thinner sugar-phosphate backbone.

(For a comparison of the

structures of B-DNA and Z-DNA, see Figure 16-8.)
O
RNA structure also depends in part on base pairing, but
Atoms Atoms in bases this pairing is usually between complementary regions within
in backbone the same strand and is much less extensive than the inter-
P
strand pairing of the DNA duplex. Of the various RNA species,
secondary and tertiary structures occur mainly in rRNA and
C tRNA (see Chapter 19). In addition, some infectious viruses
consist of double-stranded RNA held together by hydrogen
bonding between complementary base pairs.
Hydrogen Sugar-phosphate
bonds backbone 5¿
3¿ CONCEPT CHECK 3.2
5¿ 3¿
A T
Like proteins, nucleotides are important informational
macromolecules. How are they similar to proteins and how
G C
do they differ in terms of monomer types and assembly,
C G polymer structure, and cellular functions?
A T
Base pairs

T A
3.3 Polysaccharides
The next group of macromolecules we will consider are the
C G
polysaccharides, which are long-chain polymers of sug-
A T
ars and sugar derivatives. Polysaccharides usually consist of
G C a single kind of repeating unit, or sometimes an alternating
pattern of two kinds. They serve primarily in energy storage
and as cellular structures rather than carrying information.
A T However (as we will see in Chapter 7), shorter polymers called
oligosaccharides, when attached to proteins on the cell surface,
T A
play important roles in cellular recognition of extracellular
C G signal molecules and of other cells. As noted earlier, polysac-
A T charides include the storage polysaccharides starch and glyco-
gen and the structural polysaccharide cellulose. Each of these
polymers contains the six-carbon sugar glucose as its single
A T
repeating unit, but they differ in the nature of the bond be-
G C tween successive glucose units as well as in the presence and
5¿ extent of side branches on the chains.
3¿
5¿ 3¿
(a) DNA double helix (b) Space-filling model The Monomers Are Monosaccharides
The repeating units of polysaccharides are simple sugars
Figure 3-19 The Structure of Double-Stranded DNA. (a) A
Chemistry
called monosaccharides (from the Greek mono, meaning
schematic representation of the double-helical structure of DNA. The
Review–
continuously turning strips represent the sugar-phosphate backbones “single,” and sakkharon, meaning “sugar”). A sugar can be de-
Nucleic
Acids: The of the molecule, and the horizontal bars represent paired bases of the fined as an aldehyde or ketone that has two or more hydroxyl
Double Helix groups. Thus, there are two categories of sugars: the aldo-
Activity: DNA two strands. (b) A space-filling model of the DNA double helix, with
Double Helix color-coded atoms as shown at the top of the figure. sugars, with a terminal carbonyl group (Figure 3-20a), and
the ketosugars, with an internal carbonyl group at carbon 2

helix is just sufficient to accommodate one of each kind of O

base. If we envision the sugar-phosphate backbones of the 1 1
H C CH2 OH
two strands as the sides of a circular staircase, then each step
2
or rung of the stairway corresponds to a pair of bases held in H
2
C OH C O
place by hydrogen bonding (Figure 3-19).
The right-handed Watson–Crick helix shown in Figure (H C OH) n-3 (H C OH) n-3
3-19 is actually an idealized version of what is called B-DNA. nCH nCH
OH
OH 2
B-DNA is the main form of DNA in cells, but two other forms 2

may also exist, perhaps in short segments interspersed within (a) Aldosugar (b) Ketosugar
molecules consisting mainly of B-DNA. A-DNA has a right- Figure 3-20 Structures of Monosaccharides. (a) Aldosugars
handed, helical configuration that is shorter and thicker than have a carbonyl group on carbon atom 1. (b) Ketosugars have a
B-DNA. Z-DNA, on the other hand, is a left-handed double he- carbonyl group on carbon atom 2. The number of carbon atoms in a
lix that derives its name from the zigzag pattern of its longer, monosaccharide (n) varies from three to seven.
86

M03_HARD7694_09_GE_C03.indd 86 22/02/17 2:37 pm

 (Figure 3-20b). Within these categories, sugars are named ge-
nerically according to the number of carbon atoms they con-
tain. Most sugars have between three and seven carbon atoms
and thus are classified as trioses (three carbons), tetroses (four
carbons), pentoses (five carbons), hexoses (six carbons), or hep-
toses (seven carbons). We have already encountered two pen-
toses—the ribose of RNA and the deoxyribose of DNA.
The single most common monosaccharide in the biolog-
ical world is the aldohexose D-glucose, represented by the for-
mula C6H12O6 and by the structure shown in Figure 3-21.
The formula CnH2nOn is characteristic of sugars and gave
rise to the general term carbohydrate because compounds
of this sort were originally thought of as “hydrates of car-
bon”—Cn(H2O)n. Although carbohydrates are not simply
hydrated carbons, we will see in Chapter 11 that, for every
CO2 molecule incorporated into sugar during photosynthe-
sis, one water molecule is also added (see Reaction 11-2 on
page 308).
In keeping with the general rule for numbering carbon
atoms in organic molecules, the carbons of glucose are num-
bered beginning with the more oxidized end of the molecule, the
carbonyl group. Because glucose has four asymmetric carbon
atoms (carbon atoms 2, 3, 4, and 5), there are 24 = 16 differ-
ent possible stereoisomers of the aldosugar C6H12O6. Here, we
will concern ourselves only with D-glucose, which is the most
stable of the 16 isomers.
Figure 3-21a illustrates D-glucose as it appears in what
chemists call a Fischer projection, with the —H and —OH
groups intended to project slightly out of the plane of the pa-
per. This structure depicts glucose as a linear molecule, and it
is often a useful representation of glucose for teaching purpos-
es. Note that the carbon atoms are numbered from the more
oxidized end of the molecule.
In reality, however, glucose exists in the cell in a dynamic
equilibrium between the linear (or straight-chain) configura-
tion of Figure 3-21a and the ring form shown in Figure 3-21b.
This ring forms when the oxygen atom of the hydroxyl group
on carbon atom 5 forms a bond with carbon atom 1. This six-
membered ring, formed by five carbon atoms and one oxygen
atom, is called a pyranose ring. This pyranose ring form is the
predominant structure because it is more stable energetically
than the linear form.
H O
1C 6
CH2OH
2 5
H C OH O
H H
3
HO C H H ring known as a furanose ring, a type also found in ribose and
4 1
4 OH H deoxyribose.
H C OH HO OH
5
H C OH 3 2
H OH
6
H C OH
H
(a) Fischer projection (b) Haworth projection
Figure 3-21 The Structure of D-Glucose. The D-glucose
molecule can be represented by (a) the Fischer projection of the
straight-chain form or (b) the Haworth projection of the ring form.
M03_HARD7694_09_GE_C03.indd 87
6
CH2OH
6
CH2OH
O O
5 5
OH
4 1 4 1
OH OH
HO 3 2 OH HO 3 2
OH OH
a-D-glucose, the b-D-glucose, the
repeating unit of repeating unit of
starch and glycogen cellulose
Figure 3-22 The Ring Forms of D-Glucose. The hydroxyl
group on carbon atom 1 (blue oval) points downward in the a form
and upward in the b form.
Therefore, the more satisfactory representation of glu-
cose is the Haworth projection shown in Figure 3-21b.
This view shows the spatial relationship of different parts of
the molecule and makes the spontaneous formation of a bond
between an oxygen atom and carbon atoms 1 and 5 appear
more likely. In the Haworth projection, carbon atoms 2 and 3
Chapter 3
are intended to stick out of the plane of the paper, and carbon
atoms 5 and 6 are behind the plane of the paper. The —H and
—OH groups then project upward or downward, as indicated.
Either of the representations of glucose shown in Figure 3-21
| The Macromolecules of the Cell
is valid, but the Haworth projection is generally preferred be-
cause it indicates both the ring form and the spatial relation-
ship of the carbon atoms.
Notice that formation of the pyranose ring structure re-
sults in the generation of one of two alternative forms of the
molecule, depending on the spatial orientation of the hydroxyl
group on carbon atom 1. These alternative forms of glucose
are designated a and b. As shown in Figure 3-22, a-D-glucose
has the hydroxyl group on carbon atom 1 pointing downward
in the Haworth projection, and b-D-glucose has the hydroxyl
group on carbon atom 1 pointing upward. Starch and glyco-
gen both have a-D-glucose as their repeating unit, whereas
cellulose consists of strings of b-D-glucose.
In addition to the free monosaccharide and the long-
chain polysaccharides, glucose also occurs in disaccharides,
which consist of two monosaccharide units linked covalent-
ly. Three common disaccharides are shown in Figure 3-23.
Maltose (malt sugar) consists of two glucose units linked to-
gether, whereas lactose (milk sugar) contains a glucose linked
to a galactose and sucrose (table sugar) has a glucose linked
to a fructose. Note that fructose contains a five-membered
Each of these disaccharides is formed by a condensation
reaction in which two monosaccharides are linked together
via an oxygen atom following the elimination of water. The
resulting glycosidic bond is characteristic of linkages be-
tween sugars. Note that the “corners” on the glycosidic bonds
do not imply the presence of additional atoms—there is only
a single oxygen atom connecting the two monomers. In malt-
ose, both of the constituent glucose molecules are in the a
form, and the glycosidic bond forms between carbon atom 1
of one glucose and carbon atom 4 of the other (Figure 3-23a).
87
22/02/17 2:37 pm
 a glycosidic bond found in animal cells and bacteria (Figure 3-24b). Both of
CH2OH CH2OH these polymers consist of a-D-glucose units linked together
O O by a glycosidic bonds. In addition to a(1 S 4) bonds that link
carbon atoms 1 and 4 of adjacent glucose units, these poly-
OH
O
OH saccharides may contain occasional a(1 S 6) linkages along
HO OH
the backbone, giving rise to side chains (Figure 3-24c). Stor-
OH OH age polysaccharides can therefore be branched or unbranched
a-D-glucose a-D-glucose polymers, depending on the presence or absence of a(1 S 6)
linkages.
(a) Maltose
Glycogen is highly branched, with a(1 S 6) linkages oc-
curring every 8 to 10 glucose units along the backbone and
b glycosidic bond
giving rise to short side chains of about 8 to 12 glucose units
CH2OH CH2OH
(Figure 3-24b). In our bodies, glycogen is stored mainly in the
HO O O OH liver and in muscle tissue. In the liver, it is used as a source of
OH
O
OH
glucose to maintain blood sugar levels. In muscle, it serves as
a fuel source to generate ATP for muscle contraction. Bacteria
also commonly store glycogen as a glucose reserve.
OH OH
Starch, the glucose reserve commonly found in plant tis-
b-D-galactose b-D-glucose sue, occurs both as unbranched amylose and as branched
(b) Lactose amylopectin. Like glycogen, amylopectin has a(1 S 6)
branches, but these occur less frequently along the backbone
a glycosidic bond (once every 12 to 25 glucose units) and give rise to longer
CH2OH side chains (lengths of 20 to 25 glucose units are common;
O Figure 3-24a). Starch deposits are usually 10–30% amylose
HOCH2 O
and 70–90% amylopectin. Starch is stored in plant cells as
OH OH starch grains within the plastids—either within the chloro-
O
HO CH2OH
plasts that are the sites of carbon fixation and sugar synthesis
OH OH in photosynthetic tissue or within the amyloplasts, which are
a-D-glucose b-D-fructose specialized plastids for starch storage. The potato tuber, for ex-
ample, is filled with starch-laden amyloplasts.
(c) Sucrose
A common example of a structural polysaccharide is
Figure 3-23 Some Common Disaccharides. (a) Maltose the cellulose found in plant cell walls (Figure 3-25). Cellu-
consists of two molecules of a-D-glucose; (b) lactose consists of lose is an important polymer quantitatively—more than half
a molecule of b-D-galactose linked to b-D-glucose; and (c) sucrose of the carbon in many plants is typically present in cellulose.
consists of a molecule of a-D-glucose linked to b-D-fructose. Note Like starch and glycogen, cellulose is a polymer of glucose;
that monomers in maltose and lactose are joined by a glycosidic however, the repeating monomer is b-D-glucose, and the link-
bonds, but by a b glycosidic bond in sucrose age is therefore b(1 S 4). This bond has structural conse-
quences that we will get to shortly, but it also has nutritional
implications. Mammals do not possess an enzyme that can hy-
This is called an a glycosidic bond because it involves a carbon
drolyze this b(1 S 4) bond and therefore cannot use cellulose
atom 1 with its hydroxyl group in the a configuration. Lac-
as food. As a result, you can digest potatoes (starch) but not
tose, on the other hand, is characterized by a b glycosidic bond
grass and wood (cellulose).
because the hydroxyl group on carbon atom 1 of the galac-
Animals such as cows and sheep might seem to be excep-
tose is in the b configuration (Figure 3-23b). Some people lack
tions because they do eat grass and similar plant products.
the enzyme needed to hydrolyze this b glycosidic bond and are
But they cannot cleave b glycosidic bonds either; they rely
considered lactose intolerant due to their difficulty in metabo-
on microorganisms (bacteria and protozoa) in their digestive
lizing this disaccharide. Sucrose consists of a molecule of a-D-
systems to do this for them. The microorganisms digest the
glucose linked to a molecule of b-D-fructose by an a glycosidic
cellulose, and the host animal then obtains the end-products
bond (Figure 3-23c). The distinction between a and b again
of microbial digestion, which are in a form the animal can
becomes critical when we get to the polysaccharides because
use (glucose). Even termites do not actually digest wood, but
both the three-dimensional configuration and the biological
simply chew it into small pieces that are then hydrolyzed
role of the polymer depend critically on the nature of the bond
to glucose monomers by microorganisms in the termite’s
between the repeating monosaccharide units.
digestive tract.
Although b(1 S 4)-linked cellulose is the most abun-
The Polymers Are Storage and Structural dant structural polysaccharide, others are also known. The
Polysaccharides celluloses of fungal cell walls, for example, contain either b
Polysaccharides typically perform either storage or structural (1 S 4) or b(1 S 3) linkages, depending on the species. The
roles in cells. The most familiar storage polysaccharides are cell wall of most bacteria is somewhat more complex and
starch, found in plant cells (Figure 3-24a), and glycogen, contains two kinds of sugars, N-acetylglucosamine (GlcNAc)
88

M03_HARD7694_09_GE_C03.indd 88 22/02/17 2:37 pm

 Chloroplast Starch

Amylopectin
molecule

(a) Starch

Plant leaf cell with starch grains in chloroplast

1 mm

Glycogen granules Mitochondrion

Chapter 3
| The Macromolecules of the Cell
Glycogen
molecule

(b) Glycogen
Liver cell with glycogen granules in the cytosol
0.5 mm

OH
CH Sid
e ch
2 ain
O
OH OH
CH
2
O
OH O
OH
1
a(1 6)
OH OH O bond OH

CH2 6 CH CH2
2
O O O
Figure 3-24 The Structure of Starch and Glycogen.
1 4
(a) Starch from plant cells and (b) glycogen from animal cells and OH
O
OH
O
OH
O
bacteria are both storage polysaccharides composed of linear
chains of a-D-glucose units, with or without occasional branch points
OH OH OH
(TEMs). Glycogen occurs as the branched form shown in a(1 4)
part b. (c) The straight-chain portions consist solely of a-D-glucose bond
units linked by a(1 S 4) glycosidic bonds, whereas branch chains
originate at a(1 S 6) glycosidic bonds. (c) Glycogen or amylopectin structure

89

M03_HARD7694_09_GE_C03.indd 89 22/02/17 2:37 pm

 Cellulose
microfibrils in
plant cell wall
Cell
walls
Plant cells
Cellulose
chains Microfibril
b(1 4) bond
CH2OH CH2OH
O O
OH
O
OH
O 3.4 Lipids
OH OH
Figure 3-25 The Structure of Cellulose. Cellulose consists
of long, unbranched chains of b-D-glucose units linked together by
b(1 S 4) glycosidic bonds. Many such chains associate laterally and
are held together by hydrogen bonds to form microfibrils, which can
be seen in the micrograph of a primary plant cell wall shown here
(TEM).
and N-acetylmuramic acid (MurNAc). These two sugars occur
in a strict alternating sequence. As shown in Figure 3-26a,
GlcNAc and MurNAc are derivatives of b-glucosamine, a glu-
cose molecule with the hydroxyl group on carbon atom 2
replaced by an amino group. GlcNAc is formed by adding a
two-carbon acetyl group to the amino group, and MurNAc
requires the further addition of a three-carbon lactyl group
to carbon atom 3. The cell wall polysaccharide is then formed
by the linking of GlcNAc and MurNAc in a strictly alternating
sequence with b(1 S 4) bonds (Figure 3-26b). Figure 3-26c
shows the structure of yet another structural polysaccharide,
the chitin found in insect exoskeletons, crustacean shells, and
fungal cell walls. Chitin consists of GlcNAc units only, joined
by b(1 S 4) bonds.
Polysaccharide Structure Depends on the
Kinds of Glycosidic Bonds Involved
The distinction between the a and b glycosidic bonds of stor-
age and structural polysaccharides has more than just nu-
tritional significance. Because of the difference in linkages
and therefore in the spatial relationship between successive
glucose units, the two classes of polysaccharides differ mark-
edly in secondary structure. The helical shape already estab-
lished as a characteristic of both proteins and nucleic acids
is also found in polysaccharides. Both starch and glycogen
coil spontaneously into loose helices, but often the structure
is not highly ordered due to the numerous side chains of
amylopectin and glycogen.
90
M03_HARD7694_09_GE_C03.indd 90
Cellulose, by contrast, forms rigid, linear rods. These in
turn aggregate laterally into microfibrils (see Figure 3-25).
Microfibrils are about 5–20 nm in diameter and are com-
posed of about 36 cellulose chains. Plant and fungal cell walls
consist of these rigid microfibrils of cellulose embedded in a
noncellulosic matrix containing a rather variable mixture of
several other polymers (hemicellulose and pectin, mainly) and
a protein called extensin that occurs only in the cell wall. Cell
walls have been aptly compared to reinforced concrete, in
which steel rods are embedded in the cement before it hardens
to add strength. In cell walls, the cellulose microfibrils are the
“rods” and the noncellulosic matrix is the “cement.”
CONCEPT CHECK 3.3
Polysaccharides are also important macromolecules in cell
structure and function. How are they similar to proteins and
nucleic acids, and how do they differ?
Strictly speaking, lipids differ from the macromolecules dis-
cussed so far in this chapter because they are not formed by the
kind of linear polymerization that gives rise to proteins, nucleic
acids, and polysaccharides. However, they are commonly regard-
ed as macromolecules because of their high molecular weights
and their presence in important cellular structures, particularly
membranes. Also, the final steps in the synthesis of triglycerides,
phospholipids, and other large lipid molecules involve condensa-
tion reactions similar to those used in polymer synthesis.
Lipids constitute a rather heterogeneous category of cel-
lular components that resemble one another more in their
solubility properties than in their chemical structures. The
distinguishing feature of lipids is their hydrophobic nature. Al-
though they have little, if any, affinity for water, they are read-
ily soluble in nonpolar solvents such as chloroform or ether.
Accordingly, we can expect to find that they are rich in nonpo-
lar hydrocarbon regions and have relatively few polar groups.
Some lipids, however, are amphipathic, having both a polar and
a nonpolar region. As we have already seen in Figures 2-11
and 2-12, this characteristic has important implications for
membrane structure.
Because they are defined in terms of solubility characteris-
tics rather than chemical structure, it should not be surprising
that lipids as a group include molecules that are quite diverse
in terms of structure, chemistry, and function. Functionally,
lipids play at least three main roles in cells. Some serve as
forms of energy storage, others are involved in membrane struc-
ture, and still others have specific biological functions, such as
the transmission of chemical signals into and within the cell.
We will discuss lipids in terms of six main classes, based on
their chemical structure: fatty acids, triacylglycerols, phospho-
lipids, glycolipids, steroids, and terpenes. Note that because of
the wide variety of lipids and the fact that members of differ-
ent classes sometimes share structural and chemical similari-
ties, this is only one of several different ways to classify lipids.
The six main classes of lipids discussed here are illustrated in
Figure 3-27, which includes representative examples of each
class. We will look briefly at each of these six kinds of lipids,
pointing out their functional roles in the process.
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