• Classification, types, important characteristics

and structure of Carbohydrates;

• Disaccharides their types structure and
function;
• Polysaccharides, Storage and Structural types;
Structure and major functions of
polysaccharides; Glycogen, Starch, Cellulose,
Chitin; Homo- and Hetero-polysaccharides;
Peptidoglycans of bacterial cell wall.
• Carbohydrates are an abundant biomolecule.
• More than 50% of the carbon in organic
compounds is found in carbohydrates
• Saccharides are either an aldehyde or a ketone.

• “If the carbonyl carbon is terminal carbon, then it

is an aldehyde, or it is not a terminal carbon, then
it is a ketone”.

• The aldehyde saccharides are called aldose and

the ketone saccharides are called ketose.
 H H
C O H C OH
H C OH C O
H C OH H C OH
H H
glycer aldehyde dihydroxy acetone
2,3-dihydroxypropanal 1,3-dihydroxy-2-propanone

Not Terminal Carbonyl

Terminal Carbonyl
Carbon Atom
Carbon Atom
 Monosaccharides Stereoisomers
• The stereoisomer is a special type geometric isomer. The
connectivity is the same between two stereoisomers, the difference is
their arrangement in 3-dimensional space.
•
• Organic compounds that contain an asymmetric (chiral) Carbon
usually have two non-superimposable structures. These two structures
are mirror images of each other and are, thus, commonly called
enantiomorphs

• They are not super imposable. Your hands are mirror images of each
other, they are the same, but opposites.

• Asymmetric (Chiral) Carbon – has covalent bonds to four different

groups, cannot be superimposed on its mirror image.
• Isomers:
same chemical formulas, different structures

• Conformation:
the spatial arrangement of substituent groups

• chiral centers:
asymmetric carbons, i.e carbon atom with four different
substituents

• Enantiomers : mirror images Stereoisomers

 CHIRALITY RULES

1. Monosaccharides contain one or more asymmetric C-

atoms: get D- and L-forms, where D- and L-
designate absolute configuration
2. D-form: -OH group is attached to the right of the
asymmetric carbon
3. L-form: -OH group is attached to the left of the
asymmetric carbon
 H H
C O C O
H C OH HO C H
H C OH H C OH
H H
D-glycer aldehyde L-glycer aldehyde
D-2,3-dihydroxypropanal L-2,3-dihydroxypropanal
 Linear Structure
The linear form is called Fischer projection
The Fischer projection is named after Emil Hermann Fischer, winner of the
1902 Nobel Prize in Chemistry . This structure is an L enantiomer. The –OH
on the carbon before the terminal carbon is on the left.
The simplest aldose, glyceraldehyde, contains one chiral center (the middle
carbon atom) and has two different optical isomers, or enantiomers
 Linear Structure

H
CHO C O OH
OHC
H OH H C OH H

H C OH OH
H OH H
HO H HO C H H
HOH2C OH
CH2OH H C OH
H

L-aldopentose
 Ring Structure
• Ring know as a “Haworth projection”
• Cyclization via intramolecular hemiacetal
(hemiketal) formation
• Chair conformation usual (as opposed to boat)
• Axial and equatorial bonds
• The carbon to the far right on each ring shows the
hydroxyl group in different location.
• The alpha structure has the hydroxyl group down
and the beta group has the hydroxyl group up.
 Ring Structure
• in aqueous solution, monosaccharides with
five or more carbon atoms in the backbone
occur predominantly as cyclic (ring) structures
in which the carbonyl group has formed a
covalent bond with the oxygen of a hydroxyl
group along the chain
 Ring formation / Ring structure

An aldose: Glucose

from http://ntri.tamuk.edu/cell/carbohydrates.html
 A ketose: Fructose

from
http://ntri.tamuk.edu/cell/carbohydrates.html
Two different forms of b-D-Glucose

Preferred
 Carbohydrate Polymer

Carbohydrates are also referred to as

saccharides. Saccharides can be found in
several forms.

• Single monosaccharide
• Pair disaccharide
• Many polysaccharide
 Monosaccharide

• basic unit of metabolism

• normally 3, 4, 5, 6 or 7 carbons in length
• classified as aldose or ketose
• classified as D or L isomers based on the
stereochemistry
 Disaccharide

• use to transport monosaccharides

• water soluble – as they are short hydrocarbon
chains
• are sweet to taste
• sucrose, galactose and lactose
 Polysaccharides

• structure of plants – cellulose

• storage of monosaccharides
 Importance of Carbohydrates

Very effective energy yield

– contains carbon
– has a reactive bond – carbonyl carbon and is a polar
area
Effective building material
– strong not brittle – will bend and not break
H2O soluble
– easily transported through the blood stream
– easily passes through cell walls
 Sugars are carbohydrates
Sucrose was used as the standard, all other sugars sweetness is
based on sucrose
relative
relative common
carbohydrate sweetness class
sweetness name
sucrose
sucrose 1.00 disaccharide table sugar

lactose lactose 0.16 disaccharide milk sugar

maltose maltose 0.32 disaccharide malt sugar

monosacch
glucose glucose 0.74 blood sugar
aride
monosacch
galactose galactose 0.22 -
aride
monosacch
fructose fructose 1.74 fruit sugar
aride
 Saccharide Monomers
Glucose
• Most carbohydrates are converted to glucose
to be metabolized for energy.
• dextrose and blood sugar are both common
names for glucose
• A monomers of sucrose, maltose, lactose,
starch, cellulose and glycogen
• 25% less sweet than table sugar, sucrose
• 70-150mg per dl of blood
D-Glucose Importance
D-glucose (dextrose) is the primary fuel in
living cells especially in brain cells that have
few or no mitochondria.

Cells such as eyeballs have limited oxygen

supply and use large amount of glucose to
generate energy

Dietary sources include plant starch, and

the disaccharides lactose, maltose, and
sucrose
 H H
C O C O
H OH H OH
HO H HO H
H OH H OH
HO H H OH
CH2OH CH2OH

L-glucose D-glucose
 Galactose
• Classified as an aldohexose – as it is an aldehyde and a
6-carbon compound
• combined with glucose to form the disaccharide
lactose
• 80% less sweet than table sugar, sucrose
• Galactosemia
– genetic disease – inability of body to metabolize galactose
– elevated levels of galactose in blood and urine
– vomiting, diarrhea, liver enlargement
– can cause death in days
– Galactose must be removed from their diet
 H H
C O C O
H OH H OH
HO H HO H
HO H carbon #5 HO H carbon #5
HO H H OH
CH2OH CH2OH

L-galactose D-galactose
 Fructose

• classified as a ketohexose as this molecule is a

ketone and is a 6-carbon chain
• found in fruit juice and honey
• combined with glucose to form the
disaccharide sucrose
• 175% sweeter than table sugar, sucrose
 CH2OH CH2OH
C O C O
HO H HO H
H OH H OH
HO H H OH
CH2OH CH2OH

L-fructose D-fructose
 Cyclic Saccharides
The straight form of saccharides is very reactive.

For the saccharide to be stable enough to transport, it

forms a cyclic structure.
 • The reaction breaks the
double bond of the carbonyl
group and shifts hydrogen of
the hydroxyl group on the
H
C O
number 5 carbon to the
H OH
carbonyl group’s oxygen
HO H • Rings of different numbers
carbon 5
H OH of sides are given different
H O H names. A five-sided ring is
H C OH called a furanose and a six-
H
sided ring is called a
D-glucose
puranose.
 carbon 6

carbon 5
CH2OH CH2OH
carbon 4 C O
O carbon 1 H H
H H
H H
C C OH H
OH H HO OH
HO C C OH

H HO carbon 2 H HO

carbon 3
CH2OH CH2OH
O OH O
H H H
H H
OH H OH H
HO H HO OH

H HO H HO
-D-glucose -D-glucose

The alpha structure has the hydroxyl group down and the beta group has the
hydroxyl group up.
 CH2OH
C O HOH2C CH2OH
O
HO H
H HO
H OH H OH
H O H
OH H
CH2OH

D-fructose -D-fructose
HOH2C O CH2OH HOH2C O OH

H H HO
HO H CH2OH
H OH

OH H OH H
-D-fructose
-D-fructose
 GLYCOSIDES
• Monosaccharides can be linked by glycosidic bonds (joining of
2 hydroxyl groups of sugars by splitting out water molecule) to
create larger structures.
• Disaccharides contain 2 monosaccharides e.g. lactose
(galactose+glucose); maltose (glucose+glucose);
sucrose (glucose+fructose)
• Oligosaccharides – 3 to 12 monosaccharides units e.g.
glycoproteins
• Polysaccharides – more than 12 monosaccharides units e.g.
glycogen (homopolysaccharide) having hundreds of sugar
units; glycosaminoglycans (heteropolysaccharides) containing
a number of different monosaccharides species.
 Disaccharides

• The three most important disaccharides are

sucrose, lactose and maltose.
• always the D form.
• Disaccharides are formed through a
dehydration reaction.
• This reaction releases a water molecule.
• To break this bond, named a glycosidic bond,
add water, this reaction is named hydrolysis.
 Sucrose:

• most common disaccharide, table sugar

• 20% of sugar cane is sucrose
• it is composed of one -D-glucose and one -
D-fructose monomer
• in an acidic solution sucrose undergoes
hydrolysis, the resulting solution containing
glucose and fructose is sweeter than the original
sucrose
• this can be observed in jams and jellies, the acid
in the fruit’s juice, normally citric acid, causes
the sucrose to undergo hydrolysis
• linked -1  -2
• this linkage information tells you that the -D-
glucose molecule uses its #1 carbon, whose OH
group is down, to bond to the #2 carbon on the
-D-fructose molecule, whose OH group is up
 CH2OH -D-glucose CH2OH
H O H O
H H
4 H 1 4 H 1
OH H OH H
HO OH HO
H HO O
H HO
H2O
HOH2C O
2
H HO
HOH2C O OH H CH2OH
1
2
H HO OH H
H CH2OH
1
sucrose
OH H -D-fructose
 Lactose
• milk sugar
• by mass composes 7% of human milk, 5% of
bovine milk
• being lactose intolerant is a fairly common
condition, especially in adults who drink less
milk, the body forgets how to make the enzyme,
lactase, needed to break lactose’s glycosidic bond
• it is composed of one -D-glucose or -D-
glucose and one -D-galactose monomer
• Lactose is odd in the fact that the second
monomer can have either  or  stereochemistry
• in an acidic solution lactose undergoes hydrolysis,
the resulting solution containing glucose and
galactose
• linked -1 4
• this linkage information tells you that the -D-
glucose molecule uses its #4 carbon to bond to the
#1 carbon on the -D-galactose molecule, both of
which have a OH group in the up position
• -D-glucose
 -D-glucose
CH2OH
H O H
4 H 1
OH H
-D-galactose HO OH
CH2OH
H HO
O OH CH2OH
HO
4 H 1
H O H
OH H H
H H CH2OH 4 1
OH H
HO O O OH
H HO
H2O 4 H 1
OH H H HO
H H

H HO lactose
 Lactose intolerance
• Lactose (milk sugar) in infants is hydrolyzed by
intestinal enzyme lactase to its component
monosacch for absorption into the bloodstream
• Most adult mammals have low levels of beta-
galactosidase. Hence, much of the lactose they
ingest moves to the colon, where bacterial
fermentation generates large quantities of CO2, H2
and irritating organic acids.
• These products cause painful digestive upset known
as lactose intolerance and is common in the African
and Asian
 Maltose

• malt sugar
• it is composed of -D-glucose monomers
• in an acidic solution maltose undergoes hydrolysis,
the resulting solution containing glucose
• linked -1 4
• this linkage information tells you that one -D-
glucose molecule uses its #1 carbon to bond to the
#4 carbon on the other -D-glucose molecule, both
of which have a OH group in the down position
 CH2OH CH2OH
-D-glucose
O H O H
H H
4 H 1 4 H 1
OH H OH H
HO OH HO OH

H HO H HO
-D-glucose

CH2OH CH2OH
O H O H
H H
4 H 1 4 H 1
OH H OH H H2O
O OH
HO

H HO H HO
maltose
 OLIGOSACCHARIDE SUGARS

• Oligosaccharides are small polymers often

found attached to polypeptides in
glycoproteins and some glycolipids.

• They are attached to membrane and secretory

proteins found in endoplasmic reticulum and
Golgi complex of various cells
Polysaccharides

• Composed of large number of monosaccharide units

connected by glycosidic linkages

• Polysaccharides are more hydrophobic if they have a

greater number of internal hydrogen bonds, and as
their hydrophobicity increases there is less direct
interaction with water

Divided into
• homopolysaccharides (e.g.Starch, glycogen, cellulose,
and chitin)
• heteropolysaccharides (glycoaminoglycans or GAGs,
murein).
Classification of Polisacharides
HOMOSACCHARIDES
• Found in abundance in nature
• Important examples: starch, glycogen, cellulose, and
chitin
• Starch, glycogen, and cellulose all yield D-glucose
when they are hydrolyzed
• Cellulose - primary component of plant cells
• Chitin – principal structural component of
exoskeletons of arthropods and cell walls of many
fungi; yield glucose derivative N-acetyl glucosamine
when it is hydrolyzed.
 Starch

• There are 2 classes of starch, animal and plant. Glycogen in

animal starch; amylose and amylopectin are plant starch.

• Starch is composed of a mixture of two polymers, an essentially

linear polysaccharide -amylose, and a highly branched
polysaccharide - amylopectin.

• Amylose – unbranched chains of D-glucose residues linked with

alfa(1,4,)glycosidic bonds.

• Amylopectin – a branched polymer containing both alfa(1,4,)

and alfa(1,6) glcosidic linkages; the alfa(1,6) branch points may
occur every 20-25 glucose residues to prevent helix formation
 STARCH (Homosaccharide)

• A naturally abundant nutrient carbohydrate

found chiefly in the seeds, fruits, tubers, roots.

• Starch digestion begins in the mouth; alfa-

amylase in the saliva initiates hydrolysis of the
gycosidic linkages
 
 Amylose
• The constituent of starch in which anhydros
glucose units are linked by -D-1 4
glucosidic bonds to form linear chains.

• Amylose molecules are typically made from

200-2000 anhydros glucose units.
 Animal Starch GLYCOGEN (Homosaccharide)
• Glycogen is the storage form of glucose in animals and
humans which is analogous to the starch in plants.
• Glycogen is synthesized and stored mainly in the liver and the
muscles.
• Glycogen can be quickly hydrolyzed to form glucose and
deposited into the blood stream for transport to cells.
• Structurally, glycogen is very similar to amylopectin but has
even more branching and more glucose units are present than
in amylopectin.
• The chain glycosidic linkage is -1 4, the branching occurs
with a glycosidic linkage of -1 6.
• Various samples of glycogen have been measured at 1,700-
600,000 units of glucose.
• In glycogen, the branches occur at intervals of 8-10 glucose
units, while in amylopectin the branches are separated by 12-
20 glucose units.
 Cellulose
• Cellulose is polymer of the monosaccharide
glucose.

• Cellulose gives plants their structure, in their

cell walls.

•  The glucose monomers are connected by a -

1 4 linkage, this prevents most organisms,
including humans from breaking the glucose
monomers apart.
• Some animals, such as cows and termites,
contain bacteria in their digestive tract that
help them to digest cellulose. 

• Despite the fact that it cannot be used as an

energy source in most animals, cellulose fiber
is essential in the diet because it helps
exercise the digestive track and keep it clean
and healthy.
 CELLULOSE (Homosaccharide)
• Cellulose is found in plants as microfibrils (2-20 nm diameter
and 100 - 40 000 nm long).

• Cellulose is mostly prepared from wood pulp.

• Cellulose has many uses as an anticake agent, emulsifier,

stabilizer, dispersing agent, thickener, and gelling agent but
these are generally subsidiary to its most important use of
holding on to water.

• Water cannot penetrate crystalline cellulose but dry

amorphous cellulose absorbs water becoming soft and
flexible.
 CHITIN (Homosaccharide)

• Chitin is a polymer that can be abudantly found in crabs, beetles,

worms and mushrooms.

• It is sometimes considered to be a spinoff of cellulose, because the

two are very molecularly similar.

• Chitin is also a "natural polymer," or a combination of elements that

exists naturally on earth.

• Chitin is a very firm material, and it help protect an insect against

harm and pressure
 CHITOSAN
• Chitosan is drived from chitin

• This is a man-made molecule that is often used to dye shirts

and jeans in the clothing industry.

• Chitosan can be used within the human body to regulate diet

programs.
 Artificial Sweeteners

• These sweeteners are normally used to reduce a person’s the

caloric intake.
• They work two ways.

• First, your body will not be able to metabolize the molecule,

even though it can taste it.

• Second, the artificial sweeteners are much sweeter, so you

need much less than you would for conventional sugars.
 
• For example Sucralose, an artificial sweetener is approximately
6000 times sweeter than sucrose. Meaning you would need
6000 times less Sucralose than sucrose.
 CH2OH CH2OH
Cl O H O H
H
H H
OH H OH H
H HO
O O
H HO H HO
CH2Cl O HOH2C O

H HO H HO
H CH2Cl H CH2OH

OH H OH H

Sucralose sucrose