Carbohydrates

Chapter
Chapter 11

DR. LEONARDO C. MEDINA, JR.

1
 Chapter Outline
1. Carbohydrates: A First 4. Monosaccharides
Class of Biochemicals
5. Structure of Glucose and
2. Classification of Other Aldoses
Carbohydrates
3. Importance of
Carbohydrates

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 Chapter Outline (continued)
6. Cyclic Structure of 11. Structures and Properties
Glucose; Mutarotation of Disaccharides
7. Hemiacetals and Acetals 12. Sweeteners and Diet
8. Structures of Galactose 13. Redox Reactions of
and Fructose Monosaccharides
9. Pentoses 14. Polysaccharides Derived
10. Disaccharides from Glucose

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Carbohydrates:
A First Class of
Biochemicals
4
• Carbohydrates are generally defined as
polyhydroxy aldehydes or ketones or
substances that yield these compounds
when hydrolyzed. H

CHO H C OH

H C OH C O

H C OH H C OH

H H
glyceraldehyde dihydroxyacetone 5
Classification
of
Carbohydrates
6
A carbohydrate can be classified
as:
1.monosaccharide
2.disaccharide
3.oligosaccharide
4.polysaccharide
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 Monosaccharides
• A monosaccharide is a carbohydrate that
cannot be hydrolyzed to simpler
carbohydrate units.
• The monosaccharide is the basic
carbohydrate unit of cellular metabolism.

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 Disaccharides
• A disaccharide yields two
monosaccharides – either alike or
different – when hydrolyzed:
H+ or
disaccharide + water  2 monosaccharides
enzymes

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 Monosaccharides & Disaccharides
• Disaccharides are often used by plants or
animals to transport monosaccharides from
one cell to another.
• The monosaccharides and disaccharides
generally have the ending –ose – for example,
glucose, sucrose, and lactose.
• These are water-soluble carbohydrates, which
have a characteristically sweet taste and are
called sugars.
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 Oligosaccharides
• An oligosaccharide has two to six
monosaccharide units linked together.

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 Polysaccharides
• A polysaccharide is a macromolecular substance
that can be hydrolyzed to yield many
monosaccharide units:

H+ or
polysaccharide + water  monosaccharides
enzymes

• Polysaccharides are important structural

supports, particularly in plants, and also serve
as a storage depot for monosaccharides, which
cells use for energy.
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Other Ways to Classify Carbohydrates
• As a triose, tetrose, pentose, hexose, or
heptose
• As an aldose or ketose
• As a D or L isomer
• As a (+) or (-) isomer
• As a furanose or a pyranose
• As having an alpha () or beta ()
configuration
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Importance of
Carbohydrates

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 Importance of Carbohydrates
1. Carbohydrates are very effective
energy-yielding nutrients.
2. Carbohydrates can serve as very
effective building materials.
3. Carbohydrates are important water-
soluble molecules.

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Monosaccharides

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 Monosaccharides
• The hexose monosaccharides are the most
important carbohydrate sources of cellular
energy.
• Three hexoses – glucose, galactose, and
fructose – are of major significance in
nutrition.
– All three have the same formula, C6H12O6, and
thus deliver the same amount of cellular energy.
– They differ in structure, but are biologically
interconvertible.

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• Glucose (dextrose) is the most important of
the monosaccharides.
• It is an aldohexose and is found in the free
state in plant and animal tissue.
CHO

H OH

HO H

H OH

H OH

CH2OH 18
• Galactose is also an aldohexose and
occurs, along with glucose, in lactose and
in many oligo- and polysaccharides such
as pectin and gums. CHO

H OH

HO H

HO H

H OH

CH2OH 19
• Fructose, also know as levulose, is a ketohexose
that occurs in fruit juices, honey, and along
with glucose, as a constituent of sucrose.
CH2OH

HO H

H OH

H OH

CH2OH 20
Structures of Glucose
and Other Aldoses

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 Epimers
• Any two monosaccharides that differ
only in the configuration around a
single carbon atom are called epimers.
• D- and L-glyceraldehyde are epimers.
CHO CHO

H C OH HO C H

CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde 22
 Configurations of the D-family of aldoses. The
hydroxyl group on the new chiral carbon atom,
added in going from triose to tetrose to pentose to
hexose, is shown in red.
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Configurations of the D-family of aldoses.
The hydroxyl group on the new chiral carbon
atom, added in going from triose to tetrose to
pentose to hexose, is shown in red.

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Configurations of the D-family of aldoses. The
hydroxyl group on the new chiral carbon atom,
added in going from triose to tetrose to pentose to
hexose, is shown in red.
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 An example of the Kilani-Fischer synthesis in which two
aldotetrose molecules are formed from an aldotriose
molecule. 26
 Cyclic Structure of
Glucose; Mutarotation

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Mutarotation
of D-glucose

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 Anomers
• When two cyclic isomers differ only
in their stereo arrangement about the
carbon involved in mutarotation, they
are called anomers.

• Mutarotation is the process by

which anomers are interconverted.

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 Three-dimensional representations of the chair form
of -D-glucopyranose
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Hemiacetals and
Acetals
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• Cyclic structures of monosaccharides are
intramolecular hemiacetals.
• Five- or six-membered rings are especially
stable.
CH2OH
hemiacetal structure
O in -D-glucopyranose

OH

HO HO
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HO
 Glycoside
• When a monosaccharide hemiacetal reacts with
an alcohol, the product is an acetal.
• In carbohydrate terminology, this acetal
structure is called a glycoside.
CH2OH
acetal structure
O
OH

HO RO
glycosidic linkage
HO 33
Structures of Galactose
and Fructose

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 Galactose
CHO CH2OH
CH2OH

H OH
OH OH O OH
O
HO H 
OH OH
HO H

H OH HO

CH2OH OH HO

D-galactose -D-galactopyranose -D-galactopyranose

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 Fructose
CH2OH

O
CH2OH OH

HO H O 

H OH OH

H OH
CH2OH

CH2OH
OH 36
Disaccharides

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 Disaccharides
• Disaccharides are carbohydrates composed
of two monosaccharide residues united by a
glycosidic linkage.
• sucrose + water H+ or
sucrase
glucose + fructose

• lactose + water 
H+ or
lactase
galactose + glucose

or glucose + glucose

• maltose + water H+
maltase
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Structures and
Properties of
Disaccharides
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• Disaccharides contain an acetal
structure (glycosidic linkage), and
some also contain a hemiacetal
CH2OH CH2OH
structure.
• Maltose: O O
HO OH

OH O HO

OH HO

-1,4-glycosidic linkage 40
••Sweeteners
Sweeteners
and Diet

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42
Redox Reactions of
Monosaccharides

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 Oxidation
• The aldehyde groups in monosaccharides can
be oxidized to monocarboxylic acids by mild
oxidizing agents such as bromine water.
CHO COOH

H OH H OH

HO H HO H
+ Br2 + H2O + 2HBr
H OH H OH

H OH H OH
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CH2OH CH2OH
 Reduction
• Monosaccharides can be reduced to their
corresponding polyhydroxy alcohols by
reducing agents such as H2/Pt or sodium
amalgam, Na(Hg).
CHO CH2OH

H OH H OH

HO H HO H
+ H2 / Pt
H OH H OH

H OH H OH

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CH2OH CH2OH
 Redox Test for Carbohydrates
• Under prescribed conditions, some
sugars reduce silver ions to free silver,
and copper (II) ions to copper (I) ions.

• Such sugars are called reducing

sugars.

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Polysaccharides
Derived from
Glucose
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 Starch
• Starch is found in plants, mainly in the seeds,
roots, or tubers.
• Corn, wheat potatoes, rice and cassava are the
chief sources of dietary starch.
• The two main components of starch are
amylose and amylopectin.
– Amylose molecules are unbranched chains
composed of about 25-1300 -D-glucose units
joined by -1,4-glycosidic linkages.

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Representation of amylose.
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 Glycogen
• Glycogen is the energy-storage carbohydrate of
the animal kingdom.
• It is formed by the polymerization of glucose
and is stored in the liver and in muscle tissues.
• Structurally, it is very similar to the
amylopectin fraction of starch, except that it is
more highly branched.
• The -1,6-glycosidic linkages occur on one of
every 12-18 glucose units.
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 Cellulose
• Cellulose is the most abundant organic
substance found in nature.
• It is the chief structural component of
plants and wood.

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Two representations of
cellulose. In the three-
dimensional drawing,
note the hydrogen
bonding that links the
extended cellulose
polymers to form
cellulose fibers.

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