Biochemistry

• Biochemistry is the study of the chemical

substances found in living organisms and the
chemical interactions of these substances with
each other
• A biochemical substance is a chemical
Biochemistry substance found within a living organism
• Bioinorganic substances include water and
inorganic salts
• Bioorganic substances include carbohydrates,
lipids, proteins, and nucleic acids
Carbohydrates
 Carbohydrates are the most abundant class of bioorganic
molecules on planet Earth.

1. Carbohydrate oxidation provides energy.

2. Carbohydrate storage, in the form of glycogen, provides a short-

term energy reserve.

Functions of 3. Carbohydrates supply carbon atoms for the synthesis of other

biochemical substances (proteins, lipids, and nucleic acids).
Carbohydrates
4. Carbohydrates form part of the structural framework of DNA and
RNA molecules.

5. Carbohydrates linked to lipids are structural components of cell

membranes.

6. Carbohydrates linked to proteins function in a variety of cell–cell

and cell–molecule recognition processes.
 Carbohydrates

• A carbohydrate is a
polyhydroxy aldehyde, a
polyhydroxy ketone, or a
compound that yields
polyhydroxy aldehydes or
polyhydroxy ketones upon
hydrolysis
 Carbohydrates are classified on the basis of molecular size

A monosaccharide is a carbohydrate that contains a single polyhydroxy

aldehyde or polyhydroxy ketone unit. Monosaccharides cannot be
broken down into simpler units by hydrolysis reactions

Classification
of An oligosaccharide is a carbohydrate that contains two to ten
monosaccharide units covalently bonded to each other

Carbohydrates
A disaccharide is a carbohydrate that contains two monosaccharide
units covalently bonded to each other

A polysaccharide is a polymeric carbohydrate that contains many

monosaccharide units covalently bonded to each other. Polysaccharides
often contain several thousand monosaccharide units.
 Chirality:
Handedness
in Molecules
Most monosaccharides exist in
two forms: a “left-handed” form
and a “right-handed” form
 • A mirror image is the reflection of an object in a
mirror.
• Superimposable mirror images are images that
coincide at all points when the images are laid
Mirror Images upon each other
• Nonsuperimposable mirror images are images
where not all points coincide when the images
are laid upon each other
Chirality
Any organic molecule that contains a carbon atom with four different groups
attached to it in a tetrahedral orientation possesses handedness.

A chiral center is an atom in a molecule that has four different groups

tetrahedrally bonded to it.

A chiral molecule is a molecule whose mirror images are not superimposable.

An achiral molecule is a molecule whose mirror images are superimposable.

 Chirality
Organic molecules, especially monosaccharides, may contain more than one chiral center.
Chirality
• In human body chemistry, right-handed and left-handed forms of a molecule
often elicit different responses within the body.
• Sometimes both forms are biologically active, each form giving a different
response; sometimes both elicit the same response, but one form’s response is
many times greater than that of the other; and sometimes only one of the two
forms is biochemically active.
 Stereoisomerism:
Enantiomers and
Diastereomers

• Stereoisomers are isomers that

have the same molecular and
structural formulas but differ in
the orientation of atoms in space.
• Enantiomers are stereoisomers
whose molecules are
nonsuperimposable mirror
images of each other.
• Diastereomers are stereoisomers
whose molecules are not mirror
images of each other.
 Fischer Projection Formula

• A Fischer projection formula is a two-dimensional structural notation for showing the

spatial arrangement of groups about chiral centers in molecules.
Fischer Projection
Formula

• In a Fischer projection formula a

chiral center is represented as the
intersection of vertical and
horizontal lines. The atom at the
chiral center, which is almost
always carbon, is not explicitly
shown.
 Fischer • In Fischer projection formulas for
monosaccharides, the monosaccharide carbon
Projection chain is positioned vertically with the carbonyl
Formula group (aldehyde or ketone) at or near the top.
 Fischer
Projection
Formula
The smallest monosaccharide
that has a chiral center is the
compound glyceraldehyde
 • The handedness (right and left) of these two enantiomers is specified by using
the designations D and L.
• The enantiomer with the chiral center —OH group on the right in the Fischer
Fischer Projection Formula projection formula is by definition the right-handed isomer (D-glyceraldehyde),
and the enantiomer with the chiral center —OH group on the left in the Fischer
projection formula is by definition the left-handed isomer (L-glyceraldehyde).
 Fischer Projection
Formula

• Now consider Fischer

projection formulas for the
compound 2,3,4-
trihydroxybutanal, a
monosaccharide with four
carbons and two chiral
centers.
Fischer Projection Formula
 Fischer • The carbon chain is numbered starting at the
carbonyl group end of the molecule, and the
Projection highest-numbered chiral center is used to
Formula determine D or L configuration.
Properties of Enantiomers

Nearly all the properties of a pair of enantiomers are the same; they
have identical boiling points and melting points

Enantiomers exhibit different properties in only two areas: (1) their

interaction with plane-polarized light and (2) their interaction with
other chiral substances.
Interaction of
Enantiomers with
Plane-Polarized Light
• All light moves through space with
a wave motion. Ordinary light
waves—that is, unpolarized light
waves—vibrate in all planes at right
angles to their direction of travel.
• Plane-polarized light waves, by
contrast, vibrate in only one plane
at right angles to their direction of
travel.
Interaction of Enantiomers with Plane-
Polarized Light

Ordinary light can be converted to plane-polarized light by passing it through

a polarizer, an instrument with lenses or filters containing special types of
crystals.

When plane-polarized light is passed through a solution containing a single

enantiomer, the plane of the polarized light is rotated counterclockwise (to
the left) or clockwise (to the right), depending on the enantiomer.
Interaction of Enantiomers with Plane-
Polarized Light
The extent of rotation depends on the concentration of the enantiomer as
well as on its identity.

Furthermore, the two enantiomers of a pair rotate the plane-polarized

light the same number of degrees, but in opposite directions.

If a 0.50 M solution of one enantiomer rotates the light 30 degrees to the

right, then a 0.50 M solution of the other enantiomer rotates the light 30
degrees to the left.
 Enantiomers are said to be optically active
because of the way they interact with plane-
polarized light.
An optically active compound is a compound
Dextrorotatory that rotates the plane of polarized light
and
Levorotatory A dextrorotatory compound is a chiral
Compounds compound that rotates the plane of polarized
light in a clockwise direction.
A levorotatory compound is a chiral compound
that rotates the plane of polarized light in a
counterclockwise direction.
Dextrorotatory • A plus or minus sign inside parentheses is used
to denote the direction of rotation of plane-
and polarized light by a chiral compound. The
notation (+) means rotation to the right
Levorotatory (clockwise), and (-) means rotation to the left
Compounds (counterclockwise).
Dextrorotatory and Levorotatory Compounds
The handedness of enantiomers (D or L) and the direction of rotation of plane-
polarized light by enantiomers [(+) or (-)] are not connected entities.

There is no way of knowing which way an enantiomer will rotate light until it is
examined with a polarimeter.

Not all D enantiomers rotate plane-polarized light in the same direction, nor do
all L enantiomers rotate plane-polarized light in the same direction.

Some D enantiomers are dextrorotatory; others are levorotatory.

Dextrorotatory and Levorotatory Compounds

Both handedness and direction of rotation of plane-polarized light can

be incorporated into the name of an enantiomer.

For example, the notation D-(+)-mannose specifies that the right-

handed isomer of the monosaccharide mannose rotates plane-
polarized light in a clockwise direction (to the right).
Interactions between Chiral Compounds
The two members of an enantiomeric pair have the same interaction with achiral molecules and different interactions with chiral
molecules. We find that

1. Enantiomers have identical boiling points, melting points, and densities because such properties depend on the strength of
intermolecular forces, and intermolecular force strength does not depend on chirality. Intermolecular force strength is the same for
both forms of a chiral molecule because both forms have identical sets of functional groups.

2. A pair of enantiomers have the same solubility in an achiral solvent, such as ethanol, but differing solubilities in a chiral solvent,
such as D-2-butanol.

3. The rate and extent of reaction of enantiomers with another reactant are the same if the reactant is achiral but differ if the
reactant is chiral.

4. Receptor sites for molecules within the body have chirality associated with them. Thus enantiomers always generate different
responses within the human body as they interact at such sites. Sometimes the responses are only slightly different, and at other
times they are very different.
Classification of Monosaccharides

Monosaccharides can be classified according to the number of carbon

atoms present

A three-carbon monosaccharide is called a triose, and those that

contain four, five, and six carbon atoms are called tetroses, pentoses,
and hexoses, respectively.
Classification of Monosaccharides

Monosaccharides are classified as aldoses or ketoses on

the basis of type of carbonyl group present

An aldose is a monosaccharide that contains an aldehyde

functional group.

A ketose is a monosaccharide that contains a ketone

functional group
 Monosaccharides are often classified by both their
number of carbon atoms and their functional group.

A six-carbon monosaccharide with an aldehyde functional

group is an aldohexose; a five-carbon monosaccharide
Classification of with a ketone functional group is a ketopentose.
Monosaccharides

Monosaccharides are also often called sugars. The word

sugar is associated with “sweetness,” and most (but not
all) monosaccharides have a sweet taste. The designation
sugar is also applied to disaccharides, many of which also
have a sweet taste.
Biochemically Important Monosaccharides
Of the many monosaccharides, six that are particularly important in the
functioning of the human body are the trioses D-glyceraldehyde and
dihydroxyacetone and the D forms of glucose, galactose, fructose, and ribose

Glucose and galactose are aldohexoses, fructose is a ketohexose, and ribose is

an aldopentose.

All six of these monosaccharides are water soluble, white, crystalline solids.
D-glyceraldehyde
and
Dihydroxyacetone
• The simplest of the
monosaccharides, these two
trioses are important intermediates
in the process of glycolysis, a series
of reactions whereby glucose is
converted into two molecules of
pyruvate
 D-glucose

• Of all monosaccharides, D-
glucose is the most
abundant in nature and the
most important from a
human nutritional
standpoint.
 Ripe fruits, particularly ripe grapes (20%–30%
glucose by mass), are a good source of glucose,
which is often referred to as grape sugar.

The name dextrose draws attention to the fact

that the optically active D-glucose, in aqueous
solution, rotates plane-polarized light to the right.
D-glucose
The term blood sugar draws attention to the fact
that blood contains dissolved glucose

Cells use glucose as a primary source of energy

D-glucose

• Two hormones, insulin and

glucagon, have important roles in
keeping glucose blood
concentrations within the normal
range, which is required for normal
body function.
D-galactose
D-galactose
D-Galactose is seldom encountered as a free monosaccharide. It is, however, a
component of numerous important biochemical substances.

In the human body, galactose is synthesized from glucose in the mammary glands for use
in lactose (milk sugar), a disaccharide consisting of a glucose unit and a galactose unit.

D-Galactose is sometimes called brain sugar because it is a component of glycoproteins

(protein–carbohydrate compounds) found in brain and nerve tissue.

D-Galactose is also present in the chemical markers that distinguish various types of
blood—A, B, AB, and O
 D-fructose

• D-Fructose is biochemically the

most important ketohexose. It is
also known as levulose and fruit
sugar
• Aqueous solutions of naturally
occurring D-fructose rotate
plane-polarized light to the left;
hence the name levulose.
• The sweetest-tasting of all
sugars, D-fructose is found in
many fruits and is present in
honey in equal amounts with
glucose.
 D-ribose

• D-Ribose is a pentose.
• If carbon 3 and its
accompanying —H and —
OH groups were eliminated
from the structure of D-
glucose, the remaining
structure would be that of
D-ribose.
 • D-Ribose is a component of a variety of complex molecules,
including ribonucleic acids (RNAs) and energy-rich compounds
D-ribose such as adenosine triphosphate (ATP).
• The compound 2-deoxy-D-ribose is also important in nucleic acid
chemistry. This monosaccharide is a component of DNA molecules.
 Cyclic Forms of
Monosaccharides

• The cyclic forms of

monosaccharides result
from the ability of their
carbonyl group to react
intramolecularly with a
hydroxyl group, resulting to
cyclic hemiacetal
• hemiacetals have both an —
OH group and an —OR
group attached to the same
carbon atom.
 Addition across the carbon–oxygen double bond with
its accompanying ring formation produces a chiral
center at carbon 1, so two stereoisomers are possible.

These two forms differ in the orientation of the —OH

group on the hemiacetal carbon atom (carbon 1).
Cyclic Forms of
Monosaccharides In a-D-glucose, the —OH group is on the opposite side
of the ring from the CH2OH group attached to carbon
5.

In b-D-glucose, the CH2OH group on carbon 5 and the

—OH group on carbon 1 are on the same side of the
ring.
 • In an aqueous solution, a dynamic equilibrium exists among the a, b, and open-
chain forms, and there is continual interconversion among them
Cyclic Forms of
• For example, a freshly mixed solution of pure a-D-glucose slowly converts to a
Monosaccharides mixture of both a- and b-D-glucose by an opening and a closing of the cyclic
structure.
 Intramolecular cyclic hemiacetal
formation and the equilibrium between
forms associated with it are not restricted
to glucose.
Cyclic Forms of
Monosaccharides
All aldoses with five or more carbon
atoms establish similar equilibria, but
with different percentages of the alpha,
beta, and open-chain forms. Fructose and
other ketoses with a sufficient number of
carbon atoms also cyclize.
 Cyclic Forms of
Monosaccharides

• Galactose, like glucose, forms a

six-membered ring, but both D-
fructose and D-ribose form a
five-membered ring.
• d-Fructose cyclization involves
carbon 2 (the keto group) and
carbon 5, which results in two
CH2OH groups being outside the
ring (carbons 1 and 6).
• D-Ribose cyclization involves
carbon 1 (the aldehyde group)
and carbon 4.
 A cyclic monosaccharide containing a six-
atom ring is called a pyranose, and one
containing a five-atom ring is called furanose

Such nomenclature leads to more specifc

Cyclic Forms of names for the cyclic forms of
Monosaccharides monosaccharides— names that specify ring
size.

The more specific name for a-D-glucose is a-

D-glucopyranose, and the more specific name
for a-D-fructose is a-D-fructofuranose
 Haworth • A Haworth projection formula is a two-
dimensional structural notation that specifies
Projection the three-dimensional structure of a cyclic form
Formulas of a monosaccharide
 Haworth
Projection
Formulas

• In a Haworth projection, the hemiacetal ring system is viewed “edge on”

with the oxygen ring atom at the upper right (six-membered ring) or at
the top (five-membered ring).

Haworth Projection Formulas
• The D or L form of a monosaccharide is determined by the position of
the terminal CH2OH group on the highest-numbered ring carbon atom.
• In the D form, this group is positioned above the ring. In the L form,
which is not usually encountered in biochemical systems, the terminal
CH2OH group is positioned below the ring.
 • a or b configuration is determined by the position of the —OH group
on carbon 1 relative to the CH2OH group that determines D or L series.
Haworth Projection Formulas
• In a b configuration, both of these groups point in the same direction;
in an a configuration, the two groups point in opposite directions
 • In situations where a or b configuration does not matter, the —OH
Haworth Projection Formulas group on carbon 1 is placed in a horizontal position, and a wavy
line is used as the bond that connects it to the ring.
 • Any —OH group at a chiral center that is to the right in a Fischer
projection formula points down in the Haworth projection formula.
Haworth Projection Formulas
• Any group to the left in a Fischer projection formula points up in
the Haworth projection formula.
Which of the monosaccharides glucose, fructose, galactose, and ribose has each of
the following structural characteristics? There may be more than one correct
answer for a given characteristic
a. It is a hexose.
b. It is an aldose.
c. Its cyclic form has a 5-membered ring.
d. Its cyclic form exists in alpha and beta forms
Which of the monosaccharides glucose, fructose, galactose, and ribose has each of
the following structural characteristics? There may be more than one correct
answer for a given characteristic.
a. It is a pentose.
b. It is a ketose.
c. Its cyclic form has a 6-membered ring.
d. Its cyclic form has two carbon atoms outside the ring.
Reaction of Monosaccharides
• Five important reactions of monosaccharides are oxidation to acidic sugars, reduction to
sugar alcohols, glycoside formation, phosphate ester formation, and amino sugar
formation.
Oxidation to Produce Acidic Sugars
Oxidation to Produce
Acidic Sugars

• Monosaccharide oxidation can

yield three different types of
acidic sugars. The oxidizing agent
used determines the product.
• Weak oxidizing agents, such as
Tollens and Benedict’s solutions
oxidize the aldehyde end of an
aldose to give an aldonic acid.
• Oxidation of the aldehyde end of
glucose produces gluconic acid,
and oxidation of the aldehyde
end of galactose produces
galactonic acid.
 Because aldoses act as reducing agents in
such reactions, they are called reducing
sugars.
Oxidation to With Tollens solution, glucose reduces Ag+
Produce ion to Ag, and with Benedict’s solution,
glucose reduces Cu2+ ion to Cu+ ion
Acidic Sugars
A reducing sugar is a carbohydrate that
gives a positive test with Tollens and
Benedict’s solutions
 Under the basic conditions associated
with Tollens and Benedict’s solutions,
ketoses are also reducing sugars.
Oxidation to
Produce
Acidic Sugars In this situation the ketose undergoes a
structural rearrangement that produces
an aldose, and the aldose then reacts.
Thus all monosaccharides, both aldoses
and ketoses, are reducing sugars.
Oxidation to Produce
Acidic Sugars

• Strong oxidizing agents can

oxidize both ends of a
monosaccharide at the same
time (the carbonyl group and
the terminal primary alcohol
group) to produce a
dicarboxylic acid. Such
polyhydroxy dicarboxylic
acids are known as aldaric
acids.
• For glucose, this oxidation
produces glucaric acid.
Oxidation to Produce
Acidic Sugars

• In biochemical systems
enzymes can oxidize the
primary alcohol end of an
aldose such as glucose,
without oxidation of the
aldehyde group, to produce
an alduronic acid.
• For glucose, such an
oxidation produces D-
glucuronic acid.
Reduction to Produce
Sugar Alcohols

• The carbonyl group present in

a monosaccharide (either an
aldose or a ketose) can be
reduced to a hydroxyl group,
using hydrogen as the
reducing agent.
• For aldoses and ketoses, the
product of the reduction is
the corresponding
polyhydroxy alcohol, which is
sometimes called a sugar
alcohol.
 Glycoside Formation

• Hemiacetals can react with

alcohols in acid solution to
produce acetals.
• Acetals have two —OR groups
attached to the same carbon
atom.
• Because the cyclic forms of
monosaccharides are
hemiacetals, they react with
alcohols to form acetals, as is
illustrated here for the reaction
of b-D-glucose with methyl
alcohol.
 Glycoside Formation

• The general name for

monosaccharide acetals is
glycoside. A glycoside is an
acetal formed from a cyclic
monosaccharide by
replacement of the
hemiacetal carbon —OH
group with an —OR group
• Glycosides, like the
hemiacetals from which they
are formed, can exist in both
a and b forms
 Phosphate Ester
Formation

• The hydroxyl groups of a

monosaccharide can react with
inorganic oxyacids to form inorganic
esters
• Phosphate esters, formed from
phosphoric acid and various
monosaccharides, are commonly
encountered in biochemical systems
• For example, specific enzymes in the
human body catalyze the esterification
of the hemiacetal group (carbon 1) and
the primary alcohol group (carbon 6) in
glucose to produce the compounds
glucose 1-phosphate and glucose 6-
phosphate, respectively.
 Amino Sugar
Formation

• If one of the hydroxyl groups

of a monosaccharide is
replaced with an amino
group, an amino sugar is
produced.
• In naturally occurring amino
sugars, of which there are
three common ones, the
amino group replaces the
carbon 2 hydroxyl group.
 Amino Sugar
Formation

• Amino sugars and their N-

acetyl derivatives are
important building blocks of
polysaccharides found in
chitin and hyaluronic acid.
• The N-acetyl derivatives of D-
glucosamine and D-
galactosamine are present in
the biochemical markers on
red blood cells, which
distinguish the various blood
types.
 • A monosaccharide that has cyclic forms
(hemiacetal forms) can react with an alcohol to
form a glycoside (acetal)
Disaccharides • In disaccharide formation, one of the
monosaccharide reactants functions as a
hemiacetal, and the other functions as an
alcohol.
Disaccharides

• The bond that links the two monosaccharides of

a disaccharide (glycoside) together is called a
glycosidic linkage.
• A glycosidic linkage is the bond in a disaccharide
resulting from the reaction between the
hemiacetal carbon atom —OH group of one
monosaccharide and an —OH group on the
other monosaccharide. It is always a carbon–
oxygen–carbon bond in a disaccharide.
Maltose

• Maltose, often called malt sugar, is

produced whenever the
polysaccharide starch breaks down
• It is a common ingredient in baby
foods and is found in malted milk
• Maltose is made up of two D-
glucose units, one of which must
be a-D-glucose.
 The glycosidic linkage between the
two glucose units is called an
a(1 —> 4) linkage.

Maltose
The two —OH groups that form the
linkage are attached, respectively,
to carbon 1 of the first glucose unit
(in an a configuration) and to
carbon 4 of the second.
 Maltose

• Maltose is a reducing sugar

because the glucose unit on the
right has a hemiacetal carbon
atom (C-1). Thus this glucose unit
can open and close; it is in
equilibrium with its open-chain
aldehyde form
• This means there are actually
three forms of the maltose
molecule: a-maltose, b-maltose,
and the open-chain form
• In the solid state, the b form is
dominant
 • The most important chemical reaction of maltose is that of
hydrolysis.
Maltose • Hydrolysis of D-maltose, whether in a laboratory flask or in a living
organism, produces two molecules of D-glucose. Acidic conditions
or the enzyme maltase is needed for the hydrolysis to occur.
 • Cellobiose is produced as an
intermediate in the hydrolysis of the
polysaccharide cellulose
• Like maltose, cellobiose contains two
D-glucose monosaccharide units. It
differs from maltose in that one of the
Cellobiose D-glucose units—the one functioning
as a hemiacetal—must have a b
configuration instead of the a
configuration for maltose.
• This change in configuration results in a
b(1 —> 4) glycosidic linkage.
 Cellobiose

• Like maltose, cellobiose is a

reducing sugar, has three
isomeric forms in aqueous
solution, and upon
hydrolysis produces two D-
glucose molecules.
Cellobiose

Maltose and cellobiose have different biochemical behaviors.

These differences are related to the stereochemistry of their glycosidic linkages. Maltase, the
enzyme that breaks the glucose–glucose a(1 —> 4) linkage present in maltose, is found both in the
human body and in yeast. Consequently, maltose is digested easily by humans and is readily
fermented by yeast.

Both the human body and yeast lack the enzyme cellobiase needed to break the glucose–glucose b
(1 —> 4) linkage of cellobiose. Thus cellobiose cannot be digested by humans or fermented by yeast.
 Lactose

• Lactose is made up of a b-D-

galactose unit and a D-
glucose unit joined by a b(1
—> 4) glycosidic linkage.
 Lactose

• The glucose hemiacetal

center is unaffected when
galactose bonds to glucose
in the formation of lactose,
so lactose is a reducing
sugar (the glucose ring can
open to give an aldehyde).
 Lactose is the major sugar found in milk. This accounts for
its common name, milk sugar.

Lactose is an important ingredient in commercially

produced infant formulas that are designed to simulate
Lactose mother’s milk. Souring of milk is caused by the conversion
of lactose to lactic acid by bacteria in the milk.

Pasteurization of milk is a quick-heating process that kills

most of the bacteria and retards the souring process.
 Lactose

• Lactose can be hydrolyzed by acid

or by the enzyme lactase, forming
an equimolar mixture of galactose
and glucose.
• The enzyme needed to break the
b(1 —> 4) linkage in lactose is
different from the one needed to
break the b(1 —> 4) linkage in
cellobiose. Because the two
disaccharides have slightly different
structures, different enzymes are
required—lactase for lactose and
cellobiase for cellobiose.
 • For many people, the digestion and absorption of
lactose are a problem. This problem, called lactose
intolerance, is a condition in which people lack the
enzyme lactase, which is needed to hydrolyze
lactose to galactose and glucose.
• Deficiency of lactase can be caused by a genetic
Lactose defect, by physiological decline with age, or by
injuries to the mucosa lining the intestines. When
Intolerance lactose molecules remain in the intestine
undigested, they attract water to themselves,
causing fullness, discomfort, cramping, nausea, and
diarrhea.
• Bacterial fermentation of the lactose further along
the intestinal tract produces acid (lactic acid) and
gas, adding to the discomfort.
Sucrose
Sucrose, common table sugar, is the most abundant The two monosaccharide units present in a D-
of all disaccharides and occurs throughout the plant sucrose molecule are a-D-glucose and b-D-fructose.
kingdom. It is produced commercially from the juice
of sugar cane and sugar beets.
 Sucrose

• The glycosidic linkage is a,

b(1 —> 2) glycosidic linkage
• The —OH group on carbon 2
of D-fructose (the
hemiacetal carbon) reacts
with the —OH group on
carbon 1 of D-glucose (the
hemiacetal carbon).
 Sucrose, unlike maltose,
cellobiose, and lactose, is a
nonreducing sugar.

Sucrose
No hemiacetal is present in the
molecule, because the glycosidic
linkage involves the reducing
ends of both monosaccharides
 Sucrose

• Sucrase, the enzyme

needed to break the a, b(1
—> 2) linkage in sucrose, is
present in the human body.
Hence sucrose is an easily
digested substance.
General Characteristics
of Polysaccharides

• A polysaccharide is a polymer that contains

many monosaccharide units bonded to each
other by glycosidic linkages. Polysaccharides
are often also called glycans.
 • Important parameters that distinguish various
polysaccharides (or glycans) from each other
are:
General 1. The identity of the monosaccharide repeating
unit(s) in the polymer chain
Characteristics A homopolysaccharide is a polysaccharide
of in which only one
monomer is present.
type of monosaccharide

Polysaccharides A heteropolysaccharide is a
polysaccharide in which more than one (usually
two) type of monosaccharide monomer is
present.
 2. The length of the polymer chain.
3. The type of glycosidic linkage between
monomer units.
General 4. The degree of branching of the polymer chain
Characteristics • Unlike monosaccharides and most
disaccharides, polysaccharides are not sweet
of and do not test positive in Tollens and
Benedict’s solutions.
Polysaccharides
• They have limited water solubility because of
their size.
 • A storage polysaccharide is a polysaccharide
that is a storage form for monosaccharides and
is used as an energy source in cells.
Storage
• In cells, monosaccharides are stored in the form
Polysaccharides of polysaccharides rather than as individual
monosaccharides in order to lower the osmotic
pressure within cells.
 Starch is a homopolysaccharide containing only
glucose monosaccharide units. It is the energy-
storage polysaccharide in plants.

Two different polyglucose polysaccharides can be

Starch isolated from most starches: amylose and
amylopectin.

Amylose, a straight-chain glucose polymer, usually

accounts for 15%–20% of the starch; amylopectin, a
branched glucose polymer, accounts for the
remaining 80%–85% of the starch.
Amylose

• In amylose’s non-branched structure, the glucose units are connected by

a(1--->4) glycosidic linkages.
 • Amylopectin, the other polysaccharide in
starch, has a high degree of branching in its
polyglucose structure. A branch occurs about
once every 25–30 glucose units. The branch
points involve a(1 —> 6) linkages
Amylopectin • All of the glycosidic linkages in starch (both
amylose and amylopectin) are of the a type. In
amylose, they are all (1 —> 4); in amylopectin,
both (1 —> 4) and (1 —> 6) linkages are
present.
Glycogen

GLYCOGEN, LIKE STARCH, IS A POLYSACCHARIDE ITS FUNCTION IS THUS SIMILAR TO THAT OF LIVER CELLS AND MUSCLE CELLS ARE THE
CONTAINING ONLY GLUCOSE UNITS. IT IS THE STARCH IN PLANTS, AND IT IS SOMETIMES STORAGE SITES FOR GLYCOGEN IN HUMANS.
GLUCOSE STORAGE POLYSACCHARIDE IN REFERRED TO AS ANIMAL STARCH.
HUMANS AND ANIMALS.
Glycogen
Glycogen has a structure similar to that of amylopectin; all glycosidic
linkages are of the a type, and both (1 —> 4) and (1 —> 6) linkages are
present.

Glycogen and amylopectin differ in the number of glucose units between

branches and in the total number of glucose units present in a molecule.

Glycogen is about three times more highly branched than amylopectin,

and it is much larger, with up to 1,000,000 glucose units present.
 A structural polysaccharide is a
polysaccharide that serves as a
structural element in plant cell
walls and animal exoskeletons.
Structural
Polysaccharides
Two of the most important
structural polysaccharides are
cellulose and chitin. Both are
homopolysaccharides.
 • Cellulose, the structural component of plant cell
walls, is the most abundant naturally occurring
polysaccharide. The “woody” portions of plants—
stems, stalks, and trunks— have particularly high
concentrations of this fibrous, water-insoluble
substance
• The structural difference between cellulose and
Cellulose amylose, which gives them completely different
properties, is that the glucose residues present in
cellulose have a beta-configuration whereas the
glucose residues in amylose have an alpha-
configuration.
• The glycosidic linkages in cellulose are therefore b(1
---> 4) linkages rather than a(1 ---> 4) linkages..
 Even though it is a glucose polymer, cellulose is not a
source of nutrition for human beings. Humans lack
the enzymes capable of catalyzing the hydrolysis of
b(1 —> 4) linkages in cellulose.

Despite its nondigestibility, cellulose is still an

Cellulose important component of a balanced diet. It serves as
dietary fiber.

Dietary fiber provides the digestive tract with “bulk”

that helps move food through the intestinal tract and
facilitates the excretion of solid wastes. Cellulose
readily absorbs water, leading to softer stools and
frequent bowel action.
 Chitin is a polysaccharide that is
similar to cellulose in both
function and structure.

Chitin
Its function is to give rigidity to the
exoskeletons of crabs, lobsters,
shrimp, insects, and other
arthropods. It also occurs in the
cell walls of fungi.
 An acidic polysaccharide is a polysaccharide
with a disaccharide repeating unit in which
one of the disaccharide components is an
amino sugar and one or both disaccharide
components has a negative charge due to a
sulfate group or a carboxyl group.
Acidic
Polysaccharides
Acidic polysaccharides are
heteropolysaccharides; two different
monosaccharides are present in an
alternating pattern.
 Hyaluronic Acid

• The structure of hyaluronic

acid contains alternating
residues of N-acetyl-b-D-
glucosamine and D-
glucuronic acid.
 • Highly viscous hyaluronic acid solutions serve as
Hyaluronic lubricants in the fluid of joints and they are also
associated with the jelly-like consistency of the
Acid vitreous humor of the eye.
 Heparin

• The best known of heparin’s

biochemical functions is
that of an anticoagulant; it
helps prevent blood clots. It
binds strongly to a protein
involved in terminating the
process of blood clotting,
thus inhibiting blood
clotting.
 Molecules called glycolipids and glycoproteins
often govern how individual cells of differing
function within a biochemical system recognize
Glycolipids each other and how cells interact with invading
and bacteria and viruses.
Glycoproteins:
Cell The lipid or protein part of the glycolipid or
glycoprotein is incorporated into the cell
Recognition membrane structure and the carbohydrate
(oligosaccharide) part functions as a marker on
the outer cell membrane surface
 Cell recognition generally involves the interaction
between the carbohydrate marker of one cell and a
protein imbedded into the cell membrane of another cell.

Glycolipids
In the human reproductive process, fertilization involves a
and binding interaction between oligosaccharide markers on
Glycoproteins: the outer membrane surface of an ovulated egg and
protein receptor sites on a sperm cell membrane.
Cell
Recognition This binding process is followed by release of enzymes by
the sperm cell which dissolve the egg cell membrane
allowing for entry of the sperm and the ensuing egg–
sperm fertilization process.