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i
890
Chapter 16 Carbohydrates

Chapter 16
Carbohydrates

891
Chapter 16 Carbohydrates

Opening Essay

In the United States, 17.9 million people have been diagnosed with diabetes, and experts estimate that at least
another 5.7 million people have the disease but have not been diagnosed. In 2006, diabetes was the seventh
leading cause of death, listed on 72,507 death certificates. Moreover, it was a contributing factor in over 200,000
deaths in which the cause was listed as something else, such as heart or kidney disease.

People with diabetes are impaired in their ability to metabolize glucose, a sugar needed by the body for energy;
as a result, excessive quantities of glucose accumulate in the blood and the urine. The characteristic symptoms
of diabetes are weight loss, constant hunger, extreme thirst, and frequent urination (the kidneys excrete large
amounts of water in an attempt to remove the excess sugar from the blood).

An important diagnostic test for diabetes is the oral glucose tolerance test, which measures the level of glucose in
blood plasma. A first measurement is made after a fast of at least 8 h, followed by another measurement 2 h after
the person drinks a flavored solution of 75 g of glucose dissolved in water. At the second measurement, the
glucose plasma level should be no higher than 139 mg/dL. Individuals with a value between 140 and 199 mg/dL
are diagnosed with prediabetes, while those with a value of 200 mg/dL or above are diagnosed with diabetes.
Following a diagnosis of diabetes a person will need to monitor his or her blood glucose levels daily (or more
often) using a glucose meter.

Figure 16.1
Using a Glucose Meter to Test Blood Glucose Level

© Thinkstock

892
Chapter 16 Carbohydrates

Glucose is one of the carbohydrates you will learn about in this chapter as we begin
the study of biochemistry1—the chemistry of molecules found in living organisms.
Later we will study the other three major types of macromolecules found in living
organisms: lipids, proteins, and nucleic acids.

1. The chemistry of molecules

found in living organisms.

893
Chapter 16 Carbohydrates

16.1 Carbohydrates

LEARNING OBJECTIVE

1. Recognize carbohydrates and classify them as mono-, di-, or

polysaccharides.

All carbohydrates2 consist of carbon, hydrogen, and oxygen atoms and are
polyhydroxy aldehydes or ketones or are compounds that can be broken down to
form such compounds. Examples of carbohydrates include starch, fiber, the sweet-
tasting compounds called sugars, and structural materials such as cellulose. The
term carbohydrate had its origin in a misinterpretation of the molecular formulas of
many of these substances. For example, because its formula is C 6H12O6, glucose was
once thought to be a “carbon hydrate” with the structure C6·6H2O.

2. A compound composed of
carbon, hydrogen, and oxygen
atoms that is a polyhydroxy
aldehyde or ketone or a
compound that can be broken
down to form such a
compound. It is one of the
three main components of the
human diet.

894
Chapter 16 Carbohydrates

EXAMPLE 1

Which compounds would be classified as carbohydrates?

1.

2.

3.

4.

Solution

1. This is a carbohydrate because the molecule contains an aldehyde

functional group with OH groups on the other two carbon atoms.
2. This is not a carbohydrate because the molecule does not contain an
aldehyde or a ketone functional group.
3. This is a carbohydrate because the molecule contains a ketone
functional group with OH groups on the other two carbon atoms.
4. This is not a carbohydrate; although it has a ketone functional group,
one of the other carbons atoms does not have an OH group attached.

16.1 Carbohydrates 895

Chapter 16 Carbohydrates

SKILL-BUILDING EXERCISE

Which compounds would be classified as carbohydrates?

1.

2.

3.

4.

Green plants are capable of synthesizing glucose (C6H12O6) from carbon dioxide
(CO2) and water (H2O) by using solar energy in the process known as
photosynthesis3:

6CO2 + 6H2O + 686 kcal → C6H12O6 + 6O2

(The 686 kcal come from solar energy.) Plants can use the glucose for energy or
3. The process by which plants convert it to larger carbohydrates, such as starch or cellulose. Starch provides
use solar energy to convert energy for later use, perhaps as nourishment for a plant’s seeds, while cellulose is
carbon dioxide and water to the structural material of plants. We can gather and eat the parts of a plant that
glucose.

16.1 Carbohydrates 896

Chapter 16 Carbohydrates

store energy—seeds, roots, tubers, and fruits—and use some of that energy
ourselves. Carbohydrates are also needed for the synthesis of nucleic acids and
many proteins and lipids.

Animals, including humans, cannot synthesize carbohydrates from carbon dioxide

and water and are therefore dependent on the plant kingdom to provide these vital
compounds. We use carbohydrates not only for food (about 60%–65% by mass of the
average diet) but also for clothing (cotton, linen, rayon), shelter (wood), fuel
(wood), and paper (wood).

The simplest carbohydrates—those that cannot be hydrolyzed to produce even

smaller carbohydrates—are called monosaccharides4. Two or more
monosaccharides can link together to form chains that contain from two to several
hundred or thousand monosaccharide units. Prefixes are used to indicate the
number of such units in the chains. Disaccharide5 molecules have two
monosaccharide units, trisaccharide molecules have three units, and so on. Chains
with many monosaccharide units joined together are called polysaccharides6. All
these so-called higher saccharides can be hydrolyzed back to their constituent
monosaccharides.

Note

Compounds that cannot be hydrolyzed will not react with water to form two or
more smaller compounds.

CONCEPT REVIEW EXERCISES

1. Why is photosynthesis important?

2. Identify the differences among monosaccharides, disaccharides, and

polysaccharides.
4. The simplest carbohydrate that
cannot be hydrolyzed to
produce smaller carbohydrate
molecules.

5. A carbohydrate containing two

monosaccharide units.

6. A carbohydrate containing
many monosaccharide units.

16.1 Carbohydrates 897

Chapter 16 Carbohydrates

ANSWERS

1. Photosynthesis is the process by which solar energy is used to reduce carbon

dioxide to carbohydrates, which are needed for energy by plants and other
living organisms that eat plants.

2. A monosaccharide is the simplest carbohydrate and cannot be hydrolyzed to

produce a smaller carbohydrate; a disaccharide is composed of two
monosaccharide units; and a polysaccharide contains many saccharide units.

KEY TAKEAWAYS

• Carbohydrates are an important group of biological molecules that

includes sugars and starches.
• Photosynthesis is the process by which plants use energy from sunlight
to synthesize carbohydrates.
• A monosaccharide is the simplest carbohydrate and cannot be
hydrolyzed to produce a smaller carbohydrate molecule. Disaccharides
contain two monosaccharide units, and polysaccharides contain many
monosaccharide units.

EXERCISES

1. When an aqueous solution of trehalose is heated, two molecules of glucose are

produced for each molecule of trehalose. Is trehalose a monosaccharide, a
disaccharide, or a polysaccharide?

2. When an aqueous solution of arabinose is heated, no other molecules are

produced. Is arabinose a monosaccharide, a disaccharide, or a polysaccharide?

ANSWER

1. Trehalose is a disaccharide because it is hydrolyzed into two molecules of

glucose (a monosaccharide).

16.1 Carbohydrates 898

Chapter 16 Carbohydrates

16.2 Classes of Monosaccharides

LEARNING OBJECTIVES

1. Classify monosaccharides as aldoses or ketoses and as trioses, tetroses,

pentoses, or hexoses.
2. Distinguish between a D sugar and an L sugar.

The naturally occurring monosaccharides contain three to seven carbon atoms per
molecule. Monosaccharides of specific sizes may be indicated by names composed
of a stem denoting the number of carbon atoms and the suffix -ose. For example, the
terms triose, tetrose, pentose, and hexose signify monosaccharides with, respectively,
three, four, five, and six carbon atoms. Monosaccharides are also classified as
aldoses or ketoses. Those monosaccharides that contain an aldehyde functional
group are called aldoses7; those containing a ketone functional group on the second
carbon atom are ketoses8. Combining these classification systems gives general
names that indicate both the type of carbonyl group and the number of carbon
atoms in a molecule. Thus, monosaccharides are described as aldotetroses,
aldopentoses, ketopentoses, ketoheptoses, and so forth. Glucose and fructose are
specific examples of an aldohexose and a ketohexose, respectively.

7. A monosaccharide that
contains an aldehyde
functional group.

8. A monosaccharide that
contains a ketone functional
group on the second carbon
atom.

899
Chapter 16 Carbohydrates

EXAMPLE 2

Draw an example of each type of compound.

1. a ketopentose
2. an aldotetrose

Solution

1. The structure must have five carbon atoms with the second
carbon atom being a carbonyl group and the other four carbon
atoms each having an OH group attached. Several structures are
possible, but one example is shown.

2. The structure must have four carbon atoms with the first carbon
atom part of the aldehyde functional group. The other three
carbon atoms each have an OH group attached. Several
structures are possible, but one example is shown.

16.2 Classes of Monosaccharides 900

Chapter 16 Carbohydrates

SKILL-BUILDING EXERCISE

Draw an example of each type of compound.

1. an aldohexose

2. a ketotetrose

The simplest sugars are the trioses. The possible trioses are shown in part (a) of
Figure 16.2 "Structures of the Trioses"; glyceraldehyde is an aldotriose, while
dihydroxyacetone is a ketotriose. Notice that two structures are shown for
glyceraldehyde. These structures are stereoisomers9, isomers having the same
structural formula but differing in the arrangement of atoms or groups of atoms in
three-dimensional space. If you make models of the two stereoisomers of
glyceraldehyde, you will find that you cannot place one model on top of the other
and have each functional group point in the same direction. However, if you place
one of the models in front of a mirror, the image in the mirror will be identical to
the second stereoisomer in part (b) of Figure 16.2 "Structures of the Trioses".
Molecules that are nonsuperimposable (nonidentical) mirror images of each other
are a type of stereoisomer called enantiomers10 (Greek enantios, meaning
“opposite”).

Note

Cis-trans (geometric) isomers were discussed in Chapter 13 "Unsaturated and

Aromatic Hydrocarbons", Section 13.2 "Cis-Trans Isomers (Geometric
Isomers)". These are another type of stereoisomers.

9. An isomer that has the same

structural formula but differs
in the arrangement of atoms or
groups of atoms in three-
dimensional space.

10. Stereoisomers that are

nonsuperimposable mirror
images of each other.

16.2 Classes of Monosaccharides 901

Chapter 16 Carbohydrates

Figure 16.2 Structures of the Trioses

(a) D- and L-glyceraldehyde are mirror images of each other and represent a pair of enantiomers. (b) A ball-and-
stick model of D-glyceraldehyde is reflected in a mirror. Note that the reflection has the same structure as L-
glyceraldehyde.

A key characteristic of enantiomers is that they have a carbon atom to which four
different groups are attached. Note, for example, the four different groups attached
to the central carbon atom of glyceraldehyde (part (a) of Figure 16.2 "Structures of
the Trioses"). A carbon atom that has four different groups attached is a chiral
carbon11. If a molecule contains one or more chiral carbons, it is likely to exist as
two or more stereoisomers. Dihydroxyacetone does not contain a chiral carbon and
thus does not exist as a pair of stereoisomers. Glyceraldehyde, however, has a chiral
carbon and exists as a pair of enantiomers. Except for the direction in which each
enantiomer rotates plane-polarized light, these two molecules have identical
physical properties. One enantiomer has a specific rotation of +8.7°, while the other
has a specific rotation of −8.7°.

H. Emil Fischer, a German chemist, developed the convention commonly used for
11. A carbon atom that has four writing two-dimensional representations of the monosaccharides, such as those in
different groups attached to it. part (a) of Figure 16.2 "Structures of the Trioses". In these structural formulas, the

16.2 Classes of Monosaccharides 902

Chapter 16 Carbohydrates

aldehyde group is written at the top, and the hydrogen atoms and OH groups that
are attached to each chiral carbon are written to the right or left. (If the
monosaccharide is a ketose, the ketone functional group is the second carbon
atom.) Vertical lines represent bonds pointing away from you, while horizontal
lines represent bonds coming toward you. The formulas of chiral molecules
represented in this manner are referred to as Fischer projections.

The two enantiomers of glyceraldehyde are especially important because

monosaccharides with more than three carbon atoms can be considered as being
derived from them. Thus, D- and L-glyceraldehyde provide reference points for
designating and drawing all other monosaccharides. Sugars whose Fischer
projections terminate in the same configuration as D-glyceraldehyde are designated
as D sugars12; those derived from L-glyceraldehyde are designated as L sugars13.

Note

By convention, the penultimate (next-to-last) carbon atom has been chosen as

the carbon atom that determines if a sugar is D or L. It is the chiral carbon
farthest from the aldehyde or ketone functional group.

12. A sugar whose Fischer

projection terminates in the
same configuration as D-
glyceraldehyde.

13. A sugar whose Fischer

projection terminates in the
same configuration as L-
glyceraldehyde.

16.2 Classes of Monosaccharides 903

Chapter 16 Carbohydrates

Looking Closer: Polarized Light

A beam of ordinary light can be pictured as a bundle of waves; some move up

and down, some sideways, and others at all other conceivable angles. When a
beam of light has been polarized, however, the waves in the bundle all vibrate
in a single plane. Light altered in this way is called plane-polarized light. Much of
what chemists know about stereoisomers comes from studying the effects they
have on plane-polarized light. In this illustration, the light on the left is not
polarized, while that on the right is polarized.

Sunlight, in general, is not polarized; light from an ordinary light bulb or an

ordinary flashlight is not polarized. One way to polarize ordinary light is to pass
it through Polaroid sheets, special plastic sheets containing carefully oriented
organic compounds that permit only light vibrating in a single plane to pass
through. To the eye, polarized light doesn’t “look” any different from
nonpolarized light. We can detect polarized light, however, by using a second
sheet of polarizing material, as shown here.

16.2 Classes of Monosaccharides 904

Chapter 16 Carbohydrates

In the photo on the left, two Polaroid sheets are aligned in the same direction;
plane-polarized light from the first Polaroid sheet can pass through the second
sheet. In the photo on the right, the top Polaroid sheet has been rotated 90° and
now blocks the plane-polarized light that comes through the first Polaroid
sheet.

Certain substances act on polarized light by rotating the plane of vibration.

Such substances are said to be optically active. The extent of optical activity is
measured by a polarimeter, an instrument that contains two polarizing lenses
separated by a sample tube, as shown in the accompanying figure. With the
sample tube empty, maximum light reaches the observer’s eye when the two
lenses are aligned so that both pass light vibrating in the same plane. When an
optically active substance is placed in the sample tube, that substance rotates
the plane of polarization of the light passing through it, so that the polarized
light emerging from the sample tube is vibrating in a different direction than
when it entered the tube. To see the maximum amount of light when the
sample is in place, the observer must rotate one lens to accommodate the
change in the plane of polarization.

16.2 Classes of Monosaccharides 905

Chapter 16 Carbohydrates

Figure 16.3
Diagram of a Polarimeter

Some optically active substances rotate the plane of polarized light to the right
(clockwise) from the observer’s point of view. These compounds are said to be
dextrorotatory; substances that rotate light to the left (counterclockwise) are
levorotatory. To denote the direction of rotation, a positive sign (+) is given to
dextrorotatory substances, and a negative sign (−) is given to levorotatory
substances.

CONCEPT REVIEW EXERCISES

1. What is a chiral carbon?

2. Describe how enantiomers differ.

16.2 Classes of Monosaccharides 906

Chapter 16 Carbohydrates

ANSWERS

1. A chiral carbon is a carbon atom with four different groups attached to it.

2. Enantiomers are mirror images of each other; they differ in the arrangements
of atoms around a chiral carbon.

KEY TAKEAWAYS

• Monosaccharides can be classified by the number of carbon atoms in the

structure and/or the type of carbonyl group they contain (aldose or
ketose).
• Most monosaccharides contain at least one chiral carbon and can form
stereoisomers.
• Enantiomers are a specific type of stereoisomers that are mirror images
of each other.

16.2 Classes of Monosaccharides 907

Chapter 16 Carbohydrates

EXERCISES

1. Identify each sugar as an aldose or a ketose and then as a triose, tetrose,

pentose, or hexose.

a. D-glucose

b. L-ribulose

c. D-glyceraldehyde

16.2 Classes of Monosaccharides 908

Chapter 16 Carbohydrates

2. Identify each sugar as an aldose or a ketose and then as a triose, tetrose,

pentose, or hexose.

a. dihydroxyacetone

b. D-ribose

c. D-galactose

16.2 Classes of Monosaccharides 909

Chapter 16 Carbohydrates

3. Identify each sugar as an aldose or a ketose and then as a D sugar or an L sugar.

a.

16.2 Classes of Monosaccharides 910

Chapter 16 Carbohydrates

b.

4. Identify each sugar as an aldose or a ketose and then as a D sugar or an L sugar.

a.

b.

16.2 Classes of Monosaccharides 911

Chapter 16 Carbohydrates

ANSWERS

1. a. aldose; hexose
b. ketose; pentose
c. aldose; triose

3. a. aldose; D sugar
b. ketose; L sugar

16.2 Classes of Monosaccharides 912

Chapter 16 Carbohydrates

16.3 Important Hexoses

LEARNING OBJECTIVE

1. Identify the structures of D-glucose, D-galactose, and D-fructose and

describe how they differ from each other.

Although a variety of monosaccharides are found in living organisms, three hexoses

are particularly abundant: D-glucose, D-galactose, and D-fructose (Figure 16.4
"Structures of Three Important Hexoses"). Glucose and galactose are both
aldohexoses, while fructose is a ketohexose.

Figure 16.4 Structures of Three Important Hexoses

Each hexose is pictured with a food source in which it is commonly found.

Source: Photos © Thinkstock.

913
Chapter 16 Carbohydrates

Glucose

D-Glucose, generally referred to as simply glucose, is the most abundant sugar

found in nature; most of the carbohydrates we eat are eventually converted to it in
a series of biochemical reactions that produce energy for our cells. It is also known
by three other names: dextrose, from the fact that it rotates plane-polarized light in
a clockwise (dextrorotatory) direction; corn sugar because in the United States
cornstarch is used in the commercial process that produces glucose from the
hydrolysis of starch; and blood sugar because it is the carbohydrate found in the
circulatory system of animals. Normal blood sugar values range from 70 to 105 mg
glucose/dL plasma, and normal urine may contain anywhere from a trace to 20 mg
glucose/dL urine.

The Fischer projection of D-glucose is given in Figure 16.5 "Cyclization of D-

Glucose". Glucose is a D sugar because the OH group on the fifth carbon atom (the
chiral center farthest from the carbonyl group) is on the right. In fact, all the OH
groups except the one on the third carbon atom are to the right.

Galactose

D-Galactose does not occur in nature in the uncombined state. It is released when
lactose, a disaccharide found in milk, is hydrolyzed. The galactose needed by the
human body for the synthesis of lactose is obtained by the metabolic conversion of
D-glucose to D-galactose. Galactose is also an important constituent of the
glycolipids that occur in the brain and the myelin sheath of nerve cells. (For more
information about glycolipids, see Chapter 17 "Lipids", Section 17.3 "Membranes
and Membrane Lipids".) For this reason it is also known as brain sugar. The structure
of D-galactose is shown in Figure 16.4 "Structures of Three Important Hexoses".
Notice that the configuration differs from that of glucose only at the fourth carbon
atom.

Fructose

D-Fructose, also shown in Figure 16.4 "Structures of Three Important Hexoses", is

the most abundant ketohexose. Note that from the third through the sixth carbon
atoms, its structure is the same as that of glucose. It occurs, along with glucose and
sucrose, in honey (which is 40% fructose) and sweet fruits. Fructose (from the Latin
fructus, meaning “fruit”) is also referred to as levulose because it has a specific
rotation that is strongly levorotatory (−92.4°). It is the sweetest sugar, being 1.7
times sweeter than sucrose, although many nonsugars are several hundred or
several thousand times as sweet (Table 16.1 "The Relative Sweetness of Some
Compounds (Sucrose = 100)").

16.3 Important Hexoses 914

Chapter 16 Carbohydrates

Table 16.1 The Relative Sweetness of Some Compounds (Sucrose = 100)

Compound Relative Sweetness

lactose 16

maltose 32

glucose 74

sucrose 100

fructose 173

aspartame 18,000

acesulfame K 20,000

saccharin 30,000

sucralose 60,000

16.3 Important Hexoses 915

Chapter 16 Carbohydrates

Looking Closer: Artificial Sweeteners

Although sweetness is commonly associated with mono- and disaccharides, it is

not a property found only in sugars. Several other kinds of organic compounds
have been synthesized that are far superior as sweetening agents. These so-
called high-intensity or artificial sweeteners are useful for people with diabetes
or other medical conditions that require them to control their carbohydrate
intake. The synthetic compounds are noncaloric or used in such small
quantities that they do not add significantly to the caloric value of food.

The first artificial sweetener—saccharin—was discovered by accident in 1879. It

is 300 times sweeter than sucrose, but it passes through the body unchanged
and thus adds no calories to the diet. After its discovery, saccharin was used
until it was banned in the early 1900s. However, during the sugar-short years of
World War I, the ban was lifted and was not reinstated at the war’s end. One
drawback to the use of saccharin is its bitter, metallic aftertaste. The initial
solution to this problem was to combine saccharin with cyclamate, a second
artificial sweetener discovered in 1937.

In the 1960s and 1970s, several clinical tests with laboratory animals implicated
both cyclamate and saccharin as carcinogenic (cancer-causing) substances. The
results from the cyclamate tests were completed first, and cyclamate was
banned in the United States in 1969. Then a major study was released in Canada
in 1977 indicating that saccharin increased the incidence of bladder cancer in
rats. The US Food and Drug Administration (FDA) proposed a ban on saccharin
that raised immediate public opposition because saccharin was the only
artificial sweetener still available. In response, Congress passed the Saccharin
Study and Labeling Act in 1977, permitting the use of saccharin as long as any
product containing it was labeled with a consumer warning regarding the
possible elevation of the risk of bladder cancer. Today this warning is no longer
required; moreover, the FDA is currently reviewing the ban on cyclamate, as 75
additional studies and years of usage in other countries, such as Canada, have
failed to show that it has any carcinogenic effect.

A third artificial sweetener, aspartame, was discovered in 1965. This white

crystalline compound is about 180 times sweeter than sucrose and has no
aftertaste. It was approved for use in 1981 and is used to sweeten a wide variety
of foods because it blends well with other food flavors. Aspartame is not used in
baked goods, however, because it is not heat stable.

16.3 Important Hexoses 916

Chapter 16 Carbohydrates

In the body (or when heated), aspartame is initially hydrolyzed to three

molecules: the amino acids aspartic acid and phenylalanine and an alcohol
methanol. Repeated controversy regarding the safety of aspartame arises partly
from the fact that the body metabolizes the released methanol to
formaldehyde. It should be noted, though, that a glass of tomato juice has six
times as much methanol as a similar amount of a diet soda containing
aspartame. The only documented risk connected to aspartame use is for
individuals with the genetic disease phenylketonuria (PKU); these individuals
lack the enzyme needed to metabolize the phenylalanine released when
aspartame is broken down by the body. Because of the danger to people with
PKU, all products containing aspartame must carry a warning label.

Acesulfame K, discovered just two years after aspartame (1967), was approved
for use in the United States in 1988. It is 200 times sweeter than sugar and,
unlike aspartame, is heat stable. It has no lingering aftertaste.

One of the newest artificial sweeteners to gain FDA approval (April 1998) for use
in the United States is sucralose, a white crystalline solid approximately 600
times sweeter than sucrose. Sucralose is synthesized from sucrose and has
three chlorine atoms substituted for three OH groups. It is noncaloric because it
passes through the body unchanged. It can be used in baking because it is heat
stable.

All of the extensive clinical studies completed to date have indicated that these
artificial sweeteners approved for use in the United States are safe for
consumption by healthy individuals in moderate amounts.

16.3 Important Hexoses 917

Chapter 16 Carbohydrates

CONCEPT REVIEW EXERCISES

1. Describe the similarities and differences in the structures of D-glucose and D-

galactose.

2. Describe similarities and differences in the structures of D-glucose and D-

fructose.

ANSWERS

1. Both monosaccharides are aldohexoses. The two monosaccharides differ in the

configuration around the fourth carbon atom.

2. Both monosaccharides are hexoses. D-glucose is an aldohexose, while D-

fructose is a ketohexose.

16.3 Important Hexoses 918

Chapter 16 Carbohydrates

KEY TAKEAWAY

• Three abundant hexoses in living organisms are the aldohexoses D-

glucose and D-galactose and the ketohexose D-fructose.

EXERCISES

1. Identify each sugar by its common chemical name.

a. blood sugar
b. levulose

2. Identify each sugar by its common chemical name.

a. dextrose
b. brain sugar

3. Identify each sugar as an aldohexose or a ketohexose.

a. glucose
b. galactose
c. fructose

4. What hexose would you expect to be most abundant in each food?

a. honey
b. milk
c. cornstarch

ANSWERS

1. a. D-glucose
b. D-fructose

3. a. aldohexose
b. aldohexose
c. ketohexose

16.3 Important Hexoses 919

Chapter 16 Carbohydrates

16.4 Cyclic Structures of Monosaccharides

LEARNING OBJECTIVES

1. Define what is meant by anomers and describe how they are formed.
2. Explain what is meant by mutarotation.

So far we have represented monosaccharides as linear molecules, but many of them

also adopt cyclic structures. This conversion occurs because of the ability of
aldehydes and ketones to react with alcohols:

In some cases, OH and carbonyl groups on the same molecule are able to react with
one another in an intramolecular reaction. Thus, monosaccharides larger than
tetroses exist mainly as cyclic compounds (Figure 16.5 "Cyclization of D-Glucose").
You might wonder why the aldehyde reacts with the OH group on the fifth carbon
atom rather than the OH group on the second carbon atom next to it. Recall from
Chapter 12 "Organic Chemistry: Alkanes and Halogenated Hydrocarbons", Section
12.9 "Cycloalkanes", that cyclic alkanes containing five or six carbon atoms in the
ring are the most stable. The same is true for monosaccharides that form cyclic
structures: rings consisting of five or six carbon atoms are the most stable.

920
Chapter 16 Carbohydrates

Figure 16.5 Cyclization of D-Glucose

D-Glucose can be represented with a Fischer projection (a) or three dimensionally (b). By reacting the OH group on
the fifth carbon atom with the aldehyde group, the cyclic monosaccharide (c) is produced.

When a straight-chain monosaccharide, such as any of the structures shown in

Figure 16.4 "Structures of Three Important Hexoses", forms a cyclic structure, the
carbonyl oxygen atom may be pushed either up or down, giving rise to two
stereoisomers, as shown in Figure 16.6 "Monosaccharides". The structure shown on
the left side of Figure 16.6 "Monosaccharides", with the OH group on the first
carbon atom projected downward, represent what is called the alpha (α) form. The
structures on the right side, with the OH group on the first carbon atom pointed
upward, is the beta (β) form. These two stereoisomers of a cyclic monosaccharide are
known as anomers14; they differ in structure around the anomeric carbon15—that
is, the carbon atom that was the carbonyl carbon atom in the straight-chain form.

14. Stereoisomers that differ in

structure around what was the
carbonyl carbon atom in the
straight-chain form of a
monosaccharide.

15. The carbon atom that was the

carbonyl carbon atom in the
straight-chain form of a
monosaccharide.

16.4 Cyclic Structures of Monosaccharides 921

Chapter 16 Carbohydrates

Figure 16.6 Monosaccharides

In an aqueous solution, monosaccharides exist as an equilibrium mixture of three forms. The interconversion
between the forms is known as mutarotation, which is shown for D-glucose (a) and D-fructose (b).

It is possible to obtain a sample of crystalline glucose in which all the molecules

have the α structure or all have the β structure. The α form melts at 146°C and has a
specific rotation of +112°, while the β form melts at 150°C and has a specific rotation
of +18.7°. When the sample is dissolved in water, however, a mixture is soon
produced containing both anomers as well as the straight-chain form, in dynamic
equilibrium (part (a) of Figure 16.6 "Monosaccharides"). You can start with a pure
crystalline sample of glucose consisting entirely of either anomer, but as soon as
the molecules dissolve in water, they open to form the carbonyl group and then
reclose to form either the α or the β anomer. The opening and closing repeats
continuously in an ongoing interconversion between anomeric forms and is
referred to as mutarotation16 (Latin mutare, meaning “to change”). At equilibrium,
the mixture consists of about 36% α-D-glucose, 64% β-D-glucose, and less than
0.02% of the open-chain aldehyde form. The observed rotation of this solution is
+52.7°.

Even though only a small percentage of the molecules are in the open-chain
aldehyde form at any time, the solution will nevertheless exhibit the characteristic
16. The ongoing interconversion reactions of an aldehyde. As the small amount of free aldehyde is used up in a
between anomeric forms of a reaction, there is a shift in the equilibrium to yield more aldehyde. Thus, all the
monosaccharide to form an
equilibrium mixture.

16.4 Cyclic Structures of Monosaccharides 922

Chapter 16 Carbohydrates

molecules may eventually react, even though very little free aldehyde is present at
a time.

In Figure 16.5 "Cyclization of D-Glucose" and Figure 16.6 "Monosaccharides", and

elsewhere in this book, the cyclic forms of sugars are depicted using a convention
first suggested by Walter N. Haworth, an English chemist. The molecules are drawn
as planar hexagons with a darkened edge representing the side facing toward the
viewer. The structure is simplified to show only the functional groups attached to
the carbon atoms. Any group written to the right in a Fischer projection appears
below the plane of the ring in a Haworth projection, and any group written to the
left in a Fischer projection appears above the plane in a Haworth projection.

The difference between the α and the β forms of sugars may seem trivial, but such
structural differences are often crucial in biochemical reactions. This explains why
we can get energy from the starch in potatoes and other plants but not from
cellulose, even though both starch and cellulose are polysaccharides composed of
glucose molecules linked together. We will examine the effects of these differences
more closely in Section 16.7 "Polysaccharides" and when we discuss enzyme
specificity in Chapter 18 "Amino Acids, Proteins, and Enzymes", Section 18.5
"Enzymes".

CONCEPT REVIEW EXERCISES

1. Define each term.

a. mutarotation
b. anomer
c. anomeric carbon

2. How can you prove that a solution of α-D-glucose exhibits mutarotation?

16.4 Cyclic Structures of Monosaccharides 923

Chapter 16 Carbohydrates

ANSWERS

1. a. the ongoing interconversion between anomers of a particular

carbohydrate to form an equilibrium mixture
b. a stereoisomer that differs in structure around what was the carbonyl
carbon atom in the straight-chain form of a monosaccharide
c. the carbon atom that was the carbonyl carbon atom in the straight-chain
form of a monosaccharide

2. Place a sample of pure α-D-glucose in a polarimeter and measure its observed

rotation. This value will change as mutarotation occurs.

KEY TAKEAWAYS

• Monosaccharides that contain five or more carbons atoms form cyclic

structures in aqueous solution.
• Two cyclic stereoisomers can form from each straight-chain
monosaccharide; these are known as anomers.
• In an aqueous solution, an equilibrium mixture forms between the two
anomers and the straight-chain structure of a monosaccharide in a
process known as mutarotation.

EXERCISES

1. Draw the cyclic structure for β-D-glucose. Identify the anomeric carbon.

2. Draw the cyclic structure for α-D-fructose. Identify the anomeric carbon.

3. Given that the aldohexose D-mannose differs from D-glucose only in the
configuration at the second carbon atom, draw the cyclic structure for α-D-
mannose.

4. Given that the aldohexose D-allose differs from D-glucose only in the
configuration at the third carbon atom, draw the cyclic structure for β-D-
allose.

16.4 Cyclic Structures of Monosaccharides 924

Chapter 16 Carbohydrates

ANSWERS

1.

3.

16.4 Cyclic Structures of Monosaccharides 925

Chapter 16 Carbohydrates

16.5 Properties of Monosaccharides

LEARNING OBJECTIVE

1. Identify the physical and chemical properties of monosaccharides.

Monosaccharides such as glucose and fructose are crystalline solids at room

temperature, but they are quite soluble in water, each molecule having several OH
groups that readily engage in hydrogen bonding. The chemical behavior of these
monosaccharides is likewise determined by their functional groups.

An important reaction of monosaccharides is the oxidation of the aldehyde group,

one of the most easily oxidized organic functional groups. Aldehyde oxidation can
be accomplished with any mild oxidizing agent, such as Tollens’ reagent or
Benedict’s reagent. (For more information about aldehyde oxidation, see Chapter 14
"Organic Compounds of Oxygen", Section 14.5 "Reactions of Alcohols".) With the
latter, complexed copper(II) ions are reduced to copper(I) ions that form a brick-red
precipitate [copper(I) oxide; Figure 16.7 "Benedict’s Test"].

Any carbohydrate capable of reducing either Tollens’ or Benedict’s reagents

17. Any carbohydrate capable of
reducing a mild oxidizing without first undergoing hydrolysis is said to be a reducing sugar17. Because both
agent, such as Tollens’ or the Tollens’ and Benedict’s reagents are basic solutions, ketoses (such as fructose)
Benedict’s reagents, without
first undergoing hydrolysis.

926
Chapter 16 Carbohydrates

also give positive tests due to an equilibrium that exists between ketoses and
aldoses in a reaction known as tautomerism.

Figure 16.7 Benedict’s Test

Benedict’s test was performed on three carbohydrates, depicted from left to right: fructose, glucose, and sucrose. The
solution containing sucrose remains blue because sucrose is a nonreducing sugar.

These reactions have been used as simple and rapid diagnostic tests for the
presence of glucose in blood or urine. For example, Clinitest tablets, which are used
to test for sugar in the urine, contain copper(II) ions and are based on Benedict’s
test. A green color indicates very little sugar, whereas a brick-red color indicates
sugar in excess of 2 g/100 mL of urine.

CONCEPT REVIEW EXERCISES

1. Why are monosaccharides soluble in water?

2. What is a reducing sugar?

16.5 Properties of Monosaccharides 927

Chapter 16 Carbohydrates

ANSWERS

1. Monosaccharides are quite soluble in water because of the numerous OH

groups that readily engage in hydrogen bonding with water.

2. any carbohydrate capable of reducing a mild oxidizing agent, such as Tollens’

or Benedict’s reagents, without first undergoing hydrolysis

KEY TAKEAWAYS

• Monosaccharides are crystalline solids at room temperature and quite

soluble in water.
• Monosaccharides are reducing sugars; they reduce mild oxidizing
agents, such as Tollens’ or Benedict’s reagents.

EXERCISES

1. Which gives a positive Benedict’s test—L-galactose, levulose, or D-glucose?

2. Which gives a positive Benedict’s test—D-glyceraldehyde, corn sugar, or L-

fructose?

3. D-Galactose can be oxidized at the sixth carbon atom to yield D-galacturonic

acid and at both the first and sixth carbon atoms to yield D-galactaric acid.
Draw the Fischer projection for each oxidation product.

4. D-Glucose can be oxidized at the first carbon atom to form D-gluconic acid, at
the sixth carbon atom to yield D-glucuronic acid, and at both the first and sixth
carbon atoms to yield D-glucaric acid. Draw the Fischer projection for each
oxidation product.

16.5 Properties of Monosaccharides 928

Chapter 16 Carbohydrates

ANSWERS

1. All three will give a positive Benedict’s test because they are all
monosaccharides.

3.

16.5 Properties of Monosaccharides 929

Chapter 16 Carbohydrates

16.6 Disaccharides

LEARNING OBJECTIVES

1. Identify the structures of sucrose, lactose, and maltose.

2. Identify the monosaccharides that are needed to form sucrose, lactose,
and maltose.

In Section 16.4 "Cyclic Structures of Monosaccharides", you learned that

monosaccharides can form cyclic structures by the reaction of the carbonyl group
with an OH group. These cyclic molecules can in turn react with another alcohol.
Disaccharides (C12H22O11) are sugars composed of two monosaccharide units that
are joined by a carbon–oxygen-carbon linkage known as a glycosidic linkage18.
This linkage is formed from the reaction of the anomeric carbon of one cyclic
monosaccharide with the OH group of a second monosaccharide.

18. The carbon–oxygen-carbon

linkage between
monosaccharide units in more
complex carbohydrates, such
as disaccharides or
polysaccharides.

930
Chapter 16 Carbohydrates

The disaccharides differ from one another in their monosaccharide constituents

and in the specific type of glycosidic linkage connecting them. There are three
common disaccharides: maltose, lactose, and sucrose. All three are white crystalline
solids at room temperature and are soluble in water. We’ll consider each sugar in
more detail.

Maltose

Maltose occurs to a limited extent in sprouting grain. It is formed most often by the
partial hydrolysis of starch and glycogen. In the manufacture of beer, maltose is
liberated by the action of malt (germinating barley) on starch; for this reason, it is
often referred to as malt sugar. Maltose is about 30% as sweet as sucrose. The human
body is unable to metabolize maltose or any other disaccharide directly from the
diet because the molecules are too large to pass through the cell membranes of the
intestinal wall. Therefore, an ingested disaccharide must first be broken down by
hydrolysis into its two constituent monosaccharide units. In the body, such
hydrolysis reactions are catalyzed by enzymes such as maltase. The same reactions
can be carried out in the laboratory with dilute acid as a catalyst, although in that
case the rate is much slower, and high temperatures are required. Whether it
occurs in the body or a glass beaker, the hydrolysis of maltose produces two
molecules of D-glucose.

H+ or maltase
maltose ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ 2 D-glucose

Maltose is a reducing sugar. Thus, its two glucose molecules must be linked in such
a way as to leave one anomeric carbon that can open to form an aldehyde group.
The glucose units in maltose are joined in a head-to-tail fashion through an α-
linkage from the first carbon atom of one glucose molecule to the fourth carbon
atom of the second glucose molecule (that is, an α-1,4-glycosidic linkage; see Figure
16.8 "An Equilibrium Mixture of Maltose Isomers"). The bond from the anomeric
carbon of the first monosaccharide unit is directed downward, which is why this is
known as an α-glycosidic linkage. The OH group on the anomeric carbon of the
second glucose can be in either the α or the β position, as shown in Figure 16.8 "An
Equilibrium Mixture of Maltose Isomers".

16.6 Disaccharides 931

Chapter 16 Carbohydrates

Figure 16.8 An Equilibrium Mixture of Maltose Isomers

Lactose

Lactose is known as milk sugar because it occurs in the milk of humans, cows, and
other mammals. In fact, the natural synthesis of lactose occurs only in mammary
tissue, whereas most other carbohydrates are plant products. Human milk contains
about 7.5% lactose, and cow’s milk contains about 4.5%. This sugar is one of the
lowest ranking in terms of sweetness, being about one-sixth as sweet as sucrose (see
Table 16.1 "The Relative Sweetness of Some Compounds (Sucrose = 100)" in Section
16.3 "Important Hexoses"). Lactose is produced commercially from whey, a by-
product in the manufacture of cheese. It is important as an infant food and in the
production of penicillin.

Lactose is a reducing sugar composed of one molecule of D-galactose and one

molecule of D-glucose joined by a β-1,4-glycosidic bond (the bond from the
anomeric carbon of the first monosaccharide unit being directed upward). The two
monosaccharides are obtained from lactose by acid hydrolysis or the catalytic
action of the enzyme lactase:

16.6 Disaccharides 932

Chapter 16 Carbohydrates

Many adults and some children suffer from a deficiency of lactase. These
individuals are said to be lactose intolerant19 because they cannot digest the
lactose found in milk. A more serious problem is the genetic disease
galactosemia20, which results from the absence of an enzyme needed to convert
galactose to glucose. Certain bacteria can metabolize lactose, forming lactic acid as
one of the products. This reaction is responsible for the “souring” of milk.

19. The inability to digest the

lactose found in milk or dairy
products due to a deficiency of
the enzyme lactase.

20. A genetic disease caused by the

absence of one of the enzymes
needed to convert galactose to
glucose.

16.6 Disaccharides 933

Chapter 16 Carbohydrates

EXAMPLE 3

For this trisaccharide, indicate whether each glycosidic linkage is α or β.

Solution

The glycosidic linkage between sugars 1 and 2 is β because the bond is

directed up from the anomeric carbon. The glycosidic linkage between
sugars 2 and 3 is α because the bond is directed down from the anomeric
carbon.

SKILL-BUILDING EXERCISE

1. For this trisaccharide, indicate whether each glycosidic linkage is α or β.

16.6 Disaccharides 934

Chapter 16 Carbohydrates

To Your Health: Lactose Intolerance and Galactosemia

Lactose makes up about 40% of an infant’s diet during the first year of life.
Infants and small children have one form of the enzyme lactase in their small
intestines and can digest the sugar easily; however, adults usually have a less
active form of the enzyme, and about 70% of the world’s adult population has
some deficiency in its production. As a result, many adults experience a
reduction in the ability to hydrolyze lactose to galactose and glucose in their
small intestine. For some people the inability to synthesize sufficient enzyme
increases with age. Up to 20% of the US population suffers some degree of
lactose intolerance.

In people with lactose intolerance, some of the unhydrolyzed lactose passes

into the colon, where it tends to draw water from the interstitial fluid into the
intestinal lumen by osmosis. At the same time, intestinal bacteria may act on
the lactose to produce organic acids and gases. The buildup of water and
bacterial decay products leads to abdominal distention, cramps, and diarrhea,
which are symptoms of the condition.

The symptoms disappear if milk or other sources of lactose are excluded from
the diet or consumed only sparingly. Alternatively, many food stores now carry
special brands of milk that have been pretreated with lactase to hydrolyze the
lactose. Cooking or fermenting milk causes at least partial hydrolysis of the
lactose, so some people with lactose intolerance are still able to enjoy cheese,
yogurt, or cooked foods containing milk. The most common treatment for
lactose intolerance, however, is the use of lactase preparations (e.g., Lactaid),
which are available in liquid and tablet form at drugstores and grocery stores.
These are taken orally with dairy foods—or may be added to them directly—to
assist in their digestion.

Galactosemia is a condition in which one of the enzymes needed to convert

galactose to glucose is missing. Consequently, the blood galactose level is
markedly elevated, and galactose is found in the urine. An infant with
galactosemia experiences a lack of appetite, weight loss, diarrhea, and jaundice.
The disease may result in impaired liver function, cataracts, mental
retardation, and even death. If galactosemia is recognized in early infancy, its
effects can be prevented by the exclusion of milk and all other sources of
galactose from the diet. As a child with galactosemia grows older, he or she
usually develops an alternate pathway for metabolizing galactose, so the need

16.6 Disaccharides 935

Chapter 16 Carbohydrates

to restrict milk is not permanent. The incidence of galactosemia in the United

States is 1 in every 65,000 newborn babies.

Sucrose

Sucrose, probably the largest-selling pure organic compound in the world, is known
as beet sugar, cane sugar, table sugar, or simply sugar. Most of the sucrose sold
commercially is obtained from sugar cane and sugar beets (whose juices are
14%–20% sucrose) by evaporation of the water and recrystallization. The dark
brown liquid that remains after the recrystallization of sugar is sold as molasses.

The sucrose molecule is unique among the common disaccharides in having an

α-1,β-2-glycosidic (head-to-head) linkage. Because this glycosidic linkage is formed
by the OH group on the anomeric carbon of α-D-glucose and the OH group on the
anomeric carbon of β-D-fructose, it ties up the anomeric carbons of both glucose
and fructose.

This linkage gives sucrose certain properties that are quite different from those of
maltose and lactose. As long as the sucrose molecule remains intact, neither
monosaccharide “uncyclizes” to form an open-chain structure. Thus, sucrose is
incapable of mutarotation and exists in only one form both in the solid state and in

16.6 Disaccharides 936

Chapter 16 Carbohydrates

solution. In addition, sucrose does not undergo reactions that are typical of
aldehydes and ketones. Therefore, sucrose is a nonreducing sugar.

The hydrolysis of sucrose in dilute acid or through the action of the enzyme sucrase
(also known as invertase) gives an equimolar mixture of glucose and fructose. This
1:1 mixture is referred to as invert sugar because it rotates plane-polarized light in
the opposite direction than sucrose. The hydrolysis reaction has several practical
applications. Sucrose readily recrystallizes from a solution, but invert sugar has a
much greater tendency to remain in solution. In the manufacture of jelly and candy
and in the canning of fruit, the recrystallization of sugar is undesirable. Therefore,
conditions leading to the hydrolysis of sucrose are employed in these processes.
Moreover, because fructose is sweeter than sucrose, the hydrolysis adds to the
sweetening effect. Bees carry out this reaction when they make honey.

The average American consumes more than 100 lb of sucrose every year. About
two-thirds of this amount is ingested in soft drinks, presweetened cereals, and
other highly processed foods. The widespread use of sucrose is a contributing factor
to obesity and tooth decay. Carbohydrates such as sucrose, are converted to fat
when the caloric intake exceeds the body’s requirements, and sucrose causes tooth
decay by promoting the formation of plaque that sticks to teeth.

CONCEPT REVIEW EXERCISE

1. What monosaccharides are obtained by the hydrolysis of each disaccharide?

a. sucrose
b. maltose
c. lactose

ANSWER

1. a. D-glucose and D-fructose

b. two molecules of D-glucose
c. D-glucose and D-galactose

16.6 Disaccharides 937

Chapter 16 Carbohydrates

KEY TAKEAWAYS

• Maltose is composed of two molecules of glucose joined by an

α-1,4-glycosidic linkage. It is a reducing sugar that is found in sprouting
grain.
• Lactose is composed of a molecule of galactose joined to a molecule of
glucose by a β-1,4-glycosidic linkage. It is a reducing sugar that is found
in milk.
• Sucrose is composed of a molecule of glucose joined to a molecule of
fructose by an α-1,β-2-glycosidic linkage. It is a nonreducing sugar that
is found in sugar cane and sugar beets.

16.6 Disaccharides 938

Chapter 16 Carbohydrates

EXERCISES

1. Identify each sugar by its common chemical name.

a. milk sugar
b. table sugar

2. Identify each sugar by its common chemical name.

a. cane sugar
b. malt sugar

3. For each disaccharide, indicate whether the glycosidic linkage is α or β.

a.

b.

4. For each disaccharide, indicate whether the glycosidic linkage is α or β.

a.

b.

16.6 Disaccharides 939

Chapter 16 Carbohydrates

5. Identify each disaccharide in Exercise 3 as a reducing or nonreducing sugar. If

it is a reducing sugar, draw its structure and circle the anomeric carbon. State
if the OH group at the anomeric carbon is in the α or the β position.

6. Identify each disaccharide in Exercise 4 as a reducing or nonreducing sugar. If

it is a reducing sugar, draw its structure and circle the anomeric carbon. State
if the OH group at the anomeric carbon is in the α or β position.

7. Melibiose is a disaccharide that occurs in some plant juices. Its structure is as

follows:

a. What monosaccharide units are incorporated into melibiose?

b. What type of linkage (α or β) joins the two monosaccharide units of
melibiose?
c. Melibiose has a free anomeric carbon and is thus a reducing sugar. Circle
the anomeric carbon and indicate whether the OH group is α or β.

8. Cellobiose is a disaccharide composed of two glucose units joined by a

β-1,4-glycosidic linkage.

a. Draw the structure of cellobiose.

b. Is cellobiose a reducing or nonreducing sugar? Justify your answer.

16.6 Disaccharides 940

Chapter 16 Carbohydrates

ANSWERS

1. a. lactose
b. sucrose

a.

3. b.
5. 3a: nonreducing; 3b: reducing

7. a. galactose and glucose

b. α-glycosidic linkage

c.

16.6 Disaccharides 941

Chapter 16 Carbohydrates

16.7 Polysaccharides

LEARNING OBJECTIVE

1. Compare and contrast the structures and uses of starch, glycogen, and
cellulose.

The polysaccharides are the most abundant carbohydrates in nature and serve a
variety of functions, such as energy storage or as components of plant cell walls.
Polysaccharides are very large polymers composed of tens to thousands of
monosaccharides joined together by glycosidic linkages. The three most abundant
polysaccharides are starch, glycogen, and cellulose. These three are referred to as
homopolymers because each yields only one type of monosaccharide (glucose) after
complete hydrolysis. Heteropolymers may contain sugar acids, amino sugars, or
noncarbohydrate substances in addition to monosaccharides. Heteropolymers are
common in nature (gums, pectins, and other substances) but will not be discussed
further in this textbook. The polysaccharides are nonreducing carbohydrates, are
not sweet tasting, and do not undergo mutarotation.

Starch

Starch is the most important source of carbohydrates in the human diet and
accounts for more than 50% of our carbohydrate intake. It occurs in plants in the
form of granules, and these are particularly abundant in seeds (especially the cereal
grains) and tubers, where they serve as a storage form of carbohydrates. The
breakdown of starch to glucose nourishes the plant during periods of reduced
photosynthetic activity. We often think of potatoes as a “starchy” food, yet other
plants contain a much greater percentage of starch (potatoes 15%, wheat 55%, corn
65%, and rice 75%). Commercial starch is a white powder.

Starch is a mixture of two polymers: amylose21 and amylopectin22. Natural

starches consist of about 10%–30% amylase and 70%–90% amylopectin. Amylose is a
linear polysaccharide composed entirely of D-glucose units joined by the
α-1,4-glycosidic linkages we saw in maltose (part (a) of Figure 16.9 "Amylose").
Experimental evidence indicates that amylose is not a straight chain of glucose
units but instead is coiled like a spring, with six glucose monomers per turn (part
21. A linear polymer of glucose
units found in starch. (b) of Figure 16.9 "Amylose"). When coiled in this fashion, amylose has just enough
room in its core to accommodate an iodine molecule. The characteristic blue-violet
22. A branched polymer of glucose color that appears when starch is treated with iodine is due to the formation of the
units found in starch.

942
Chapter 16 Carbohydrates

amylose-iodine complex. This color test is sensitive enough to detect even minute
amounts of starch in solution.

Figure 16.9 Amylose

(a) Amylose is a linear chain of α-D-glucose units joined together by α-1,4-glycosidic bonds. (b) Because of hydrogen
bonding, amylose acquires a spiral structure that contains six glucose units per turn.

Amylopectin is a branched-chain polysaccharide composed of glucose units linked

primarily by α-1,4-glycosidic bonds but with occasional α-1,6-glycosidic bonds,
which are responsible for the branching. A molecule of amylopectin may contain
many thousands of glucose units with branch points occurring about every 25–30
units (Figure 16.10 "Representation of the Branching in Amylopectin and
Glycogen"). The helical structure of amylopectin is disrupted by the branching of
the chain, so instead of the deep blue-violet color amylose gives with iodine,
amylopectin produces a less intense reddish brown.

16.7 Polysaccharides 943

Chapter 16 Carbohydrates

Figure 16.10 Representation of the Branching in Amylopectin and Glycogen

Both amylopectin and glycogen contain branch points that are linked through α-1,6-linkages. These branch points
occur more often in glycogen.

Dextrins are glucose polysaccharides of intermediate size. The shine and stiffness
imparted to clothing by starch are due to the presence of dextrins formed when
clothing is ironed. Because of their characteristic stickiness with wetting, dextrins
are used as adhesives on stamps, envelopes, and labels; as binders to hold pills and
tablets together; and as pastes. Dextrins are more easily digested than starch and
are therefore used extensively in the commercial preparation of infant foods.

The complete hydrolysis of starch yields, in successive stages, glucose:

starch → dextrins → maltose → glucose

In the human body, several enzymes known collectively as amylases degrade starch
sequentially into usable glucose units.

Glycogen

Glycogen is the energy reserve carbohydrate of animals. Practically all mammalian

cells contain some stored carbohydrates in the form of glycogen, but it is especially
abundant in the liver (4%–8% by weight of tissue) and in skeletal muscle cells
(0.5%–1.0%). Like starch in plants, glycogen is found as granules in liver and muscle

16.7 Polysaccharides 944

Chapter 16 Carbohydrates

cells. When fasting, animals draw on these glycogen reserves during the first day
without food to obtain the glucose needed to maintain metabolic balance.

Note

About 70% of the total glycogen in the body is stored in muscle cells. Although
the percentage of glycogen (by weight) is higher in the liver, the much greater
mass of skeletal muscle stores a greater total amount of glycogen.

Glycogen is structurally quite similar to amylopectin, although glycogen is more

highly branched (8–12 glucose units between branches) and the branches are
shorter. When treated with iodine, glycogen gives a reddish brown color. Glycogen
can be broken down into its D-glucose subunits by acid hydrolysis or by the same
enzymes that catalyze the breakdown of starch. In animals, the enzyme
phosphorylase catalyzes the breakdown of glycogen to phosphate esters of glucose.

Cellulose

Cellulose, a fibrous carbohydrate found in all plants, is the structural component of

plant cell walls. Because the earth is covered with vegetation, cellulose is the most
abundant of all carbohydrates, accounting for over 50% of all the carbon found in
the vegetable kingdom. Cotton fibrils and filter paper are almost entirely cellulose
(about 95%), wood is about 50% cellulose, and the dry weight of leaves is about
10%–20% cellulose. The largest use of cellulose is in the manufacture of paper and
paper products. Although the use of noncellulose synthetic fibers is increasing,
rayon (made from cellulose) and cotton still account for over 70% of textile
production.

Like amylose, cellulose is a linear polymer of glucose. It differs, however, in that the
glucose units are joined by β-1,4-glycosidic linkages, producing a more extended
structure than amylose (part (a) of Figure 16.11 "Cellulose"). This extreme linearity
allows a great deal of hydrogen bonding between OH groups on adjacent chains,
causing them to pack closely into fibers (part (b) of Figure 16.11 "Cellulose"). As a
result, cellulose exhibits little interaction with water or any other solvent. Cotton
and wood, for example, are completely insoluble in water and have considerable
mechanical strength. Because cellulose does not have a helical structure, it does not
bind to iodine to form a colored product.

16.7 Polysaccharides 945

Chapter 16 Carbohydrates

Figure 16.11 Cellulose

(a) There is extensive hydrogen bonding in the structure of cellulose. (b) In this electron micrograph of the cell wall
of an alga, the wall consists of successive layers of cellulose fibers in parallel arrangement.

Cellulose yields D-glucose after complete acid hydrolysis, yet humans are unable to
metabolize cellulose as a source of glucose. Our digestive juices lack enzymes that
can hydrolyze the β-glycosidic linkages found in cellulose, so although we can eat
potatoes, we cannot eat grass. However, certain microorganisms can digest
cellulose because they make the enzyme cellulase, which catalyzes the hydrolysis of
cellulose. The presence of these microorganisms in the digestive tracts of
herbivorous animals (such as cows, horses, and sheep) allows these animals to
degrade the cellulose from plant material into glucose for energy. Termites also
contain cellulase-secreting microorganisms and thus can subsist on a wood diet.
This example once again demonstrates the extreme stereospecificity of biochemical
processes.

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Chapter 16 Carbohydrates

Career Focus: Certified Diabetes Educator

Certified diabetes educators come from a variety of health professions, such as

nursing and dietetics, and specialize in the education and treatment of patients
with diabetes. A diabetes educator will work with patients to manage their
diabetes. This involves teaching the patient to monitor blood sugar levels, make
good food choices, develop and maintain an exercise program, and take
medication, if required. Diabetes educators also work with hospital or nursing
home staff to improve the care of diabetic patients. Educators must be willing
to spend time attending meetings and reading the current literature to
maintain their knowledge of diabetes medications, nutrition, and blood
monitoring devices so that they can pass this information to their patients.

© Thinkstock

CONCEPT REVIEW EXERCISES

1. What purposes do starch and cellulose serve in plants?

2. What purpose does glycogen serve in animals?

ANSWERS

1. Starch is the storage form of glucose (energy) in plants, while cellulose is a

structural component of the plant cell wall.

2. Glycogen is the storage form of glucose (energy) in animals.

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KEY TAKEAWAYS

• Starch is a storage form of energy in plants. It contains two polymers

composed of glucose units: amylose (linear) and amylopectin
(branched).
• Glycogen is a storage form of energy in animals. It is a branched
polymer composed of glucose units. It is more highly branched than
amylopectin.
• Cellulose is a structural polymer of glucose units found in plants. It is a
linear polymer with the glucose units linked through β-1,4-glycosidic
bonds.

EXERCISES

1. What monosaccharide is obtained from the hydrolysis of each carbohydrate?

a. starch
b. cellulose
c. glycogen

2. For each carbohydrate listed in Exercise 1, indicate whether it is found in

plants or mammals.

3. Describe the similarities and differences between amylose and cellulose.

4. Describe the similarities and differences between amylopectin and glycogen.

ANSWERS

1. a. glucose
b. glucose
c. glucose

3. Amylose and cellulose are both linear polymers of glucose units, but the
glycosidic linkages between the glucose units differ. The linkages in amylose
are α-1,4-glycosidic linkages, while the linkages in cellulose they are
β-1,4-glycosidic linkages.

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Chapter Summary

To ensure that you understand the material in this chapter, you should review the meanings of the bold terms in the
following summary and ask yourself how they relate to the topics in the chapter.

Carbohydrates, a large group of biological compounds containing carbon, hydrogen, and oxygen atoms, include
sugars, starch, glycogen, and cellulose. All carbohydrates contain alcohol functional groups, and either an
aldehyde or a ketone group (or a functional group that can be converted to an aldehyde or ketone). The simplest
carbohydrates are monosaccharides. Those with two monosaccharide units are disaccharides, and those with
many monosaccharide units are polysaccharides. Most sugars are either monosaccharides or disaccharides.
Cellulose, glycogen, and starch are polysaccharides.

Many carbohydrates exist as stereoisomers, in which the three-dimensional spatial arrangement of the atoms
in space is the only difference between the isomers. These particular stereoisomers contain at least one chiral
carbon, a carbon atom that has four different groups bonded to it. A molecule containing a chiral carbon is
nonsuperimposable on its mirror image, and two molecules that are nonsuperimposable mirror images of each
other are a special type of stereoisomer called enantiomers. Enantiomers have the same physical properties,
such as melting point, but differ in the direction they rotate polarized light.

A sugar is designated as being a D sugar or an L sugar according to how, in a Fischer projection of the molecule,
the hydrogen atom and OH group are attached to the penultimate carbon atom, which is the carbon atom
immediately before the terminal alcohol carbon atom. If the structure at this carbon atom is the same as that of
D-glyceraldehyde (OH to the right), the sugar is a D sugar; if the configuration is the same as that of L-
glyceraldehyde (OH to the left), the sugar is an L sugar.

Monosaccharides of five or more carbons atoms readily form cyclic structures when the carbonyl carbon atom
reacts with an OH group on a carbon atom three or four carbon atoms distant. Consequently, glucose in solution
exists as an equilibrium mixture of three forms, two of them cyclic (α- and β-) and one open chain. In Haworth
projections, the alpha form is drawn with the OH group on the “former” carbonyl carbon atom (anomeric
carbon) pointing downward; the beta form, with the OH group pointing upward; these two compounds are
stereoisomers and are given the more specific term of anomers. Any solid sugar can be all alpha or all beta.
Once the sample is dissolved in water, however, the ring opens up into the open-chain structure and then closes
to form either the α- or the β-anomer. These interconversions occur back and forth until a dynamic equilibrium
mixture is achieved in a process called mutarotation.

The carbonyl group present in monosaccharides is easily oxidized by Tollens’ or Benedict’s reagents (as well as
others). Any mono- or disaccharide containing a free anomeric carbon is a reducing sugar. The disaccharide
maltose contains two glucose units joined in an α-1,4-glycosidic linkage. The disaccharide lactose contains a

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galactose unit and a glucose unit joined by a β-1,4-glycosidic linkage. Both maltose and lactose contain a free
anomeric carbon that can convert to an aldehyde functional group, so they are reducing sugars; they also
undergo mutarotation. Many adults, and some children, have a deficiency of the enzyme lactase (which is
needed to break down lactose) and are said to be lactose intolerant. A more serious problem is the genetic
disease galactosemia, which results from the absence of an enzyme needed to convert galactose to glucose.

The disaccharide sucrose (table sugar) consists of a glucose unit and a fructose unit joined by a glycosidic linkage.
The linkage is designated as an α-1,β-2-glycosidic linkage because it involves the OH group on the first carbon
atom of glucose and the OH group on the second carbon atom of fructose. Sucrose is not a reducing sugar
because it has no anomeric carbon that can reform a carbonyl group, and it cannot undergo mutarotation
because of the restrictions imposed by this linkage.

Starch, the principal carbohydrate of plants, is composed of the polysaccharides amylose (10%–30%) and
amylopectin (70%–90%). When ingested by humans and other animals, starch is hydrolyzed to glucose and
becomes the body’s energy source. Glycogen is the polysaccharide animals use to store excess carbohydrates
from their diets. Similar in structure to amylopectin, glycogen is hydrolyzed to glucose whenever an animal
needs energy for a metabolic process. The polysaccharide cellulose provides structure for plant cells. It is a linear
polymer of glucose units joined by β-1,4-glycosidic linkages. It is indigestible in the human body but digestible
by many microorganisms, including microorganisms found in the digestive tracts of many herbivores.

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ADDITIONAL EXERCISES

1. Draw the Fischer projections for D-glucose and D-ribose. Identify all the
functional groups in each structure.

2. Draw the Fischer projections for D-galactose and D-fructose. Identify all the
functional groups in each structure.

3. L-Fucose is an aldohexose that is often incorporated into oligosaccharides

attached to cell membranes. It is also known as 6-deoxy-L-galactose. Draw the
structure of L-fucose.

4. D-glucitol, also known as sorbitol, is added to shredded coconut to keep it soft

and to pharmaceutical products to increase the absorption of nutrients. It is
prepared industrially by the reduction of D-glucose. Propose a structure for D-
glucitol.

5. Which would give a positive Benedict’s test—lactose, amylopectin, D-ribose,

sucrose, D-glyceraldehyde, or amylose?

6. Which enzyme hydrolyzes each carbohydrate?

a. maltose
b. lactose
c. cellulose
d. sucrose

7. What structural characteristics are necessary if a disaccharide is to be a

reducing sugar? Draw the structure of a hypothetical reducing disaccharide
composed of two aldohexoses.

8. Raffinose, a trisaccharide found in beans and sugar beets, contains D-galactose,

D-glucose, and D-fructose. The enzyme α-galactase catalyzes the hydrolysis of
raffinose to galactose and sucrose. Draw the structure of raffinose. (The
linkage from galactose to the glucose unit is α-1,6).

9. What reagent(s) could be used to carry out each conversion?

a.

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b.

10. What reagents are necessary to carry out each conversion?

a.

b.

11. The structure of lactulose is shown here. What monosaccharide units compose
this disaccharide?

12. N-acetylglucosamine is synthesized from D-glucosamine, which in turn is

obtained from D-glucose. What reagents are needed for the conversion of D-
glucosamine to N-acetylglucosamine?

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13. Hyaluronic acid is a heteropolymer that acts as a lubricating agent in the fluids
of joints and the eyes. Its structure consists of repeating disaccharide units
containing glucuronic acid and N-acetylglucosamine connected by a
β-1,3-linkage. Draw the structure of the disaccharide unit found in hyaluronic
acid.

14. Several artificial sweeteners are discussed in this chapter.

a. Which are currently approved for use in the United States?

b. Which has (or have) a bitter, metallic aftertaste?
c. Which was (or were) most recently approved for use in the United States?
d. Which contain(s) potassium?

15. If 3.0 mmol (3.0 × 10−3 mol) samples of saccharin, cyclamate, aspartame, and
acesulfame K were each dissolved in separate beakers containing 500 mL of
pure water, which solution would have the sweetest taste? Which solution
would have the least sweet taste? Justify your answers.

16. Identify two functional groups found in aspartame, acesulfame K, and

sucralose.

17. Why does a deficiency of lactase lead to cramps and diarrhea?

18. How does galactosemia differ from lactose intolerance in terms of the cause of
the disease and its symptoms and severity?

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ANSWERS

1.

3.
5. Lactose, D-ribose, and D-glyceraldehyde would give a positive Benedict’s test.

7. To be a reducing sugar, a disaccharide must contain an anomeric carbon atom

that can open up to form an aldehyde functional group, as shown in this
disaccharide (answers will vary).

9. a. The carbohydrate is being oxidized; Tollens’ or Benedict’s reagent could be

used.
b. To form the compound shown, an aldehyde must react with methanol
(CH3OH) and an acid catalyst.

11. galactose and fructose

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13.
15. Sucralose would be expected to have the sweetest taste because its relative
sweetness is the highest. Lactose would have the least sweet taste because it
has the lowest relative sweetness.

17. Intestinal bacteria can act on the lactose present in the intestine to produce
organic acids and gases. The buildup of water and bacterial decay products
leads to cramps and diarrhea.

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