CARBOHYDRATE

Monosaccharides, Disaccharides & Polysaccharides

CARBOHYDRATE
 The group of compounds known as carbohydrates
received their general name because of early
observations that they often have the formula
Cx(H2O)y—that is, they appear to be “hydrates of
carbon”
 Also characterized by the functional groups that
they contain.
Definition and Classification
 Carbohydrates are usually defined as polyhydroxy
aldehydes and ketones or substances that hydrolyze
to yield polyhydroxy aldehydes and ketones.
 Carbohydrates :
 Simple Carbohydrate : Monosaccharides
 Complex Carbohydrates: Disaccharides,
Oligosaccharides, Polysaccharides,
 MONOSACCHARIDES
 The simplest carbohydrates, those that cannot be
hydrolyzed into simpler carbohydrates.
 DISACCHARIDES
 On a molecular basis, carbohydrates that undergo
hydrolysis to produce only 2 molecules of
monosaccharide
 Hydrolyzed carbohydrates that yield 3 molecules of
monosaccharide are called TRISACCHARIDES; and
so on.
 Carbohydrates that hydrolyze to yield 2–10
molecules of monosaccharide are sometimes called
oligosaccharides.
 Carbohydrates that yield a large number of molecules
of monosaccharides (> 10) are known as
polysaccharides.
 Examples of MONOSACCHARIDES (1)

Glucose:
Sometimes called as blood sugar or
dextrose

FRUCTOSE:
Usually called levulose, found in
honey and fruits.
Example of MONOSACCHARIDES (2)

RIBOSE dan
DEOXYRIBOSE : a part of
nucleic acid

CHO CHO
H C OH H C H
H C OH H C OH
H C OH H C OH
GALACTOSE
CH2 OH CH2 OH

Ribose Deoxyribose
Classification of MONOSACCHARIDES

Monosaccharides are classified according to (1) the

number of carbon atoms present in the molecule and (2)
whether they contain an aldehyde or keto group.
A monosaccharide containing an aldehyde group is
called an ALDOSE; one containing a keto group is
called a KETOSE.
Thus, a monosaccharide containing three
carbon atoms is called a triose; one containing
four carbon atoms is called a tetrose; one
containing five carbon atoms is a pentose; and
one containing six carbon atoms is a hexose.
NUmber of atom in Name Aldode Ketose
Monosaccharides
3 Triose Aldotriose Ketotriose

4 Tetrose Aldotetrose Ketotetrose

5 Pentose Aldopentose Ketopentose

D-L Monosaccharides
 The simplest monosaccharides are the compounds
glyceraldehyde and dihydroxyacetone
(+)-glyceraldehyde is designated D-(+) glyceraldehyde and
(-)-glyceraldehyde is designated L-(-)-glyceraldehyde
Common Simple Sugar (1)
Common Simple Sugar (2)
 MONOSACCHARIDE
REPRESENTATION
 Monosakharida can be represented in the form of open
chain (acyclic) and closed chain (cyclic).
 There are 3 form to represent the monosaccharides:
Fischer projection, Haworth projection, and chair
conformation.
Formulas 1–3 are used for
the open-chain structure of
d-(+)-glucose.
Formulas 4–7 are used for the
two cyclic hemiacetal forms of
d-(+)-glucose
 FISHER Projection : Notasi D- dan L-

 Fisher projection : monosaccharide representation in the form of

open chain.
 Carbon chain is in vertical position, and aldehyde / ketone in top
section.
 When–OH group of asymetric
carbon is located on LEFT side,
the notation is L-
 When–OH group of asymetric
carbon is located on RIGHT
side, the notation is D-
Example of Fisher Projection
CYCLIC FORM OF
MONOSACCHARIDES
 Haworth projection is representation of cyclic
monosaccharides
 If the monosaccharide ring is six membered, the
compound is called a pyranose; if the ring is fve
membered, the compound is designated as a
furanose.
Fischer Projection  Haworth
Projection
Glucose in Pyranose Form
 Glucose in Furanose Form

 In furanose form, the –OH group is protonated and

attack carbonyl Carbon.
 Glucose in pyranose form is called glucofuranose.
Glycoside Formation
 When a small amount of gaseous hydrogen chloride is passed
into a solution of d-(+)-glucose in methanol, a reaction takes
place that results in the formation of anomeric methyl acetals:

 Carbohydrate acetals are generally called glycosides and an

acetal of glucose is called a glucoside. (Acetals of mannose
are mannosides, acetals of fructose are fructosides, and so on.)
Glycosides are stable in basic solutions because they are acetals.
In acidic solutions, however, glycosides undergo hydrolysis to produce
a sugar and an alcohol. The alcohol obtained by hydrolysis of a glycoside
is known as an aglycone:
REACTION OF MONOSACCHARIDES

 Enolization, Tautomerization, and Isomerization

 Oxidation
 Reduction
 Killiani-Fischer Synthesis
 Degradation Ruff
Enolization, Tautomerization, and Isomerization

 Dissolving monosaccharides in aqueous base causes

them to undergo a series of enolizations and keto–
enol tautomerizations that lead to isomerizations.
 For example, if a solution of d-glucose containing
calcium hydroxide is allowed to stand for several
days, a number of products can be isolated, including
d-fructose and d-mannose
MONOSACCHARIDE OXIDATION

 Benedict’s or Tollens’ Reagents (weak oxidating agent): Reducing

Sugars
ALDOSE  Aldonic Acid.
Benedict’s reagent (an alkaline solution containing a cupric citrate
complex ion) and Tollens’ solution [Ag+(NH3)2OH] oxidize and thus
give positive tests with aldoses and ketoses.  Basic condition  Ketose
rearrangement into Aldose  Aldonic Acid

Sugars that give positive tests with Tollens’ or Benedict’s solutions are known
as reducing sugars, and all carbohydrates that contain a hemiacetal group give
positive tests.
MONOSACCHARIDE OXIDATION

 Bromine Water: The Synthesis of Aldonic Acids

Bromine water is a general reagent that selectively oxidizes
the -CHO group to a -CO2H group, thus converting an aldose
to an aldonic acid:
MONOSACCHARIDE OXIDATION

 Nitric Acid Oxidation (Strong Oxidation): Aldaric Acids

Dilute nitric acid—a stronger oxidizing agent than bromine water—
oxidizes both the -CHO group and the terminal -CH2OH group of
an aldose to -CO2H groups, forming dicarboxylic acids are known
as aldaric acids:
MONOSACCHARIDE OXIDATION

 Enzyme Oxidation of Aldose

Enzyme can oxidize the terminal primary alcohol (-CH2OH)
WITHOUT oxidizing the aldehyde group to produce
ALDURONIC ACID.
REDUCTION OF
MONOSACCHARIDES
 Aldoses (and ketoses) can be reduced with sodium
borohydride to give compounds called alditols:
 LENGTHEN CHAIN OF ALDOSE

 KILLIANI-FISCHER: Heinrich Kiliani (Freiburg, Germany)

discovered that an aldose can be converted to have one
additional carbon

D-arabinose D-glucononitril D-mannanonitril

 Development of Kiliani-Fischer synthesis is
performed by reduction of cyanohydrin by Paladium
and Barium sulphate catalysist with water as solven
to form imine.
SHORTEN CHAIN OF ALDOSE

 Shorten chain of aldose is called RUFF DEGRADATION.

DISACCHARIDES
 Consist of 2 simple sugar link with a glycosidic
bond
DISACCHARIDES (1)

 MALTOSE
Obtain form starch hydrolysis by
enzime
Starch  Maltose  D-glucose
 Ethanol
 CELLOBIOSE
Obtain form partial hydrolisis of
cellulose
SUCROSE
It usually called ‘sugar”
consist of -glucopiranose and -fructofuranose.
LACTOSE

Consist of D-GLUCOSE dan D-GALACTOSE.

POLYSACCHARIDES
 Polysaccharides, also known as glycans, consist of
monosaccharides joined together by glycosidic linkages.
 Polysaccharides that are polymers of a single
monosaccharide are called homopolysaccharides; those
made up of more than one type of monosaccharide are
called heteropolysaccharides. Homopolysaccharides are
also classified on the basis of their monosaccharide units.
 A homopolysaccharide consisting of glucose
monomeric units is called a glucan; one consisting of
galactose units is a galactan, and so on.
STARCH
 Three important polysaccharides, all of which are
glucans, are starch, glycogen, and cellulose.
 Starch occurs as microscopic granules in the roots,
tubers, and seeds of plants. Corn, potatoes, wheat,
and rice are important commercial sources of starch.
Heating starch with water causes the granules to
swell and produce a colloidal suspension from which
two major components can be isolated. One fraction
is called amylose and the other amylopectin. Most
starches yield 10–20% amylose and 80–90%
amylopectin.
AMILOSE

 Amylose typically consists of more than 1000 d-

glucopyranoside units connected in a linkages
between C1 of one unit and C4 of the next
AMILOPECTIN

 Amylopectin has a structure similar to that of amylose [i.e.,

(14) links], except that in amylopectin the chains are
branched. Branching takes place between C6 of one glucose
unit and C1 of another and occurs at intervals of20–25
glucose units
GLICOGEN
 Glycogen has a structure very much like that of
amylopectin; however, in glycogen the chains are
much more highly branched.
 Glycogen has a very high molecular weight.
Studies of glycogens isolated under conditions that
minimize the likelihood of hydrolysis indicate
molecular weights as high as 100 million.
CELLULOSE
 Cellulose contains d-glucopyranoside units linked in (1  4)
fashion in very long unbranched chains. Unlike starch and
glycogen, however, the linkages in cellulose are b-glycosidic
linkages
 Different of Starch – Cellulose - Glycogen

 Bond configuration glycogen: starch , cellulose


 Molecular structure
SUGARS THAT CONTAIN NITROGEN

 GLYCOSAMINE : A sugar in which an amino

group replaces the anomeric –OH.
Examples are b-d-glucopyranosylamine and
adenosine
SUGARS THAT CONTAIN NITROGEN

 Glycosylamines : A sugar in which an amino group

replaces the anomeric –OH.
Examples are b-d-glucopyranosylamine and
adenosine
SUGARS THAT CONTAIN NITROGEN

 AMINO SUGAR: A sugar in which an amino group replaces a

nonanomeric -OH group. D-Glucosamine is an example of
an amino sugar. In many instances the amino group is
acetylated as in N-acetyl-d-glucosamine. N-Acetylmuramic
acid is an important component of bacterial cell walls.
 D-Glucosamine can be obtained by hydrolysis of
chitin, a polysaccharide found in the shells of
lobsters and crabs and in the external skeletons of
insects and spiders.