CHO20 19 New PDF

Carbohydrates
• Most abundant biomolecule in nature

• Many functions
– Energy (4KCal/Gram)
– energy storage
– Structural elements
– Mediator of interactions
CARBOHYDRATES in the BODY
USE OF GLUCOSE
• Energy – glucose is the primary fuel for most
cells in the body. The brain MUST have
glucose!
• Sparing body protein – if glucose is scarce,
the body will breakdown its own protein.
• Preventing ketosis – with no carbohydrate, fat
breakdown produces ketone bodies. Can
lead to ketosis.
• Storage as glycogen – liver stores are used
to maintain blood sugar, while muscle stores
are used to fuel activity.
Introduction to Carbohydrates
• Carbohydrates are sugars and provide energy

when consumed.
• Our bodies break down carbohydrates to extract

energy. Carbon dioxide and water are released
in the process.
• Glucose is the primary carbohydrate our bodies

use to produce energy.
• Carbohydrates are classified as biomolecules.

© 2011 Pearson Education, Inc. Chapter 5 3
Introduction to Carbohydrates, Continued
• Simple carbohydrates are referred to as

simple sugars and are often sweet to the taste.
• Consumption of more sugar than is needed for

energy results in conversion of these sugars to
fat.
• Complex carbohydrates include starches and

the plant and wood fibers known as cellulose.

Introduction to Carbohydrates, Continued
• Carbohydrates are found on the surface of cells

where they act as “road signs” allowing
molecules to distinguish one cell from another.
• ABO blood markers found on red blood cells

are made up of carbohydrates. They allow us to
distinguish our body’s blood type from a foreign
blood type.
• Carbohydrates in our body prevent blood clots.

They are also found in our genetic material.
Classes of Carbohydrates
• Monosaccharides are the simplest

carbohydrates. They cannot be broken down to
smaller carbohydrates.
• Disaccharides consist of two monosaccharide

units joined together; they can be split into two
monosaccharides. Sucrose, table sugar, can be
broken down into glucose and fructose.
• Oligosaccharides contain anywhere from three

to nine monosaccharide units. ABO blood
groups are oligosaccharides.
Classes of Carbohydrates, Continued
Polysaccharides are large molecules containing

10 or more monosaccharide units. Carbohydrate
units are connected in one continuous chain or
the chain can be branched.

Monosaccharides
• Monosaccharides contain the elements carbon,

hydrogen, and oxygen, and have the general
formula Cn(H2O)n, where n is a whole number 3
or greater.
• Monosaccharides contain several functional

groups. They contain the hydroxyl group
represented as –OH. They also contain a
carbonyl group, which is an oxygen double
bonded to a carbon atom. The carbonyl group
may be an aldehyde or a ketone.

Monosaccharides, Continued
Functional Groups in Monosaccharides—

Alcohols, Aldehydes, and Ketones
Alcohols
• Alcohol is an organic compound containing the
–OH group.
• Ethanol is one of the simplest alcohols and is
prepared from the fermentation of simple sugars
in grains and fruits. Ethanol is present in beer
and liquors, and is used as an alternative fuel
blend, such as gasohol and E85 (85% ethanol
and 15% gasoline).

Aldehydes
• Monosaccharides can
contain an aldehyde group
on one end of the molecule
in addition to multiple
hydroxyl groups.

Ketones
• A ketone also contains the carbonyl group, but
has an alkyl or aromatic group on both sides of
the carbonyl group.
• Acetone is the simplest ketone. It is the main
component of fingernail polish remover.

• Monosaccharides that contain an aldehyde
group are referred to as an aldose. Those that
contain a ketone group are referred to as a
ketose.
• Monosaccharides are classified according to the

number of carbon atoms. Most common
monosaccharides have three to six carbon
atoms.
– Triose contains three carbons.
– Tetrose contains four carbons.
– Pentose contains five carbons.
– Hexose contains six carbons.
• Carbohydrates are further classified on whether

they contain an aldehyde or ketone group.
• For example, glucose, the most abundant

monosaccharide found is nature, contains six
carbons and an aldehyde group. It is classified
as an aldohexose.
• Fructose, known as fruit sugar, contains six

carbons and a ketone group. It is classified as a
ketohexose.
Stereochemistry in Monosaccharides
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.


• 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?

• 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.
Representing stereoisomers—the Fischer

projection
• 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.

Representing stereoisomers—the
Fischer projection
• 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.


Examples
H H H H
C O C O C O C O
H C OH HO C H H C OH HO C H
HO C H H C OH H C OH HO C H
H C OH HO C H H C OH HO C H
H C OH HO C H H C OH H C OH
CH2OH CH2OH CH2OH CH2OH
D-glucose L-glucose D-allose D-talose

(enantiomer) (epimer at C3) (diastereomer)
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.

5.2 Monosaccharides, Continued
• Fructose, a ketose, is commonly referred to as

fruit sugar or levulose.
• Fructose is combined with glucose to give

sucrose, or table sugar.
• Fructose is the sweetest monosaccharide and is

found in fruits, vegetables, and honey.
• Fructose is 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.
Oxidation and Reduction Reactions
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.
Oxidation and Reduction Reactions,
Continued
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.
Continued
• 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.
Oxidation Reactions
Oxidation of aldehyde = Oxidation of terminal Oxidation of both = aldaric

aldonic acid CH2OH = uronic acid acid
H OH
OH
C O C O
C O
H C OH H C OH
H C OH
HO C H HO C H
HO C H
H C OH H C OH
H C OH
H C OH H C OH
H C OH
C O C O
CH2OH
OH OH
D-Gluconic acid D-Glucuronic acid D-Glucaric acid

Continued
The product of this reaction, copper(I) oxide
(Cu2O), is not soluble and forms a brick red
precipitate in solution.

Continued
• 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.

Continued
This rearrangement can be shown as:

Continued
• 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.
Continued
Reduction of glucose produces the sugar alcohol,
sorbitol, which is an artificial sweetener.

Continued
• 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.

Optical Activity
• When a plane polarized light is

passed through a solution containing
monosaccharides the light will either
be rotated towards right or left.
• This rotation is because of the

presence of asymmetric carbon atom.
• If it is rotated towards left-

levorotatory (-)
Mutarotation
a and b forms
spontaneously
interconvert in an
aqueous environment.
• Proportion of each
anomer differs for each
sugar.
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:

Cyclization
H C O H C OH
H C OH H C OH
O
HO C H HO C H
H C OH H C OH
H C OH H C
CH2OH CH2OH
Monosaccharide Structure, Continued
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 (a) 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 a 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.

5.4 Ring Formation—The Truth about
• 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
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.

Glycosidic Linkages
Glycosidic
linkage
Aglycone
Disaccharides, Continued
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.

Glycosidic Linkages
Glycosidic
linkage
Aglycone
• 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
• In the slide showing the formation of maltose, we

observed that 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—Maltose,

Lactose, and Sucrose
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.
Maltose, Continued
• The glycosidic bond is α(1→4).

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 b(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 b (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.

Oligosaccharides
• 3 - 10 or more subunits
• Often attached to proteins

or lipids to form
glycoproteins or glycolipids,
respectively.
• N-linked
– Attached via asparagine.
• O-linked
– Attached via threonine or
serine or OH on lipid
Polysaccharides
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 b-glucose

units. Two important ones are cellulose and chitin.
Chitin contains a modified b-glucose unit.
Polysaccharides, Continued
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.
Amylose and amylopectin—starch

• 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
b(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
• Cellulose is an insoluble fiber in our diet
because we lack the enzyme cellulase to
hydrolyze the b(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
b(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.

Carbohydrates and Blood, Continued
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.

Structural Elements: Animals
• Glycosaminoglycans
(GAGs)
• Heteropolysaccharides
– Disaccharide repeating
units
• Negatively charged at
physiological pH.
• Bind a lot of H2O.

5.7 Carbohydrates and Blood, Continued
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.
Chapter 5 80 © 2011 Pearson
Education, Inc.

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Carbohydrates

• Most abundant biomolecule in nature

• Carbohydrates are sugars and provide energy

• Our bodies break down carbohydrates to extract

• Glucose is the primary carbohydrate our bodies

• Carbohydrates are classified as biomolecules.

• Simple carbohydrates are referred to as

• Consumption of more sugar than is needed for

• Complex carbohydrates include starches and

© 2011 Pearson Education, Inc. Chapter 5 4

• Carbohydrates are found on the surface of cells

• ABO blood markers found on red blood cells

• Carbohydrates in our body prevent blood clots.

• Monosaccharides are the simplest

• Disaccharides consist of two monosaccharide

• Oligosaccharides contain anywhere from three

Polysaccharides are large molecules containing

© 2011 Pearson Education, Inc. Chapter 5 7

• Monosaccharides contain the elements carbon,

• Monosaccharides contain several functional

© 2011 Pearson Education, Inc. Chapter 5 8

Functional Groups in Monosaccharides—

© 2011 Pearson Education, Inc. Chapter 5 9

© 2011 Pearson Education, Inc. Chapter 5 10

© 2011 Pearson Education, Inc. Chapter 5 11

• Monosaccharides are classified according to the

• Carbohydrates are further classified on whether

• For example, glucose, the most abundant

• Fructose, known as fruit sugar, contains six

Multiple chiral centers

© 2011 Pearson Education, Inc. Chapter 5 14

Multiple chiral centers

© 2011 Pearson Education, Inc. Chapter 5 15

Representing stereoisomers—the Fischer

© 2011 Pearson Education, Inc. Chapter 5 17

© 2011 Pearson Education, Inc. Chapter 5 18

Stereoisomers that are not enantiomers

© 2011 Pearson Education, Inc. Chapter 5 19

© 2011 Pearson Education, Inc. Chapter 5 20

CH2OH CH2OH CH2OH CH2OH

D-glucose L-glucose D-allose D-talose

Some Important Monosaccharides

• Glucose is the most abundant monosaccharide

• Glucose is also known as dextrose, blood sugar,

• Glucose is broken down in cells to produce

© 2011 Pearson Education, Inc. Chapter 5 22

• Diabetics have difficulty getting glucose in their

• Glucose is one of the monosaccharides of

© 2011 Pearson Education, Inc. Chapter 5 23

• Galactose is found combined with glucose in the

• A single chiral center (carbon 4) in galactose is

• Diastereomers that differ by one chiral center

© 2011 Pearson Education, Inc. Chapter 5 24

• Mannose, a monosaccharide, is found in some

• Cranberries contain high amounts of mannose,

• Mannose is an epimer of glucose.

© 2011 Pearson Education, Inc. Chapter 5 25

• Fructose, a ketose, is commonly referred to as

• Fructose is combined with glucose to give

• Fructose is the sweetest monosaccharide and is

• Fructose is not an epimer of glucose, but it can

• Pentoses are five-carbon sugars and include

Oxidation and Reduction