7 | Carbohydrates and

Glycobiology

© 2017 W. H. Freeman and Company

 Carbohydrates

• Named so because many have formula Cn(H2O)n

• Produced from CO2 and H2O via photosynthesis in plants
• Range from as small as glyceraldehyde (Mw = 90 g/mol) to as
large as amylopectin (Mw > 200,000,000 g/mol)
• Fulfill a variety of functions, including:
– energy source and energy storage
– structural component of cell walls and exoskeletons
– informational molecules in cell-cell signaling
• Can be covalently linked with proteins and lipids
 Carbohydrates
• Basic nomenclature:
– number of carbon atoms in the carbohydrate + -ose
– example: three carbons = triose
• Common functional groups:
– All carbohydrates initially had a carbonyl functional
group.
– aldehydes = aldose
– ketones = ketose
Carbohydrates Can Be Constitutional Isomers
• An aldose is a carbohydrate with aldehyde functionality.
• A ketose is a carbohydrate with ketone functionality.
 Carbohydrates Can Be Stereoisomers
• Enantiomers
– stereoisomers that are nonsuperimposable mirror images
• In sugars that contain many chiral centers, only the one
that is most distant from the carbonyl carbon is
designated as D (right) or L (left).
• D and L isomers of a sugar are enantiomers.
– For example, L- and D-glucose have the same water solubility.
• Most hexoses in living organisms are D stereoisomers.
• Some simple sugars occur in the L form, such as
L-arabinose.
Enantiomers Are Mirror Images
Drawing Monosaccharides

• Chiral compounds can be

drawn using perspective
formulas.
• However, chiral
carbohydrates are usually
represented by Fischer
projections.
• Horizontal bonds are
pointing toward you;
vertical bonds are
projecting away from you.
 Common Carbohydrates
in Biochemistry

• Ribose is the standard five-carbon sugar.

• Glucose is the standard six-carbon sugar.
• Galactose is an epimer of glucose.
• Mannose is an epimer of glucose.
• Fructose is the ketose form of glucose.
 Cyclization of
Monosaccharides
• The nucleophilic alcohol attacks
the electrophilic carbonyl
carbon, allowing formation of a
hemiacetal.
• As a result, the linear
carbohydrate forms a ring
structure.
• At the completion of this
structure, the carbonyl carbon is
reduced to an alcohol
• The orientation of the alcohol
around the carbon is variable
and transient.
 Cyclization of Monosaccharides
• Pentoses and hexoses readily undergo intramolecular
cyclization.
• The former carbonyl carbon becomes a new chiral
center, called the anomeric carbon.
– When the former carbonyl oxygen becomes a hydroxyl group,
the position of this group determines if the anomer is  or .
– If the hydroxyl group is on the opposite side (trans) of the ring
as the CH2OH moiety, the configuration is .
– If the hydroxyl group is on the same side (cis) of the ring as
the CH2OH moiety, the configuration is .
 Cyclization of Monosaccharides:
Pyranoses and Furanoses
• Six-membered oxygen-containing rings are called
pyranoses after the pyran ring structure.
• Five-membered oxygen-containing rings are called
furanoses after the furan ring structure.
• The anomeric carbon is usually drawn on the right
side.
 Conformational Formulas of Cyclized
Monosaccharides

• Cyclohexane rings have “chair” or “boat” conformations.

• Pyranose rings favor “chair” conformations.
• Multiple “chair” conformations are possible but require energy
for interconversion (~46 kJ/mole).
 Reducing Sugars
• Reducing sugars have a free anomeric carbon.
– Aldehyde can reduce Cu2+ to Cu+ (Fehling’s test).
– Aldehyde can reduce Ag+ to Ag0 (Tollens’ test).
– It allows detection of reducing sugars, such as glucose.
– Modern detection techniques use colorimetric and
electrochemical tests.
 The Glycosidic Bond
• Two sugar molecules can be joined via a glycosidic bond between an
anomeric carbon and a hydroxyl carbon.
• The glycosidic bond (an acetal) between monomers is more stable and
less reactive than the hemiacetal at the second monomer.
– The second monomer, with the hemiacetal, is reducing.
– The anomeric carbon involved in the glycosidic linkage is nonreducing.
• Disacharides can be named by the organization and linkage or a
common name.
– The disaccharide formed upon condensation of two glucose molecules via
a 1  4 bond is described as α-d-glucopyranosyl-(14)-d-glucopyranose.
– The common name for this disaccharide is maltose.
Nonreducing Disaccharides
• Two sugar molecules can be
also joined via a glycosidic
bond between two anomeric
carbons.
• The product has two acetal
groups and no hemiacetals.
• There are no reducing ends;
this is a nonreducing sugar.
 Polysaccharides
• Natural carbohydrates are usually found as polymers.
• These polysaccharides can be:
– homopolysaccharides (one monomer unit)
– heteropolysaccharides (multiple monomer units)
– linear (one type of glycosidic bond)
– branched (multiple types of glycosidic bonds)
• Polysaccharides do not have a defined molecular weight.
– This is in contrast to proteins because, unlike proteins, no
template is used to make polysaccharides.
– Polysaccharides are often in a state of flux; monomer
units are added and removed as needed by the organism.
 Homopolymers of Glucose:
Glycogen
• Glycogen is a branched homopolysaccharide of
glucose.
– Glucose monomers form (1  4) linked chains.
– There are branch points with (1  6) linkers every
8–12 residues.
– Molecular weight reaches several millions.
– It functions as the main storage polysaccharide in
animals.
 Homopolymers of Glucose:
Starch
• Starch is a mixture of two homopolysaccharides of
glucose.
• Amylose is an unbranched polymer of (1  4)
linked residues.
• Amylopectin is branched like glycogen, but the
branch points with (1  6) linkers occur every
24–30 residues.
• Molecular weight of amylopectin is up to 200
million.
• Starch is the main storage polysaccharide in plants.
Glycosidic Linkages in Glycogen and Starch
 Metabolism of Glycogen and Starch

• Glycogen and starch are insoluble due to their high

molecular weight and often form granules in cells.
• Granules contain enzymes that synthesize and degrade
these polymers.
• Glycogen and amylopectin have one reducing end but
many nonreducing ends.
• Enzymatic processing occurs simultaneously in many
nonreducing ends.
 Glycoconjugates: Glycoprotein
• A protein with small oligosaccharides attached
– Carbohydrate ia attached via its anomeric carbon to amino acids on the
protein.
• Common connections occur at Ser, Thr, and Asn.
– About half of mammalian proteins are glycoproteins.
– Only some bacteria glycosylate a few of their proteins.
– Carbohydrates play role in protein-protein recognition.
– Viral proteins are heavily glycosylated; this helps evade the immune
system.
 Glycoconjugates: Glycolipids

• Lipids with covalently bound oligosaccharide

– They are parts of plant and animal cell membranes.
– In vertebrates, ganglioside carbohydrate
composition determines blood groups.
– In gram-negative bacteria, lipopolysaccharides
cover the peptidoglycan layer.
 Chapter 7: Summary

In this chapter, we learned about:

• structures of some important monosaccharides

• structures and properties of disaccharides
• structures and biological roles of polysaccharides
• functions of glycosylaminoglycans as structural
components of the extracellular matrix
• functions glycoconjugates in regulating a variety of
biological functions