Principles of Biochemistry

L. Moran, R. Horton, G. Scrimgeour, M. Perry

Chapter VIII
Carbohydrates

Dr. Reem Arafa

Prof. of Biomedical Sciences
Biochemistry
BMS 204
Spring 2020
 Carbohydrates
• Polymers of monosaccharides (CH2O)n.

• Glycans: Oligosaccharides (2-20 units) or polysaccharides (>20).

– Homoglycans vs. heteroglycans

• Glucoconjugates: proteoglycans, peptidoglycans, glycoproteins, glycolipids.

 Monosaccharides Are Chiral Compounds
• Polyhydroxy aldehydes (aldoses, the most oxidized carbon is C1)
or polyhydroxyketones (ketoses, the most oxidized carbon is C2).

• Chirality can be expressed by the Fisher projection.

• The smallest monosaccharide is triose.

• The aldose (glyceraldehyde) is chiral and the ketose (dihydroxyacetone) isn’t.

• D- and L-stereoisomers of glyceraldehyde are non-superimposable mirror images.

• By convention, sugars are said to have the D configuration when the configuration of the
chiral carbon with the highest number—the chiral carbon most distant from the carbonyl
carbon—is the same as that of C-2 of D-glyceraldehyde (i.e., the —OH group attached to
this carbon atom is on the right side in a Fischer projection).

• Same applies for L- isomer.

• There are 2n possible stereoisomers for a compound with n chiral carbons.

• Sugar molecules that differ in configuration at only one of several chiral centers are called
epimers.
 Cyclization of Aldoses and Ketoses
• A solution of D-Glucose exists in two forms that contain five (not four) asymmetric carbons.

• Additional asymmetry is due to an intramolecular cyclization reaction that produces a new

chiral center at the carbon atom of the carbonyl group.

• This cyclization resembles the reaction of an alcohol with an aldehyde to form a hemiacetal
or with a ketone to form a hemiketal.
• The oxygen atom from the reacting hydroxyl group
becomes a member of the five- or six-membered ring
structures.

• The six-membered ring of a monosaccharide is

called a pyranose.

• The five-membered ring of a monosaccharide is

called a furanose.

• Note that, unlike pyran and furan, the rings of

carbohydrates do not contain double bonds.
• The most oxidized carbon of a cyclized
monosaccharide, the one attached to
two oxygen atoms, is referred to as the
anomeric carbon.

• In ring structures, the anomeric carbon

is chiral. Thus, the cyclized aldose or
ketose can adopt either of two
configurations (designated α or β).

• The α and β isomers are called

anomers.

• The ring drawings are called Haworth

projections.
D-Fructofuranose
 Conformations of Monosaccharides
• The geometry of the carbon atoms of a monosaccharide ring is tetrahedral (bond angles
near 110°), so monosaccharide rings are not planar.

• Cyclic monosaccharides can exist in a variety of conformations.

 Conformation of furanoses
• Furanose rings adopt envelope
conformations: one of the five ring atoms
(either C-2 or C-3) is out-of-plane and the
remaining four are approximately coplanar.

• Furanoses can also form twist conformations:

two of the five ring atoms are out-of-plane—
one on either side of the plane formed by the
other three atoms.

• The relative stability of each conformer

depends on the degree of steric interference
between the hydroxyl groups.
 Conformation of pyranoses
• Pyranose rings tend to assume one of two conformations, the chair (more stable, less steric
clashes) or the boat (less stable).

• There are two distinct chair conformers and six distinct boat conformers for each pyranose.
 Derivatives of Monosaccharides
• Monosaccharide derivatives, including
sugar phosphates, deoxy and amino
sugars, sugar alcohols, and sugar
acids.

• Sugar phosphates:
– The triose phosphates, ribose 5-phosphate,
and glucose 6-phosphate are simple
alcohol-phosphate esters.
– Glucose 1-phosphate is a hemiacetal
phosphate, which is more reactive than an
alcohol phosphate. The ability of UDP-
glucose to act as a glucosyl donor is
evidence of this reactivity.
• Deoxy Sugars: In these derivatives, a hydrogen
atom replaces one of the hydroxyl groups in the
parent monosaccharide.
– 2-Deoxy-D-ribose is an important building
block for DNA.
– L-Fucose (6-deoxy-L-galactose) is widely
distributed in plants, animals, and
microorganisms. Despite its unusual L
configuration, fucose is derived metabolically
from D-mannose.
• Amino Sugars: obtained when an amino group replaces one of the hydroxyl groups in
the parent monosaccharide. Sometimes the amino group is acetylated.

• Amino sugars formed from glucose and galactose commonly occur in glycoconjugates.
• Sugar Alcohols: In a sugar alcohol, the carbonyl oxygen of the parent monosaccharide has
been reduced, producing a polyhydroxy alcohol.
– Glycerol and myo-inositol are important components of lipids.
– Ribitol is a component of flavin mononucleotide (FMN) and flavin adenine dinucleotide
(FAD).

• In general, sugar alcohols are named by replacing the suffix -ose of the parent
monosaccharides with -itol.
• Sugar Acids: carboxylic acids derived from aldoses, either by oxidation of C-1 (the
aldehydic carbon) to yield an aldonic acid or by oxidation of C-6 to yield an alduronic acid.

• Aldonic acids exist in the open-chain form in alkaline solution and form lactones
(intramolecular esters) on acidification.

• Alduronic acids can exist as pyranoses and therefore possess an anomeric carbon.
 Disaccharides and other glycosides
• The glycosidic bond is the primary structural linkage in all polymers of monosaccharides.

• A glycosidic bond is an acetal linkage in which the anomeric carbon of a sugar is condensed
with an alcohol, an amine, or a thiol.

• Compounds containing glycosidic bonds are called glycosides.

A reducing sugar,
why???
β anomer occurs in old ice-cream Has no anomer, why???
Non-reducing, why ???
 Polysaccharides
• Homoglycans or heteroglycans

• Can be classified based on

function into:
– storage polysaccharides (e.g.
glycogen and starch) or
– structural polysaccharides
(e.g. chitin and cellulose).
 Starch and Glycogen
• Glucose residues are stored as polysaccharides until they are needed for energy production.

• The most common storage homoglycan of glucose in plants and fungi is starch and in animals
it is glycogen. Both types of polysaccharides occur in bacteria.

• Starch is stored as amylose and amylopectin

• Amylose: unbranched polymer of about 100 to 1000 D-glucose residues connected by α-

(14) glycosidic linkages

• Although it is not soluble in water, amylose forms hydrated micelles in water and can assume
a helical structure
• Amylopectin is a branched version of amylose

• Branches, or polymeric side chains, are attached via α-(16) glucosidic bonds to linear
chains of residues linked by α-(14) glucosidic bonds.

• Branching occurs once every 25 residues and the side chains contain about 15 to 25
glucose residues.

• Some side chains themselves are branched. Amylopectin molecules isolated from living
cells may contain 300 to 6000 glucose residues
 Glycoconjugates
• Polysaccharides, mostly heteroglycans, linked to (conjugated with) proteins or peptides.

• Three types of glycoconjugates:

– proteoglycans,
– peptidoglycans, and
– glycoproteins.
 Proteoglycans
• Complexes of proteins and a class of polysaccharides called
glycosaminoglycans.

• These glycoconjugates occur predominately in the

extracellular matrix (connective tissue) of multicellular
animals.

• Glycosaminoglycans are unbranched heteroglycans of

repeating disaccharide units of an amino sugar + alduronic
acid
• Amino sugar (D-galactosamine (GalN) or D-glucosamine (GlcN)).

• Amino can be acetylated and specific hydroxyl and amino groups of many
glycosaminoglycans are sulfated.

• These sulfate groups and the carboxylate groups of alduronic acids make
glycosaminoglycans polyanionic.
Hyaluronic acid a major component of cartilage
 Peptidoglycans
• Polysaccharides linked to small peptides

• In cell walls of bacteria: 4-5 peptide residues + heteroglycan (alternating N-

acetylglucosamine (GlcNAc) and N-acetylmuramic acid (MurNAc) attached by β-(14) link

• Some bacteria have an outer capsule made up of chains of polysaccharides of GlcNAc

Gm +ve and gm –ve Bacteria with
Bacteria capsule
Glycoproteins vs proteoglycans