Carbohydrates

 Broadly define as polyhydroxy aldehydes or ketones and their derivatives or as

substances that yields one of these compounds.

 The 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

Carbohydrates are the most abundant of all organic compounds in nature

 In plants, energy from the sun is used to convert carbon dioxide and water into the
carbohydrate glucose.

 Many of the glucose molecules are made into long-chain polymers of starch that store
energy.

 About 65% of the foods in our diet consist of carbohydrates.

 Each day we utilize carbohydrates in foods such as bread, pasta, potatoes and rice.

 Other carbohydrates called disaccharides include sucrose (table sugar) and lactose in
milk.

 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.

 In plants, a polymer of glucose called cellulose builds the structural framework.

Cellulose has other important uses too.

 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:

 they provide energy through oxidation

 they supply carbon for the synthesis of cell components

  they serve as a form of stored chemical energy

 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 C x(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

o monosaccharides

o disaccharides

Complex Carbohydrates

o oligosaccharides

o 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

o carbohydrate form used by the body, referred to as “blood sugar”

o basic sub-unit of other larger carbohydrate molecules

o found in fruits, vegetables, honey

 Fructose

o sweetest of the sugars

o occurs naturally in fruits & honey, “fruit sugar”

o combines with glucose to form sucrose

 Galactose

o 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

Classification is based on:

• Number of carbon atoms present

• Whether the carbonyl group is an aldehyde or ketone

Some Classes of Monosaccharides

• Aldoses: Monosaccharides that are polyhydroxy aldehydes

• Ketoses: Monosaccharides that are polyhydroxy ketones

No. of Carbons Aldose Ketose

4 Aldotetrose Ketotetrose
 5 Aldopentose Ketopentose
6 Aldohexose Ketohexose
7 Aldoheptose Ketoheptose
8 Aldooctose Ketooctose

Generic names Examples

3 Carbons trioses Glyceraldehyde
4 Carbons tetroses Erythrose
5 Carbons pentoses Ribose
6 Carbons hexoses Glucose
7 Carbons heptoses Sedoheptulose
9 Caorbons nonoses Neuraminic acid

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.

 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 2 n, where n is

the number of chiral centers present in the molecule.

 Glucose has 4 chiral centers, so there are 16 stereoisomers, 2 4 = 16.

Fischer Projection

 Place the carbonyl group at or near the top and the last achiral CH₂OH at the bottom.

 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.

 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.

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

• Is cleaved to two monosaccharides on hydrolysis.

– These two monosaccharides may be the

same or different.

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 b(1,4) glycosidic bond while
that of maltose is a(1,4).

 Obtained from hydrolysis of cellulose

Lactose

• Lactose is known as milk sugar.

• It is found in milk and milk products.

• 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 α-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 bond.

 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 makers 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.