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16.

1 Sugars: Their Structures and Stereochemistry


1. Recall Define the following terms: polysaccharide, furanose, pyranose,
aldose, ketose, glycosidic bond, oligosaccharide, glycoprotein (1. A
polysaccharide is a polymer of simple sugars, which are compounds that contain a
single carbonyl group and several hydroxyl groups. A furanose is a cyclic sugar that
contains a five-membered ring similar to that in furan. A pyranose is a cyclic sugar
that contains a six-membered ring similar to that in pyran. An aldose is a sugar that
contains an aldehyde group; a ketose is a sugar that contains a ketone group. A
glycosidic bond is the acetal link age that joins two sugars. An oligosaccharide is a
compound formed by the linking of several simple sugars (monosaccharides) by
glycosidic bonds. A glycoprotein is formed by the covalent bonding of sugars to a
protein.)
2. Recall Name which, if any, of the following are epimers of Dglucose: Dmannose, D-galactose, D-ribose.(2. D-Mannose and D-galactose are both
epimers of D-glucose, with inversion of configuration around carbon atoms 2 and 4,
respectively; D-ribose has only five carbons, but the rest of the sugars named in this
question have six. )
3. Recall Name which, if any, of the following groups are not aldose
ketose pairs: D-ribose and D-ribulose, D-glucose and D-fructose, Dglyceraldehyde and dihydroxyacetone.(3. All groups are aldoseketose pairs)
4. Recall What is the difference between an enantiomer and a
diastereomer? (4. Enantiomers are nonsuperimposable, mirror-image
stereoisomers. Diastereomers are nonsuperimposable, nonmirror-image
stereoisomers. )
5. Recall How many possible epimers of D-glucose exist? (5. Four epimers of
D-glucose exist, with inversion of configuration at a single carbon. The possible
carbons at which this is possible are those numbered two through five. )
6. Recall Why are furanoses and pyranoses the most common cyclic forms
of sugars?( 6. Furanoses and pyranoses have five-membered and six-membered
rings, respectively. It is well known from organic chemistry that rings of this size are
the most stable and the most readily formed. )
7. Recall How many chiral centers are there in the open-chain form of
glucose? In the cyclic form?(7. There are four chiral centers in the open-chain
form of glucose (carbons two through five). Cyclization introduces another chiral
center at the carbon involved in hemiacetal formation, giving a total of five chiral
centers in the cyclic form. )
8. Reflect and Apply Following are Fischer projections for a group of fivecarbon sugars, all of which are aldopentoses. Identify the pairs that are
enantiomers and the pairs that are epimers. (The sugars shown here are
not all of the possible five-carbon sugars.)(8. Enantiomers: (a) and (f), (b) and
(d). Epimers: (a) and (c), (a) and (d), (a) and (e), (b) and (f).)
9. Reflect and Apply The sugar alcohol often used in sugarless gums and
candies is L-sorbitol. Much of this alcohol is prepared by reduction of Dglucose. Compare these two structures and explain how this can be. (9. LSorbitol was named early in biochemical history as a derivative of L-sorbose.

Reduction of D-glucose gives a hydroxy sugar that could easily be named D-glucitol,
but it was originally named L-sorbitol and the name stuck. )
10. Reflect and Apply Consider the structures of arabinose and ribose.
Explain why nucleotide derivatives of arabinose, such as ara-C and ara-A,
are effective metabolic poisons.(10. Arabinose is an epimer of ribose.
Nucleosides in which arabinose is substituted for ribose act as inhibitors in reactions
of ribonucleosides.)
11. Reflect and Apply Two sugars are epimers of each other. Is it possible
to convert one to the other without breaking covalent bonds? (11.
Converting a sugar to an epimer requires inversion of configuration at a chiral
center. This can be done only by breaking and re-forming covalent bonds)
12. Reflect and Apply How does the cyclization of sugars introduce a new
chiral center? (12. Two different orientations with respect to the sugar ring are
possible for the hydroxyl group at the anomeric carbon. The two possibilities give
rise to the new chiral center. )
16.2 Reactions of Monosaccharides
13. Recall What is unusual about the structure of N-acetylmuramic acid
(Figure 16.18) compared with the structures of other carbohydrates? (13.
This compound contains a lactic acid side chain. )
14. Recall What is the chemical difference between a sugar phosphate and
a sugar involved in a glycosidic bond? (14. In a sugar phosphate, an ester bond
is formed between one of the sugar hydroxyls and phosphoric acid. A glycosidic
bond is an acetal, which can be hydrolyzed to regenerate the two original sugar
hydroxyls.)
15. Recall Define the term reducing sugar(15. A reducing sugar is one that has
a free aldehyde group. The aldehyde is easily oxidized, thus reducing the oxidizing
agent.)
16.3 Some Important Oligosaccharides
16. Biochemical Connections What are the structural differences between
vitamin C and sugars? Do these structural differences play a role in the
susceptibility of this vitamin to air oxidation? 16.3 Some Important
Oligosaccharides (16. Vitamin C is a lactone (a cyclic ester) with a double bond
between two of the ring carbons. The presence of the double bond makes it
susceptible to air oxidation. )
17. Recall Name two differences between sucrose and lactose. Name two
similarities.( 17. Similarities: sucrose and lactose are both disaccharides, and both
contain glucose. Differences: sucrose contains fructose, whereas lactose contains
galactose. Sucrose has an ,(1 3 2) glycosidic linkage, whereas lactose has a (1 3
4) glycosidic linkage.)
19. Biochemical Connections What is the metabolic basis for the
observation that many adults cannot ingest large quantities of milk
without developing gastric difficulties?( 19. In some cases, the enzyme that
degrades lactose (milk sugar) to its componentsglucose and galactoseis

missing. In other cases, the enzyme isomerizes galactose to glucose for further
metabolic breakdown.)
21. Biochemical Connections A friend asks you why some parents at her
childs school want a choice of beverages served at lunch, rather than milk
alone. What do you tell your friend?( 21. Milk contains lactose. Many people are
sensitive to lactose and require an alternative beverage. 16.4 Structures and
Functions of Polysaccharides )
22. Recall What are some of the main differences between the cell walls
of plants and those of bacteria?( 22. The cell walls of plants consist mainly of
cellulose, whereas those of bacteria consist mainly of polysaccharides with peptide
crosslinks. )
23. Recall How does chitin differ from cellulose in structure and function?
( 23. Chitin is a polymer of N-acetyl--D-glucosamine, whereas cellulose is a
polymer of D-glucose. Both polymers play a structural role, but chitin occurs in the
exoskeletons of invertebrates and cellulose primarily in plants. )
24. Recall How does glycogen differ from starch in structure and function?(
24. Glycogen and starch differ mainly in the degree of chain branching. Both
polymers serve as vehicles for energy storage, glycogen in animals and starch in
plants. )
25. Recall What is the main structural difference between cellulose and
starch?( 25. Both cellulose and starch are polymers of glucose. In cellulose, the
monomers are joined by a -glycosidic linkage, whereas in starch they are joined by
an -glycosidic linkage.)
26. Recall What is the main structural difference between glycogen and
starch? (26. Glycogen exists as a highly branched polymer. Starch can have both a
linear and a branched form, which is not as highly branched as that of glycogen. )
27. Recall How do the cell walls of bacteria differ from those of plants? (27.
Plant cell walls consist almost exclusively of carbohydrates, whereas bacterial cell
walls contain peptides.)
29. Reflect and Apply Advertisements for a food supplement to be taken
by athletes claimed that the energy bars contained the two best
precursors of glycogen. What were they? (29. Glucose and fructose. )
30. Reflect and Apply Explain how the minor structural difference between
- and -glucose is related to the differences in structure and function in
the polymers formed from these two monomers. (30. Differences in structure:
cellulose consists of linear fibers, but starch has a coil form. Differences in function:
cellulose has a structural role, but starch is used for energy storage. )
31. Reflect and Apply All naturally occurring polysaccharides have one
terminal residue, which contains a free anomeric carbon. Why do these
polysaccharides not give a positive chemical test for a reducing sugar? (31.
The concentration of reducing groups is too small to detect. )
32. Reflect and Apply An amylose chain is 5000 glucose units long. At how
many places must it be cleaved to reduce the average length to 2500
units? To 1000 units? To 200 units? What percentage of the glycosidic links

are hydrolyzed in each case? (Even partial hydrolysis can drastically alter
the physical properties of polysaccharides and thus affect their structural
role in organisms.( 32. To 2500, one place (0.02%). To 1000, four places (0.08%).
To 200, 24 places (0.48%).)
33. Reflect and Apply Suppose that a polymer of glucose with alternating
(1 3 4) and (1 3 4) glycosidic linkages has just been discovered. Draw a
Haworth projection for a repeating tetramer (two repeating dimers) of
such a polysaccharide. Would you expect this polymer to have primarily a
structural role or an energy-storage role in organisms? What sort of
organisms, if any, could use this polysaccharide as a food source?( 33. This
polymer would be expected to have a structural role. The presence of the glycosidic linkage makes it useful as food only to termites or to ruminants, such as
cows and horses; these animals harbor bacteria capable of attacking the -linkage
in their digestive tracts.)
34. Reflect and Apply Glycogen is highly branched. What advantage, if
any, does this provide an animal?( 34. Because of the branching, the glycogen
molecule gives rise to a number of available glucose molecules at a time when it is
being hydrolyzed to provide energy. A linear molecule could produce only one
available glucose at a time. )
35. Reflect and Apply No animal can digest cellulose. Reconcile this
statement with the fact that many animals are herbivores that depend
heavily on cellulose as a food source. (35. The digestive tract of these animals
contains bacteria that have the enzyme to hydrolyze cellulose.)
36. Reflect and Apply How does the presence of -bonds versus -bonds
influence the digestibility of glucose polymers by humans? Hint: There are
two effects.( 36. Humans lack the enzyme to hydrolyze cellulose. In addition, the
fibrous structure of cellulose makes it too insoluble to digest, even if humans had
the necessary enzyme. )
37. Reflect and Apply How do the sites of cleavage of starch differ from
one another when the cleavage reaction is catalyzed by -amylase and amylase? (37. The enzyme -amylase is an exoglycosidase, degrading
polysaccharides from the ends. The enzyme -amylase is an endoglycosidase,
cleaving internal glycosidic bonds. )
38. Biochemical Connections What is the benefit of fiber in the diet? (38.
Fiber binds many toxic substances in the gut and decreases the transit time of
ingested food in the digestive tract, so that harmful compounds such as carcinogens
are removed from the body more quickly than would be the case with a low-fiber
diet. )
39. Reflect and Apply How would you expect the active site of a cellulase
to differ from the active site of an enzyme that degrades starch? (39. A
cellulase (an enzyme that degrades cellulose) needs an active site that can
recognize glucose residues joined in a -glycosidic linkage and hydrolyze that
linkage. An enzyme that degrades starch has the same requirements with regard to
glucose residues joined in an -glycosidic linkage. )
40. Reflect and Apply Would you expect cross-linking to play a role in the
structure of polysaccharides? If so, how would the cross-links be formed?

(40. Cross-linking can be expected to play a role in the structures of polysaccharides


where mechanical strength is an issue. Examples include cellulose and chitin. These
crosslinks can be readily formed by extensive hydrogen bonding. (See Figure 16.19.)
)
41. Reflect and Apply Compare the information in the sequence of
monomers in a polysaccharide with that in the sequence of amino acid
residues in a protein.( 41. The sequence of monomers in a polysaccharide is not
genetically coded, and, in this sense, it does not contain information. )
42. Reflect and Apply Why is it advantageous that polysaccharides can
have branched chains? How do they achieve this structural feature? (42. It
can be useful for polysaccharides to have a number of ends, characteristic of a
branched polymer, rather than the two ends of a linear polymer. This would be the
case when it is necessary to release residues from the ends as quickly as possible.
Polysaccharides achieve this by having 1 3 4 and 1 3 6 glycosidic linkages to a
residue at a branch point. )
43. Reflect and Apply Why is the polysaccharide chitin a suitable material
for the exoskeleton of invertebrates such as lobsters? What other sort of
material can play a similar role? (43. Chitin is a suitable material for the
exoskeleton of invertebrates because of its mechanical strength. Individual polymer
strands are cross-linked by hydrogen bonding, accounting for the strength. Cellulose
is another polysaccharide cross-linked in the same way, and it can play a similar
role. )
44. Reflect and Apply Could bacterial cell walls consist largely of protein?
Why or why not? (44. Bacterial cell walls are not likely to consist largely of
protein. Polysaccharides are easily formed and confer considerable mechanical
strength. They are likely to play a large role. )
45. Reflect and Apply Some athletes eat diets high in carbohydrates
before an event. Suggest a biochemical basis for this practice. (45. Athletes
try to increase their stores of glycogen before an event. The most direct way to
increase the amount of this polymer of glucose is to eat carbohydrates. )
46. Reflect and Apply You are a teaching assistant in a general chemistry
lab. The next experiment is to be an oxidationreduction titration
involving iodine. You get a starch indicator from the stockroom. Why do
you need it? (46. Iodine is the reagent that will be added to the reaction mixture in
the titration. When the end point is reached, the next drop of iodine will produce a
characteristic blue color in the presence of the indicator. )
47. Reflect and Apply Blood samples for research or medical tests
sometimes have heparin added. Why is this done? (47. Heparin is an
anticoagulant. Its presence prevents blood clotting.)
48. Reflect and Apply Based on what you know about glycosidic bonds,
propose a scheme for formation of covalent bonds between the
carbohydrate and protein portions of glycoproteins.( 48. Glycosidic bonds
can be formed between the side-chain hydroxyls of serine or threonine residues and
the sugar hydroxyls. In addition, there is the possibility of ester bonds forming
between the side-chain carboxyl groups of aspartate or glutamate and the sugar
hydroxyls.)

16.5 Glycoproteins
49. Recall What are glycoproteins? What are some of their biochemical
roles?( 49. Glycoproteins are ones in which carbohydrates are covalently bonded to
proteins. They play a role in eukaryotic cell membranes, frequently as recognition
sites for external molecules. Antibodies (immunoglobulins) are glycoproteins.)
50. Biochemical Connections Briefly indicate the role of glycoproteins as
antigenic determinants for blood groups.(50. The sugar portions of the bloodgroup glycoproteins are the source of the antigenic difference.)
What is unique about the structures of sugars? The simplest examples of
carbohydrates are monosaccharides, compounds that each contain a single
carbonyl group and two or more hydroxyl groups. Monosaccharides
frequentlyencountered in biochemistry are sugars that contain from three to seven
carbon atoms. Sugars contain one or more chiral centers; the configurations of the
possible stereoisomers can be represented by Fischer projection formulas.What
happens if a sugar forms a cyclic molecule? Sugars exist predominantly as
cyclic molecules rather than in an open-chain form. Haworth projection formulas are
more realistic representations of the cyclic forms of sugars than are Fischer
projection formulas. Many stereoisomers are possible for five- and six-carbon
sugars, but only a few of the possibilities are encountered frequently in nature.
What are some oxidationreduction reactions of sugars? Monosaccharides
can undergo various reactions. Oxidation reactions make up one important group.
What are some important esterification reactions of sugars? Esterification of
sugars to phosphoric acid plays an important role in metabolism. What are
glycosides, and how do they form? The most important reaction of sugars by far
is the formation of glycosidic linkages, which give rise to oligosaccharides and
polysaccharides. What are some other important derivatives of sugars?
Amino sugars are the basis of cell wall structures. What makes sucrose an
important compound? Three important examples of oligosaccharides are the
disaccharides sucrose, lactose, and maltose. Sucrose is common table sugar. It is a
disaccharide formed when a glycosidic bond forms between glucose and fructose.
Are any other disaccharides important to us? Lactose occurs in milk, and
maltose is obtained via the hydrolysis of starch. How do cellulose and starch
differ from one another? In polysaccharides, the repeating unit of the polymer is
frequently limited to one or two kinds of monomer. Cellulose and starch differ in the
anomeric form of their glycosidic bonds: the form in starch and the form in
cellulose. Is there more than one form of starch? Starch exists in two polymeric
forms, the linear amylose and the branched amylopectin. How is glycogen
related to starch? Starch, found in plants, and glycogen, which occurs in animals,
differ from each other in the degree of branching in the polymer structure. What is
chitin? Cellulose and chitin are polymers based on single kinds of monomer units
glucose and N-acetylglucosamine, respectively. Both polymers play structural roles
in organisms. What role do polysaccharides play in the structure of cell
walls? In bacterial cell walls, polysaccharides are cross-linked to peptides. Plant cell
walls consist primarily of glucose. Do polysaccharides play any specific roles in
connective tissue? Glycosaminoglycans are a type of polysaccharide based on a
repeating disaccharide in which one of the sugars is an amino sugar and at least
one of them has a negative charge owing to the presence of a sulfate group or a
carboxyl group. They play a role in joint lubrication and also in the blood clotting
process. How are carbohydrates important in the immune response? In
glycoproteins, carbohydrate residues are covalently linked to the polypeptide chain.

Such glycoproteins can play a role in the recognition sites of antigens. A common
example is the ABO blood group, in which the three major blood types are
distinguished by sugar molecules attached to the protein.