• Variations in configuration of the —OH and —H occurs on carbon

atoms 2, 3, and 4
Optical Activity
• The presence of asymmetric carbon atoms also confers optical activity
on the compound.
• When a beam of plane-polarized light is passed through a solution of
an optical isomer, it rotates either to the right, dextrorotatory (+), or
to the left, levorotatory (–).
• The direction of rotation of polarized light is independent of the
stereochemistry of the sugar, so it may be designated D(–), D(+), L(–),
or L(+)
• This nomenclature is obsolete, but may sometimes can be found; it is
unrelated to D- and L-isomerism
Monosaccharides
• Monosaccharides exists in equilibrium between a linear and cyclic
form with the cyclic form being highly preferred.
• They cyclise by an intramolecular hemiacetal formation.
• When hemiacetal form it is because an alcohol attacks an aldehyde or
ketone,in this case it is an intramolecular cyclisation because the
hydroxyl group and the carbonyl group are on the same compound
Anomers
• That makes the resulting hemiacetal carbon the anomeric carbon

We can either get the alpha anomer or beta anomer depending on

which side the hydroxyl attacks from.
Haworth Projections
• When we draw cyclic monosaccharides we sometimes use Haworth
Projections.
• With these we look at the ring from the edge meaning that this part
of the ring is closer to us and this part is further away from us, and we
show the functional groups projecting straight up and straight down.
Haworth Projections
• When we draw Haworth projections the convection is to place the
anomeric carbon on the right and the group on the other side of the
ring pointing up.
• We can either have alpha or beta anomer
Haworth Projections
• If a cyclic monosaccharide has a six membered ring we call it a
pyranose

• But sometimes the hydroxyl on carbon four can do the attacking

resulting in a five membered ring which we will call a furanose.
Monosaccharides
• We should also know that monosaccharides don’t remain in alpha or
beta form,we can have an equilibrium between them since
hemiacetal formation is completely reversible.
• Alpha glucose can go back to the linear form and cyclise again to form
beta glucose.
Monosaccharides
• For glucose the beta anomer is preferred because the hydroxyl group on the
anomeric carbon is on equatorial position versus axial in the alpha anomer.
• For this reason a sample of glucose that has more of the alpha form than
beta form will undergo mutarotation which is a shift towards equilibrium
values for the two anomers which in the case of glucose is about two to one
in favour of the beta anomer.
• Sugars will not always prefer the beta anomer in some sugars like mannose
the alpha anomer is preffered due to reasons of hyperconjugation that we
call the anomeric effect.
• It is the cyclic form that is able to polymerise to form long polysaccharide
chains
Many Monosaccharides Are
Physiologically
Important
Pentoses of Physiological Importance
Many Monosaccharides Are
Physiologically
Important
Monosaccharide Derivatives
• Organisms contain a variety of sugar derivatives.

• In sugar derivatives the monosaccharide molecule have been

modified with substituents other than hydroxyl groups such as amino
groups, acid groups, phosphate groups, acetate groups e.t.c.

• Natural sugar derivatives have important biological functions.

• Majority of sugar derivatives are hexose derivatives.

Monosaccharide Derivatives
• There are two main modes of formation of sugar derivatives.

1. Hydroxyl group in the sugar is replaced with another substituent.

2. Oxidation of carbon in the chain to form carboxyl group.
The following are the important classes of sugar derivatives:
3. Aldonic acids
4. Uronic acids
5. Aldaric acids
6. Aditols
7. Deoxy Sugars
Aldonic Acids
• Aldonic acids are formed by the oxidation of an aldose (at C1) converts an aldehyde group
into a carboxylic acid group.
• Aldonic acids are named by appending the suffix-onic acid to the root name of the parent
aldose.

• Aldonic acids have a broad range of applications in pharmaceutics as anticoagulants, drug

carriers, preservatives for organ transplant and many more??
Uronic acids
• Uronic acids are formed by the oxidation of primary alcohol(the –OH group at C-6 position) of an
aldose sugar.
• Uronic acids are named by appending-uronic acid to the root name of the parent aldose.
• Uronic acids can assume the pyranose,furanose and linear forms.

• Glucuronic acid helps remove harmful substances from the body??

• Glucuronic acid is also found in cartilage and synovial fluid
Aldaric acids
• In aldaric acids the terminal carbonyl groups(at C1) and terminal
hydroxyl group(at C6 in the case of hexose) have been replaced by
terminal carboxylic acid.
• Aldaric acids do not form cyclic structures.

• Aldaric acids can be utilised as carriers during drug delivery process.

Alditols
• Alditols are polyhyroxy alchols.
• Alditols are formed by the reduction of aldoses by mild reducing
agents to yield polyhdroxy alcohols.
• Alditols are named by appending the suffix –itol to the parent aldose

• Glycerol and Myo-inositol are important components of lipids

• Xylitol is a sweetener in “ sugarless candies’’
Deoxy Sugars
• Monosaccharidses in which the –OH group is replaced by –H is called doxy sugar

• Deoxy sugar of ribose is the sugar component of DNA

• L-Fucose(6-deoxy-l-galactose):Deoxy sugar of L-galactose is one of the L sugar
components of polysaccharides(fucoidan)
• Fucoidans are sulphated polysaccharides present in cell walls of brown
algae(Read on health benefits of fucoidans)
Amino Sugars
• In amino sugars ,the –OH group at C2 is replaced by (-NH2) group.
• The attached amino group is often acetylated, and are named as N-acetyl

• Lactic acid ether(at C3) of glucosamine is called muramic acid

• Acetylated muramic acid is called N-Acetyl-muramic acid.
• N-Acetyl-Glucosamine(NAG) and N-Acetyl-Muramic acid(NAM) are the building blocks of
peptidoglycan(cell wall of bacteria)
Sialic Acids
• N-acetylmannosamine and Pyruvic acid combine to form N
Acetylneuraminic acid(NANA)
• NANA has a backbone of 9 carbons
• NANA and its further derivatives are collectively called Sialic acids.
• Sialic acids are important sugar components in glycolipids and
glycoproteins
Glycosides
• When the hemi-acetal group (hydroxyl group of the anomeric carbon)
of a monosaccharide is condensed with an alcohol or phenol group, it
is called a glycoside
• The non-carbohydrate group is called aglycone.
• Some glycosides of medical importance are given below . Digitonin is
a cardiac stimulant.
• Phlorhizin is used to produce renal damage in experimental animals.
 Glycosidic Bond

• Carbohydrates also include disaccharides, oligosaccharides and

polysaccharides which are polymers of simple sugars.
• So we need to understand the way they polymerise as well as certain
characteristics of the resulting polymers.
• Let us return to our Haworth projection of beta glucose.
• In the cyclic form we can see that there is a hemi acetal group,and we
remember the mechanism by which become an acetal,that is
essentially what will happen here
Glycosidic Bond
• We know that if this hydroxyl group is protonated it could leave and
then this carbon could be attacked by an alcohol forming what we call
a glycosidic bond as well as an acetal functional group in the process.
Glycosidic Bond
• If the hydroxyl group that attacks on another monosacharride we will
get a disaccharide.

Cellobiose
Disaccharides
• Other common disaccharides are :
Lactose Sucrose(Table Sugar)
Beta galactose + alpha glucose alpha glucose + beta fructose
Disaccharides
• Lactose is the sugar present in milk. It is a reducing disaccharide. On
hydrolysis lactose yields glucose and galactose.
• Beta glycosidic linkage is present in lactose.
• Lactose and lactate should not be confused.
• Sucrose contains glucose and fructose.
• Sucrose is not a reducing sugar because there are no free reducing
groups in the structure of sucrose.
REDUCING SUGARS VS NON
REDUCING SUGARS
Disaccharides
• Physiologically important disaccharides
Oligosacharrides
• We could continue to polymerise further to have oligosacharrides which will have 3-
10 saccharides units.
• Do not occur as free entities in humans,they occur as
conjugates(Glycolipids,Glycoproteins).
• In plants example are:
1. Raffinose( present in beans,cabbage,etc).
2. Stachyose(present in vegetables).
3. Verbacose(Legumes)
• They are fermented by intestinal bacteria and they cause flatulent
• Oligosaccharides often occur as glycoconjugates attached to proteins (called
glycoproteins) or lipids (called glycolipids) that are often found on the surface of cells
Polysaccharides
• Polysaccharides are classified into two main groups:
• Homopolydisaccharides (hemoglycans): Polymer of same
monosaccharide units, e.g. starch, glycogen, inulin,dextrins, cellulose,
etc.
• Heteropolysaccharides (heteroglycans): Polymer of different
monosaccharide units or their derivatives, e.g. mucopolysaccharides
(MPS).
Polysaccharides: Starch
• Starch which is abundant in rice and potatoes is a polysaccharide
made from glucose unit.
• Starch is composed of amylose and amylopectin.
• Amylopectin has branches every 20 to 25 glucose units.
Polysaccharides: Starch
• The branching occur between carbon 6 of one glucose molecule and
carbon one of another and another chain initiates from there.
Amlyose VS Amylopectin
Hydrolysis of Starch
Dextrins and Dextrans
Dextran
• Only drawback is that dextran can inferfere with grouping and cross
matching, as it forms false agglutination(Roleux formation).
• Hence, blood sample for grouping and crossmatching should be
collected before administration of dextran in a case of haemorrhage
and blood loss, where blood transfusion may be needed, otherwise it
can give wrong grouping.
Agar
• • Agar is a polymer of sulfated galactose units and obtained from
seaweeds.
• Biomedical importance:
• Used in constipation. It is not utilized by humans when taken orally. It
adds bulk to the feces and helps in its propulsion.
• Agar is used as a culture medium for bacterial growth and isolation
Glycogen
• Glycogen has a highly branched structure resembling amylopectin of
starch granule.
• D-glucose units in main stem and the branches are joined together by
α-1-4 glucosicidic linkage.
• The linkage at branch point is α 1-6.
• Glycogen is more bushy and branches occur for every 12 to 18 glucose
units
Glycogen
• Glycogen is a storage form of glucose and occurs principally in liver
and muscle.
• Formation of glycogen from glucose is called glycogenesis.
• Liver supplies glucose-1-Phosphate by breakdown of glycogen, called
glycogenolysis, which is converted to glucose.
• Hence, it serves as ready source of glucose in body in time of need
Glycogen
• How much glycogen can be stored in liver and muscle?
• Storage capacity is limited.
• Liver can store up to 4 to 6% of its weight, i.e. 72 to 108 gm.
• Muscle can store 0.7% of its weight, i.e. 245 gm
CELLULOSE
• Cellulose is a polymer of D-glucose, a homopolysaccharide.
• Heating with high concentrations of cellulose with acids yield cellobiose (a
disaccharide) and D-glucose.
• Cellobiose is a disaccharide made up of two molecules of D-glucose linked
together by β-glucosidic linkage between C-1 and C-4 of the glucose units.
A hydrolytic product of the cellulose.
• The biomedical importance of cellulose is that cellulose the main
constituent of the supporting tissues of plants and it forms considerable
part of our vegetable food. In humans, there is no cellulose-splitting
enzyme in the gut, hence, it is not of any nutritional value. But it gives bulk
to the intestinal contents (roughage) and helps in removal of constipation
Inulin
Polymer of D-fructose is inulin, a homopolysaccharide.
• Biomedical importance:
• Used in determination of the rate of glomerular
filtration rate (GFR)
• Also used for estimation of body water (ECF) volume.
Agar
• Agar is a polymer of sulfated galactose units and obtained from
seaweeds.
• Biomedical importance:
• Used in constipation. It is not utilized by humans when taken orally. It
adds bulk to the faeces and helps in its propulsion.
• Agar is used as a culture medium for bacterial growth and isolation