Carbohydrate = Polyhydroxy aldehyde or polyhydroxy

ketone
Functions of Carbohydrates
Provide energy for life processes through metabolism
Are structural and protective materials for living organisms
Are precursors for biosynthesis of proteins, lipids and
nucleic acids
Are components of DNA & RNA
Are components of cell membranes that aid in cell
recognition and/or trigger physiological processes such as cell
growth, immune response and fertilization.

 These are the simplest saccharides. They serve as

building blocks for the larger saccharides.
Classification: Aldoses or Ketoses

 Monosaccharides are referred to by the number of

carbon atoms in the molecule: 4 Cs = tetrose;
5 Cs = pentose; 6 Cs = hexose; etc.

 Stereoisomerism: the
monosaccharides contain
one or more chiral
carbons. Each
compound has an
enantiomer and each
pair of enantiomers is a
diastereomer of the
other stereoisomers.
The total number of
stereoisomers = 2n,
where n = # of chiral Cs

 The aldohexoses have a total of 4 C*, how many

stereoisomers are there?
Total # = 24 = 16
That means that there are 8 pairs of enantiomers; Each pair
of enantiomers is a diastereomer of the other stereoisomers.

 What is the total number of isomers for the

ketohexoses? How many pairs of enantiomers are
there?

 What is the total number of isomers for the

ketohexoses? How many pairs of enantiomers are
there?
23 = 8; there are 4 pairs of enantiomers

 Ribose is the sugar in

the nucleic acid RNA
Deoxyribose is the
sugar in the nucleic
acid DNA
Deoxy denotes a
missing OH group.
Note that the carbon is
achiral.

 An alcohol can react with an aldehyde or ketone to form a

hemiacetal.
Open chain hemiacetals are not very stable.
Cyclic hemiacetals are much more stable.
When the aldehyde and the OH are part of the same molecule, the
hemiacetal formed is cyclic. This is the case with monosaccharides.

To draw the hemiacetal structure of a

monosaccharide:
1. Draw the Fischer projection of the open
structure and then turn it sideways.

2. Rotate the bond between C4 and C5 to bring

the C5 OH group close to the carbonyl group.

3. Add the alcohol to

the carbonyl group.
The OH is bonded
to the carbon and
the H to the O.
1. If the OH is down, it
is the anomer.
2. If the OH is up, it is
the anomer.
3. Both anomers are
present in the
mixture.

 In solution, the open chain form of monosaccharides

is in equilibrium with the hemiacetals, which are
cyclic.
Each sugar has an (-OH down) and a anomer (-OH up)
Cyclic anomers with a six-membered ring are called
pyranoses
Cyclic anomers with a five-membered ring are called
furanoses
An anomer is a diastereomer that differs only in the
configuration of one chiral center. In the case of the
hemiacetals, that center is the hemiacetal carbon

Draw the furanose structures for

D-Fructose which is shown below.

Draw the furanose structures for

D-Fructose which is shown below.

 Mutarotation of sugar solution Example,

glucose
Pure -D-glucose has a rotation of +112.2o.
Pure -D-glucose has a rotation of +18.7o.
On dissolving either one, the solution
undergoes a gradual change in rotation until
it reaches an equilibrium value of +52.7o.
At this point there is 36% - and 64% -Dglucose in the mixture

 Oxidation of the Aldehyde Group

Mild oxidizing agents, such as Benedicts Reagent [copper
(II) citrate] oxidize the aldehyde carbonyl to a carboxylic
acid (blue to red indicates positive test)
Sugars with an aldehyde group are reducing sugars

 Acetal Formation: Production of Glycosides

Acid catalyzed dehydration with an alcohol present
produces an acetal
Acetals of carbohydrates are called glycosides; the bond
between the groups is called a glycosidic linkage.

Show the formation of methyl and -glycosides from the reaction

of fructose and methanol.

Show the formation of methyl aand b-glycosides from the reaction

of fructose and methanol.

 Disaccharides are sugars that consist of two

monosaccharides joined by a glycosidic linkage
The features that characterize a disaccharide are
The monosaccharides that form it
The type of glycosidic linkage ( or )
The positions of glycosidic linkage
(1 1) and (1 4) are the most common.
The first number is the hemiacetal carbon (1 for
aldehydes; 2 for ketones)
The second number indicates the position of the carbon to
which it is attached on the other sugar residue

 Corn sugar produced by partial digestion of starch by amylase

Maltose is formed by the dehydration between two D-glucose
molecules
The glycosidic linkage is (1 4)
Maltose is a reducing sugar because it is an aldehyde. It undergoes
mutarotation in solution.

In solution, maltose is in equilibrium with all three

forms.
Note: In the open chain the first sugar is cyclic, but the
second one is open because of the hemiacetal carbon.
What is the difference between -maltose and maltose?

 Produced by partial hydrolysis of cellulose by cellulase or by

acid catalysis.
Formed by the dehydration between two D-glucose molecules
Linkage is
It is a reducing sugar (why?) It undergoes mutarotation in solution.

You Cant Eat Cellobiose

The 1-4--D-glucopyranosyl linkage in cellobiose is not
attacked by any digestive enzyme
The 1-4--D-glucopyrnaosyl linkage in maltose is a
substrate for digestive enzymes and cleaves to give glucose

 Milk sugar formed by dehydration of D-galactose and

D-glucose
It is a reducing sugar and undergoes mutarotation in solution

A disaccharide that occurs naturally in milk

Lactose is a reducing sugar. It exhibits mutarotation
It is 1,4--D-galactopyranosyl-D-glucopyranoside
The structure is cleaved in digestion to glucose and
galactose

 Cane sugar, beet sugar. Made up of D-glucose and

D-fructose.
Linkage is (1 2) between the two sugars
It is an acetal not a hemiacetal. Is it a reducing sugar?

 Polysaccharides are made up of large numbers of

repeating monosaccharide residues bonded together.
Some contain only one monosaccharide unit other
contain two or more monosaccharide units.
Structural Differences
Monosaccharide units
The position of OH groups that are part of the linkage
Whether the linkage is or (when it is through the
hemiacetal carbon)
Presence or absence of branching

 Starch and glycogen are storage or nutritional

polysaccharides (they store glucose)
Starch is deposited as 10 to 30 % amylose and 70
90 % amylopectin.
Amylose is a straight chain polymer of (1 4)
linkages of D-glucose (see below)

 Amylopectin is a branched polymer with (1 4)

linkages of D-glucose in the straight chain and (1 6)
linkages that form the branches
Glycogen is similar to amylopectin but has more
branching

Cellulose is a structural polysaccharide that is formed by

(1 4) linkages of D-glucose.
The chains form ribbons that are held together by H-bonds. This
makes it very strong for structural purposes.

 Deoxy sugars have an

an H.

OH group is replaced by

Derivatives of 2-deoxyribose are the fundamental units

of DNA (deoxyribonucleic acid)

Cell-Surface Carbohydrates
Polysaccharides are centrally involved in cellcell recognition how one type of cell distinguishes itself from another
Small polysaccharide chains, covalently bound by glycosidic links
to hydroxyl groups on proteins (glycoproteins), act as biochemical
markers on cell surfaces, determining such things as blood type

This compound is:

A) an aldotetrose B) a ketotetrose C) an aldohexose D) a

ketohexose

This compound is a(an):

A) ketopentose B) aldopentose C)
ketotetrose D) aldotetrose

The following structures are:

A) enantiomers of each other B) stereoisomers (diastereomers)

of each other
C) hexoses of the L-configuration D) constitutional isomers

This compound is a(an):

A)
B)

-D-glucopyranose
-D-glucopyranose

C)
D)

-D-fructofuranose
-D-fructofuranose

A red precipitate forms when a solution of D-glucose is tested with

Benedict's reagent. Which reactions are taking place?
I mutarotation
II oxidation
III reduction
A) I and II only B) II and III only C) I and III only D) I, II, and III
When a solution of D-sorbose is tested with Benedict's reagent, a
red precipitate forms because:
A) the aldehyde group of the sugar is oxidized by copper(II) to a
carboxyl group.
B) the hemiacetal reacts with copper(II) to form an alcohol group.
C) the sugar is converted into an aldose by copper(II).
D) the sugar forms an insoluble copper(II) salt.

True or false: The sugar shown below is a reducing sugar.

True or false: The sugar shown below contains a pyranose ring.

What are the structural differences between amylose and amylopectin?

Both amylose and amylopectin contain linear polymers of D-glucose linked
by (14) glycosidic linkages, but amylose is linear and unbranched
whereas amylopectin is branched with (16) linkages for the branch.
Both compounds are starches that can be swollen by water.

What are the structural differences between cellulose and starch, and of what
significance is this difference to humans?
Both are composed of glucose; however, cellulose is a linear molecule with
(14) glycosidic linkages, while starch is made up of two types of
molecules, amylose and amylopectin, both of which contain (14)
glycosidic linkages. Humans have the enzyme amylase which facilitates
complete digestion of starch to glucose, but humans do not possess
cellulase to cleave (14) linkages. Therefore, all cellulose passes out of
the body.