Introduction

• Virtually all the foods we eat contain carbohydrates

• Not all carbohydrates occur in forms that can be readily broken down
• We cannot digest and use all the carbohydrates we eat
• Atomic composition is largely limited to C, H, and O
• Variety of biological functions from energy metabolism to cellular
structure
• also known as sugars or saccharides
Energy storage Structural materials
Continued.
• 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
Continued.
• Carbohydrates, occur as monosaccharides (simple sugars, D-glucose
is the most abundant monosacharide),
• Small polymers (disaccharides e.g.
sucrose, trisaccharides, and so on),
• Larger polysaccharides (sometimes
called complex carbohydrates
e.g. cellulose,
glycogen)
Monosaccharides
• Monosaccharides follow the molecular formula (CH2O)n, where n=3
(hence the name carbohydrate)
• The simplest sugars are the three-carbon compounds glyceraldehyde
and dihydroxyacetone
• A sugar can be a(n)
• Aldose: having carbonyl
group as aldehyde
• Ketose: carbonyl group as
ketone
Continued.
• Number of carbon atoms in the carbohydrate + -ose
• A monosaccharide could be a triose (3C), tetrose (4C), pentose (5C),
hexose (6C) etc.
• These could be aldotetroses and ketotetroses, aldopentoses and
ketopentoses etc.
• Colorless, crystalline solids freely soluble in water
• Most have a sweet taste
• The backbones of common monosaccharide molecules are
unbranched carbon chains in which all the carbon atoms are linked by
single bonds
No. of Carbon Atoms Aldose Ketose

3C Triose Glyceraldehyde Dihydroxyacetone

4C Tetrose Erythrose Erythrulose

5C Pentose Ribose, Xylose Ribulose, Xylullose

6C Hexose Glucose, Galactose, Mannose Fructose

Continued.
• Hexoses (aldohexose; D-glucose, ketohexose; D-fructose) are the
most common monosaccharides in nature
• The aldopentoses, D-ribose and 2-deoxy-D-ribose are components of
nucleotides
Isomerism
• Isomers are molecules that have the
same chemical formula but different
chemical structures
• Asymmetric Carbon is that Carbon
which is attached with four
different chemical groups
• Sterioisomers vs Epimers?
Monosaccharides Have Asymmetric Centers
• All the monosaccharides except dihydroxyacetone contain one or
more asymmetric (chiral) carbon atoms and thus occur in optically
active isomeric forms
• The simplest aldose, glyceraldehyde, contains one chiral center and
thus two isomers
Continued.
• A molecule with n chiral centers can have 2n stereoisomers
• Glyceraldehyde has 21=2, the aldohexoses, with four chiral centers,
have 24 =16 stereoisomers
• Two sugars that differ only in the configuration around one carbon
atom are called epimers
• Position of the OH on the
last asymmetric carbon
atom will tell us whether
it is a "D" sugar or an "L"
sugar
 The D-aldoses with up to six carbon atoms
D sugars have the same
absolute configuration at the
asymmetric center farthest
from their carbonyl group.

Figure 8-1
 Hemiacetals and Hemiketals
• Aldehyde and ketone carbons are electrophilic.
• Alcohol oxygen atom is nucleophilic.
• When aldehydes are attacked by alcohols, hemiacetals form.
• When ketones are attacked by alcohols, hemiketals form
• These reactions form
the basis of cyclization
of sugars
 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.
Continued.
• Isomeric forms of monosaccharides that differ only in their
configuration about the hemiacetal or hemiketal carbon atom are
called anomers
• The hemiacetal (or carbonyl) carbon atom is called the anomeric
carbon
• The alpha and beta anomers of D-glucose interconvert in aqueous
solution by a process called mutarotation.
• Thus, a solution of a-D-glucose and a solution of b-D-glucose
eventually form identical equilibrium mixtures having identical optical
properties
Pyranose and furanose
• 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
Hexose Derivatives
Monosaccharides as reducing agents
• Monosaccharides can be oxidized by relatively mild oxidizing agents
such as ferric (Fe3) or cupric (Cu2) ion
• The carbonyl carbon is oxidized to a carboxyl group
• Glucose and other sugars capable of reducing ferric or cupric ion are
called reducing sugars
• Fehling’s reaction, a qualitative test for the presence of reducing
sugar is based on this property of sugars
• The amount of oxidizing agent reduced by a solution of a sugar is
measured to estimate the concentration of that sugar
The cuprous ion (Cu) produced
under alkaline conditions forms a
red cuprous oxide precipitate. In
the hemiacetal (ring) form, C-1 of
glucose cannot be oxidized by Cu2
The reaction with Cu2 is not as
simple as the equation here
implies; in addition to D-gluconate,
a number of shorter-chain
acids are produced by the
fragmentation of glucose
Disaccharides Contain a Glycosidic Bond
• Disaccharides (maltose, lactose, and sucrose) consist of two
monosaccharides joined covalently by an O-glycosidic bond, which is
formed when a hydroxyl group of one sugar reacts with the anomeric
carbon of the other
• It is actually the formation of an acetal molecule (one sugar as
hemiacetal and OH group of another sugar as alcohol)
• Glycosidic bonds are readily hydrolyzed by acid but resist cleavage by
base
Maltose
• It contains two D-glucose residues
joined by a glycosidic linkage
between C-1 (the anomeric
carbon) of one glucose residue
and C-4 of the other
• Obtained from the breakdown of
starches
• Reducing sugar
Lactose
• Consists of D-galactose and D-glucose
• Reducing sugar
• Has a β -1,4-glycosidic bond
Sucrose (table sugar)
• A disaccharide of glucose and fructose
• It is formed by plants but not by animals
• Sucrose contains no free anomeric carbon atom both anomeric
carbons are involved in glycosidic bond
• Non-reducing sugar
Polysaccharides
• Most carbohydrates found in nature occur as polysaccharides,
polymers of medium to high molecular weight
• Polysaccharides, also called glycans, differ from each other:
• 1. In the identity of their recurring monosaccharide units,
• 2. In the length of their chains,
• 3. In the types of bonds linking the units, and
• 4. In the degree of branching
Types of polysaccharides
Homopolysaccharides
• Some homopolysaccharides serve as storage forms of
monosaccharides that are used as fuels
• Other (cellulose and chitin) serve as structural elements in plant cell
walls and animal exoskeletons
• Starch and glycogen are important storage homopolysaccharides
• Both occur intracellularly as large clusters or granules and are heavily
hydrated because of the OH groups present
• Glucans are polymers of glucose, galactans are polymers of galactose
Starch
• Abundant in potato and seeds
• Starch contains two types of glucose polymer, amylose and
amylopectin
• Amylose consists of long, unbranched chains of D-glucose residues
connected by (alpha 1→4) linkages
• Mol. Wt. varies from a few thousand to more than a million
Continued.
• Amylopectin also has a high molecular
weight (up to 100 million) but unlike
amylose is highly branched
• The glycosidic linkages joining successive
glucose residues in amylopectin chains are
(alpha 1→4); the branch points
(occurring every 24 to 30 residues) are
(alpha 1→6) linkages
Glycogen
• Main storage polysaccharide of animal cells
• It is a polymer of (alpha 1→4)-linked subunits of glucose, with (alpha
1→6)-linked branches
• Glycogen is more extensively branched (on average, every 8 to 12
residues) and more compact than starch
• Glycogen is especially abundant in the liver (7% by wet wt.)
• Also present in skeletal muscle
Structural homopolysaccharides
• Cellulose, a fibrous, tough, water-insoluble substance, is found in the
cell walls of plants, particularly in stalks, stems, trunks, and all the
woody portions of the plant body
• Cotton is pure cellulose
• Cellulose molecule is a linear, unbranched
homopolysaccharide, consisting of 10,000 to 15,000
D-glucose units
• D-glucose have beta configuration
Continued.
• The glucose residues in cellulose are linked by (beta 1→4) glycosidic
bonds
Continued.
• Glycogen and starch ingested in the diet are hydrolyzed by alpha-
amylases, enzymes in saliva and intestinal secretions that break (beta
1→4) glycosidic bonds between glucose units
• Most animals cannot use cellulose as a fuel source, because they lack
an enzyme to hydrolyze (beta 1→4) linkages
• Termites readily digest cellulose because their intestinal tract harbors
a symbiotic microorganism, Trichonympha, that secretes cellulase,
which hydrolyzes the (beta 1→4) linkages
• Wood-rot fungi also produce cellulase
Chitin
• Chitin is a linear homopolysaccharide composed of N-
acetylglucosamine residues in linkage
• The only chemical difference from cellulose is the replacement of the
hydroxyl group at C-2 with an acetylated amino group
• Chitin is the principal component of the hard exoskeletons of nearly a
million species of arthropods—insects, lobsters, and crabs
• Probably the second most abundant polysaccharide, next to cellulose,
in nature
Heteropolysaccharides
• The rigid component of bacterial cell walls is a heteropolymer of
alternating (beta 1→4)-linked N-acetylglucosamine and N-
acetylmuramic acid residues
• The linear polymers lie side by side in the cell wall, cross-linked by
short peptides, the exact structure of which depends on the bacterial
species
• The enzyme lysozyme kills bacteria by hydrolyzing the (beta 1→4)
glycosidic bond between N-acetylglucosamine and N-acetylmuramic
acid
• Lysozyme is notably present in tears, presumably as a defense against
bacterial infections of the eye
Lysozyme is also produced by certain bacterial
viruses to ensure their release from the host
bacterial cell
Penicillin and related antibiotics kill bacteria by
preventing synthesis of the cross-links, leaving
the cell wall too weak to resist osmotic lysis
When we eat more carbohydrates than we burn for
energy, our body ends up storing them as fat, and this is
the primary cause of weight gain and related ills