Carbohydrates

Carbohydrates
O Broadly define as polyhydroxyaldehydes or ketones
and their derivatives or as substances that yields
one of these compounds.

H-C=O

H-C-OH

H-C-OH

H-C-OH

CH2OH
 OThe term “carbohydrate”
comes from the fact that
when you heat sugars, you get
carbon and water.
 Composed of carbon, hydrogen and
oxygen.

 Functional groups present include hydroxyl

groups

 -ose indicates sugar

Functions of Carbohydrates

Components of genetic material; DNA and RNA

Carbohydrates are the most abundant of
all organic compounds in nature
O In plants, energy from the sun is used to convert
carbon dioxide and water into the carbohydrate
glucose.
O Many of the glucose molecules are made into long-
chain polymers of starch that store energy.

O About 65% of the foods in our diet consist of

carbohydrates.

O Each day we utilize carbohydrates in foods such as

bread, pasta, potatoes and rice.

O Other carbohydrates called disaccharides include

sucrose (table sugar) and lactose in milk.
O During digestion and cellular metabolism,
carbohydrates are converted into glucose, which is
oxidized further in our cells to provide our bodies with
energy and to provide the cells with carbon atoms for
building molecules of protein, lipids and nucleic acid.

O In plants, a polymer of glucose called cellulose builds

the structural framework. Cellulose has other important
uses too.

O The wood in our furniture, the pages in your notebook,

and the cotton in our clothing are made of cellulose.
Carbohydrates are compounds of tremendous
biological importance:

O they provide energy through oxidation

O they supply carbon for the synthesis of cell

components

O they serve as a form of stored chemical energy

O they form part of the structures of some cells and

tissues
 Carbohydrates, along with lipids,
proteins, nucleic acids, and other
compounds are known as
biomolecules because they are
closely associated with living
organisms.
Classification of Carbohydrates
• Many of this class of molecules have a common
formula Cx(H2O)y which is carbon (carbo) and
water (hydrate).

• Carbohydrate compounds are also known as

sugars or saccharides.

• Carbohydrates are polyhydroxy aldehydes

and ketones
Types of Carbohydrates
Simple Carbohydrates
 monosaccharides
 disaccharides

Complex Carbohydrates
 oligosaccharides
 polysaccharides
 glycogen
 starches
 fibers
 Classes of Carbohydrates
A. Monosaccharides- contain a single
polyhydroxy aldehyde or ketone unit (saccharo
is Greek for “sugar”) (e.g., glucose, fructose).

B. Disaccharides- consist of two

monosaccharide units linked together by a
covalent bond (e.g., sucrose).
C. Oligosaccharides- contain from 3 to 10
monosaccharide units (e.g., raffinose)

D. Polysaccharides- contain very long chains of

hundreds or thousands of monosaccharide
units, which may be either in straight or
branched chains (e.g., cellulose, glycogen,
starch).
Classification of Carbohydrates
Monosaccharides: Single Sugars
Glucose
 carbohydrate form used by the body, referred to as
“blood sugar”
 basic sub-unit of other larger carbohydrate molecules
 found in fruits, vegetables, honey
Fructose
 sweetest of the sugars
 occurs naturally in fruits & honey, “fruit sugar”
 combines with glucose to form sucrose
Galactose
 combines with glucose to form lactose, “milk sugar”
 Monosaccharides
•Is not cleaved to a simpler carbohydrate on
hydrolysis.

•Glucose (C6H12O6), for example, is a monosaccharide

Monosaccharides

 Classification is based on:

1. Number of carbon atoms present
2. Whether the carbonyl group is an
aldehyde or ketone
Trioses
Some Classes of monosaccharides
No. of carbons
 Aldose Ketose
 4 Aldotetrose Ketotetrose
 5 Aldopentose Ketopentose
 6 Aldohexose Ketohexose
 7 Aldoheptose Ketoheptose
 8 Aldooctose Ketooctose

•Aldoses: Monosaccharides that are polyhydroxy aldehydes

•Ketoses: Monosaccharides that are polyhydroxy ketones
p. 462a
STEREOCHEMISTRY IN
MONOSACCHARIDE
Multiple Chiral Centers

 Recall that a chiral center is a carbon

atom that has four different atoms or
groups of atoms attached to it.
 Glucose, a ketohexose, contains four
different chiral centers, each with a
tetrahedral geometry.
Multiple chiral centers
 Carbons 2 through 5
of glucose are
tetrahedral and have
four different atoms
or groups of atoms
attached. Carbons 1
and 6 are not chiral
centers. Why?
Multiple Chiral Centers
 Groups bonded to each chiral center have two
different arrangements or mirror images, which
result in stereoisomers.
 The number of stereoisomers for a molecule
increases with the number of chiral centers in the
molecule.
 The general formula for determining the number
of stereoisomers is 2n, where n is the number of
chiral centers present in the molecule.
 Glucose has 4 chiral centers, so there are 16
stereoisomers, 24 = 16.
FISCHER PROJECTION
 Fischer Projections
O Place the carbonyl group at or near the top and the
last achiral CH₂OH at the bottom.

O Fischer projection is a simple way of indicating chiral

molecules by showing their three-dimensional structure in
two dimensions, without showing all the wedges and
dashes on all the chiral centers.

O In the Fischer projection, horizontal lines on a chiral

center represent wedges, and vertical lines on a chiral
center represent dashes.
 Representing stereoisomers—the Fischer
projection
 In the Fischer projection, a chiral carbon is not
shown, but is implied at the intersection of
lines.
 Consider the Fischer projection of
glyceraldehyde, the simplest aldose, shown on
the next slide.
 Representing stereoisomers—
the Fischer projection
 D- and L- Monosaccharide
 D and L designations of sugars are based on
the Fischer projection positioning in
glyceraldehyde.
 All D-sugars have the –OH on the chiral carbon
farthest from the carbonyl group on the right
side of the molecule.
 All L-sugars have the –OH on the chiral carbon
farthest from the carbonyl group on the left side
of the molecule.
 Most sugars in nature have the D designation.
 Enantiomers are written as if there is a
mirror placed between the two molecules.
 Enantiomers of D- and L-glucose are:
Stereoisomers that are not
enantiomers
 How are all stereoisomers of D-glucose
related since only one mirror image exists
for any stereoisomer?
 Stereoisomers that are not enantiomers
are called diastereomers.
 Diastereomers are stereoisomers that are
not exact mirror images.
Some Important Monosaccharides

• Glucose is the most abundant

monosaccharide found in nature.

• Glucose is also known as dextrose, blood

sugar, and grape sugar.

• Glucose is broken down in cells to

produce energy.
 Diabetics have difficulty getting glucose in
their cells, which is why they must monitor
their blood glucose levels regularly.

 Glucose is one of the monosaccharides of

sucrose (table sugar) and lactose (milk
sugar) as well as the polysaccharides
glycogen, starch, and cellulose.
• Galactose is found combined with glucose
in the disaccharide lactose, which is
present in milk and other dairy products.
• A single chiral center (carbon 4) in
galactose is arranged opposite that of
glucose, which makes it a diastereomer of
glucose.
• Diastereomers that differ by one chiral
center are called epimers.
 Mannose, a monosaccharide, is found
in some fruits and vegetables.

 Cranberries contain high amounts of

mannose, which has been shown to
be effective in urinary tract infections.

 Mannose is an epimer of glucose.

Fructose
 A ketose, is commonly referred to as fruit sugar
or levulose.

 Combined with glucose to give sucrose, or table

sugar.

 The sweetest monosaccharide and is found in

fruits, vegetables, and honey.

 Not an epimer of glucose, but it can be broken

down for energy in the body.
 Pentoses are five-carbon sugars and include
ribose and 2-deoxyribose, which are parts of
nucleic acids that make up genetic material.
 Ribonucleic acid (RNA) contains ribose, and
deoxyribonucleic acid (DNA) contains
2-deoxyribose.
 The difference between these two pentoses is
the absence of an oxygen atom on carbon 2 of
deoxyribose.
 Ribose is also found in the vitamin riboflavin
and other biologically important molecules.
 REACTIONS OF
MONOSACCHARIDES
 Oxidation and Reduction
 Oxidation and reduction reactions are
commonly called redox reactions.

 Oxidation is a loss of electrons.

 Reduction is a gain of electrons.

 The mnemonic “OIL RIG” helps remember

redox reactions. Oxidation Is Loss, Reduction
Is Gain.
 When copper metal (shiny orange metal) is
exposed to oxygen, an ionic compound,
copper(II) oxide, is produced. This compound is
greenish in color. This reaction is shown as:

• The copper atoms in the reactant lose electrons

to form the Cu2+ ions in the product. The copper
has undergone oxidation.
 The electrons lost by copper atoms are
transferred to the oxygen atom, which then
becomes O2-. Oxygen has undergone
reduction.

 While the copper was being oxidized, oxygen

was being reduced.

 Copper then becomes the reducing agent

(causing oxygen to be reduced) and oxygen is
the oxidizing agent (causing copper to be
oxidized).
 Organic molecules are oxidized if they gain
oxygen or lose hydrogen, and they are reduced
if they lose oxygen or gain hydrogen.

 Some biological reactions undergo oxidation and

reduction. A summary of these characteristics
are as follows:
Monosaccharides and Redox
 An aldehyde functional group can undergo
oxidation by gaining oxygen or it can undergo
reduction by gaining hydrogen.

 During oxidation, aldehydes form carboxylic acids,

and during reduction, they form alcohols.

 In monosaccharides, oxidation produces a sugar

acid, and reduction produces a sugar alcohol.
• Benedict’s test is a useful test to determine the
presence of an oxidation reaction that occurs with
sugars.

• Aldose sugars are oxidized by Cu2+ ion, while the Cu2+

ion is reduced to Cu+ ion.
 The product of this reaction, copper(I) oxide
(Cu2O), is not soluble and forms a brick red
precipitate in solution.
 Aldoses are easily oxidized. They serve as
reducing agents and are referred to as
reducing sugars.

 Fructose and other ketoses are also reducing

sugars, even though they do not contain an
aldehyde group.

 The oxidizing agents can cause a

rearrangement of the ketose to an aldose.
This rearrangement can be shown
as:
 Benedict’s test can be used in urine dipsticks
to determine the level of glucose in urine.
Excess glucose in urine suggests high levels of
glucose in blood, which is an indicator of
diabetes.

 Aldoses or ketoses can be reduced by

hydrogen under the correct conditions,
producing sugar alcohols.

 Sugar alcohols are produced commercially as

artificial sweeteners and found in sugar-free
foods.
Reduction of glucose produces the sugar
alcohol, sorbitol, which is an artificial
sweetener.
 When glucose levels are high in the blood
stream, sorbitol can be produced by an
enzyme called aldose reductase.

 High levels of sorbitol can contribute to

cataracts, which is a clouding of the lens in the
eye.

 Cataracts are commonly seen in diabetics.

Ring Formation—The Truth about
Monosaccharide Structure
 Carbonyl groups can also react with a hydroxyl
functional group (–OH).

 When this happens, a hemiacetal functional

group is formed as shown:
 A hemiacetal can form within a
monosaccharide since it contains both a
carbonyl and several hydroxyl functional
groups.
 The carbonyl carbon that reacts to form the
hemiacetal is referred to as the anomeric carbon.

 Two ring arrangements can be produced. These

are termed anomers, and are referred to as the
alpha () and beta (β) anomer.

 The position of the –OH group on the anomeric

carbon relative to the position of the carbon
outside the ring determines the type of anomer
present.
 In the six-member ring (five carbons and an
oxygen) form of D-isomers, called a pyranose,
carbon 6 is always drawn on the top side of the
ring.

 In the  anomer, the –OH on the anomeric

carbon is trans to the carbon outside the ring.

 In the β anomer, the –OH on the anomeric

carbon is cis to the carbon outside the ring.
 D-Fructose contains both a ketone group and
several hydroxyl groups.

 The ring structure of D-fructose contains four

carbons and an oxygen to form a five-
membered ring called a furanose.

 In a furanose, carbons 1 and 6 remain outside

the ring.
 In a five-membered and six-membered ring,
the anomers are distinguished similarly.

 In the alpha anomer, the –OH on the anomeric

carbon is trans to the carbon outside the ring.

 In the beta anomer, the –OH on the anomeric

carbon is cis to the carbon outside the ring.
DISACCHARIDES
 Disaccharides

•Is cleaved to two monosaccharides on hydrolysis.

–Thesetwo monosaccharides may be the
same or different.

C12H22O11 + H2O C6H12O6 + C6H12O6

glucose
(a monosaccharide)
sucrose fructose
(a disaccharide) (a monosaccharide)
Condensation and Hydrolysis—Forming
and Breaking Glycosidic Bonds

• The –OH group that is most reactive in a

monosaccharide is the one on the
anomeric carbon.

• When this hydroxyl group reacts with

another hydroxyl group on another
monosaccharide a glycosidic bond is
formed.
• Formation of glycosides is an example of
another type of organic reaction. During
this reaction, a molecule of water is
eliminated as two molecules join.
 Condensation reaction is a type of reaction
that occurs when two molecules are joined and
a water molecule is produced. This type of
reaction is referred to as a dehydration
reaction.

 Hydrolysis reaction is the reverse of a

condensation reaction. A larger molecule forms
two smaller molecules and water is consumed
as a reactant.
 Condensation reactions occur between
different types of functional groups that
contain an –H in a polar bond, like O–H
or N–H, and an –OH group that can be
removed to form water.
NAMING GLYCOSIDIC
BONDS
 The glycosidic bond was in the alpha
position. If that bond had been in the beta
position, a different molecule would have
been formed with a different three-
dimensional structure.

 In naming glycosidic bonds, it is necessary

to name the configuration as well as the
carbons involved in the bond formation.
 In the case of maltose, the glycosidic bond is
specified as α(1→4) and is simply stated as
alpha-one-four.

 If the –OH group had been in the beta

configuration when the glycosidic bond was
formed, the bond would be in the β(1→4)
configuration. The molecule formed would be
named cellobiose and would have a different
two-dimensional and three-dimensional shape
than maltose.
THREE IMPORTANT
DISACCHARIDES
The formation of these three common
disaccharides is outlined below.
Maltose
• Maltose is known as malt sugar.
• It is formed by the breakdown of starch.
• Malted barley, a key ingredient in beer, contains
high levels of maltose.
• During germination of barley seeds, the starch
goes through hydrolysis to form maltose. This
process is halted by drying and roasting barley
seeds prior to their germination.
• One of the anomeric carbons is free, so maltose is
a reducing sugar.
The glycosidic bond is α(1→4).
Cellobiose

 Cellobiose is a stereoisomer of maltose.

 The only difference between the two is that
cellobiose has a (1,4) glycosidic bond while that
of maltose is (1,4).
 Obtained from hydrolysis of cellulose
Lactose
• Lactose is known as milk sugar.
• It is found in milk and milk products.
• An intolerance to lactose can occur in people who
inherit or lose the ability to produce the enzyme
lactase that hydrolyzes lactose into its
monosaccharide units.
• The glycosidic bond is (1→4).
• One of the anomeric carbons is free, so lactose is
a reducing sugar.
Sucrose
• Sucrose is known as table sugar.
• It is the most abundant disaccharide found in
nature.
• Sucrose is found in sugar cane and sugar beets.
• The glycosidic bond is  (1→2).
• Both anomeric carbons of the monosaccharides in
sucrose are bonded, therefore, sucrose is not a
reducing sugar. It will not react with Benedict’s
reagent.
POLYSACCHARIDES
Polysaccharides are large molecules of
monosaccharides that are connected to each
other through their anomeric carbons. There
are two types of polysaccharides:

1. Storage polysaccharides contain only  -glucose

units. Three important ones are starch, glycogen,
and amylopectin.

2. Structural polysaccharides contain only -

glucose units. Two important ones are cellulose
and chitin. Chitin contains a modified -glucose
unit.
 Storage and structural
polysaccharides are made up of
glucose units, but they are
structurally and functionally different
because of their glycosidic bonds and
difference in branching.
 STORAGE
POLYSACCHARIDES
Amylose and amylopectin—
starch
 Starch is a mixture of amylose and
amylopectin and is found in plant foods.
 Amylose makes up 20% of plant starch and is
made up of 250–4000 D-glucose units bonded
α(1→4) in a continuous chain.
 Long chains of amylose tend to coil.
 Amylopectin makes up 80% of plant starch
and is made up of D-glucose units connected
by α(1→4) glycosidic bonds.
 About every 25 glucose units of amylopectin, a
branch of glucose units are connected to the
glucose by an α(1→6) glycosidic bond.
 During fruit ripening, starch undergoes
hydrolysis of the α(1→4) bonds to produce
glucose and maltose, which are sweet.
 When we consume starch, our digestive
system breaks it down into glucose units for
use by our bodies.
Glycogen
 Glycogen is a storage polysaccharide found
in animals.
 Glycogen is stored in the liver and muscles.
 Its structure is identical to amylopectin, except
that α(1→6) branching occurs about every
12 glucose units.
 When glucose is needed, glycogen is
hydrolyzed in the liver to glucose.
 STRUCTURAL
POLYSACCHARIDES
Cellulose
 Cellulose contains glucose units bonded
(1→4).
 This glycosidic bond configuration changes the
three-dimensional shape of cellulose
compared with that of amylose.
 The chain of glucose units is straight. This
allows chains to align next to each other to
form a strong rigid structure.
 Cellulose is an insoluble fiber in our diet
because we lack the enzyme cellulase to
hydrolyze the (1→4) glycosidic bond.
 Whole grains are a good source of cellulose.
 Cellulose is important in our diet because it
assists with digestive movement in the small
and large intestine.
 Some animals and insects can digest cellulose
because they contain bacteria that produce
cellulase.
Chitin
 Chitin makes up the exoskeleton of insects and
crustaceans and cell walls of some fungi.
 It is made up of N-acetylglucosamine containing
(1→4) glycosidic bonds.
 It is structurally strong.
 Chitin is used as surgical thread that biodegrades
as a wound heals.
 It serves as a protection from water in insects.
 Chitin is also used to waterproof paper, and in
cosmetics and lotions to retain moisture.
CARBOHYDRATES AND
BLOOD
ABO Blood Types
 ABO blood types refer to carbohydrates on
red blood cells.

 These chemical markers are oligosaccharides

that contain either three or four sugar units.

 Sugar units are D-galactose, L-fucose,

N-acetylglucosamine, and N-
acetylgalactosamine.
 The following shows the carbohydrates and
their attachments in type O, type A, and type B
blood. Type AB blood has both type A and type
B sets on their blood cells.
 Type O blood is considered the universal donor
while type AB blood is considered the universal
acceptor.
 The following table shows the compatibility of
blood groups.
Heparin
 Heparin is a medically important
polysaccharide because it prevents clotting in
the bloodstream.
 It is a highly ionic polysaccharide of repeating
disaccharide units of an oxidized
monosaccharide and D-glucosamine. Heparin
also contains sulfate groups that are
negatively charged.
 It belongs to a group of polysaccharides called
glycosaminoglycans.
SUMMARY OF THE TOPIC
Classes of Carbohydrates

 Carbohydrates are classified as

monosaccharides (simple sugars),
disaccharides (two monosaccharide
units), oligosaccharides (three to
nine monosaccharide units), and
polysaccharides (many
monosaccharide units).
Monosaccharides
 A monosaccharide has a molecular formula
of Cn(H2O)n, where n = 3–6.

 Fischer projections that highlight chiral centers

are used to represent monosaccharides.

 Most monosaccharides in nature are D-

isomers.
 Multiple chiral centers lead to
enantiomers or diastereomers.

 Important monosaccharides are

glucose, galactose, fructose,
mannose, ribose, and deoxyribose.
Oxidation and Reduction
Reactions
 Oxidation is a loss of electrons and reduction
is a gain of electrons.

 These are common types of reactions in

organic molecules.

 For organic molecules, oxidation is the

addition of oxygen and reduction is the
addition of hydrogen.
 The anomeric carbon of
carbohydrates is highly reactive and
can be oxidized to a carboxylic acid or
reduced to an alcohol.

 Monosaccharides are considered

reducing sugars because their
anomeric carbon can react.
Ring Formation—The Truth about
Monosaccharide Structure
 A hydroxyl group and the carbonyl group
can react to enclose the hydroxyl’s oxygen
in a ring.

 Because the carbonyl group is planar, two

possible ring arrangements about the
anomeric carbon occur when the ring
forms. These are termed the α and 
anomers.
Disaccharides
 Condensation and hydrolysis are common
reactions that occur in biomolecules.

 Condensation reactions produce a water

molecule while bonding two molecules
together.

 Hydrolysis reactions consume a molecule of

water while a molecule is broken into two
smaller molecules.
 Carbohydrates form glycosides when an
anomeric carbon reacts with a hydroxyl group
on a second molecule. The bond formed is
called a glycosidic bond.

 Glycosidic bonds are named by designating

the anomer of the reacting monosaccharide
and the carbons that are bonded, for example,
α(1→4).
Polysaccharides
 A polysaccharide consists of many
monosaccharide units bonded together through
glycosidic bonds.

 Glucose is stored as glycogen in animals and

starch in plants.

 Starch consists of amylose, a linear chain of

glucose, and amylopectin, a branched chain of
glucose
 Glycogen contains many more branches in its
structure than amylopectin.

 Two important polysaccharides are cellulose in

plants and chitin in arthropods and fungi.

 Cellulose consists of (1→4) and is the

structural component of plants. It has a linear
structure.
 Chitin is linear. It contains N-
acetylglucosamine.

 Cellulose and chitin form strong,

water-resistant materials when the
linear chains are aligned to each
other.
Carbohydrates and Blood
 The ABO blood groups are oligosaccharides on
the surface of red blood cells.

 The O blood group is considered the universal

donor.

 Heparin, a polysaccharide, functions in the blood

as an anticoagulant and is found as a coating on
medical tubing and syringes during blood
transfusions.
END OF SLIDES