Carbohydrates

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 AAO
1. Carbohydrates Structure, Function and Metabolism (1)
Chapter i. Monosaccharides, Polysaccharides
ii. Structural Configurations and Isomerism.

overview iii. Chemicals Properties of Carbohydrates.

iv. The Central Role of ATP

AAO
2. Carbohydrates Structure, Function and Metabolism (2)
i. Glycolytic Pathways
ii. TCA Cycle
iii. Bioenergetics and Oxidative Phosphorylation
iv. Sources of Energy
AAO
3. Carbohydrates Structure, Function and Metabolism (3)
i. Gluconeogenesis. Glycogen
ii. Metabolism
iii. Pentose Phosphate Pathway.
iv. The Interrelationship Between Degradative and
Biosynthetic Pathways
LECTURE OUTLINE
1. Monosaccharide Cn(H2O)n structures
A. Aldoses and ketoses

B. Optical isomers
1. Fischer projections
2. Enantiomers
3. Diastereomers
4. Epimers

C. Cyclic structures
1. Hemiacetals and hemiketals
2. Anomers
3. Haworth projections
4. Furanoses and pyranoses
LECTURE OUTLINE (2)
2. Monosaccharide reactions
A. Oxidation-reductions
B. Esterification reactions
C. Formation of glycosides
D. Sugar derivatives

3. Oligosaccharides
A. Sucrose
B. Lactose
LECTURE OUTLINE (3)
4. Polysaccharides
A. Cellulose and starch
B. Forms of starch
1. Amylose
2. Amylopectin
C. Glycogen
D. Chitin
E. Cell walls
1. Bacterial cell walls – peptidoglycan
2. Plant cell walls – cellulose, pectin, and lignin
F. Glycosaminoglycans

5. Glycoproteins
Lesson Learning Outcomes
Upon completion of this lecture, students should be able to:

• recognize and differentiate carbohydrates

• know the functions of carbohydrates in biochemistry

such as
i. Major energy sources
ii. Oligosaccharides play a key role in processes that take
place on surfaces of the cells. (cells-cells interaction and
immune recognition)
iii. Polysaccharides are essential structural component of
several classes of organisms. Cellulose, polysaccharides..
 Sugars: Structure and Stereochemistry
 The general formula of carbohydrates - CnH2nOn,
where n varies from 3 to 8
 However only the simple sugars (monosaccharides) fit this
formula exactly
 When a few monosaccharides are linked together, they form
oligosaccharides
 When many monosaccharides are linked together, they form
polysaccharides

 Monosaccharide units (added) to a growing carbohydrate

molecule involve the loss of one H2O for each new link formed.
Carbohydrate Nomenclature
• Monosaccharides. "Simple sugars" with the formula (C H2O)n.
The word carbohydrate refers to the fact that this class of
molecules consists of hydrates of carbon.

• Oligosaccharides. Polymeric molecule of sugar comprising 2-

10 covalently linked monosaccharide units. Often found
conjugated to other classes of biomolecules including lipids
and proteins.

• Polysaccharides. Larger polymers of simple sugars. On the

order of hundreds to thousands of monosaccharide units as
linear or branched polymers.
 Monosaccharides
• The most basic units of biologically important
carbohydrates.
• They are the simplest form of sugar and are usually
colorless, water soluble.
• Some monosaccharides have a sweet taste.
glucose (dextrose), fructose(levulose), galactose
• Monosaccharides are the building blocks
of disaccharides such as sucrose and
polysaccharides (such as cellulose and starch).
Examples of disaccharides Examples of polysaccharides
Sucrose = glucose + fructose Starch, glycogen, cellulose, chitin
Lactose = glucose + galactose
Maltose = glucose + glucose
 Monosaccharides
• Monosaccharides are classified by
their number of carbon atoms

• Trioses are simplest carbohydrate

monosaccharides

• Glyceraldehyde contains a stereo

center and exists as a pair of
enantiomers

• Mirror-images stereoisomers are

called enantiomers
 Structure
• Monosaccharides can either be polyhydroxy aldehyde (aldose)
or polyhydroxy ketone (ketose)

Aldehyde group

*look at the position of carbonyl group (C=O)

 Structure
● Monosaccharides are classified by their number of carbon
atoms

Name Formula
trios e C3 H6 O 3
tetrose C4 H8 O 4
pentose C 5 H1 0 O5
hexose C 6 H1 2 O6
heptose C 7 H1 4 O7
octose C 8 H1 6 O8
●There are only two trioses
CHO CH2 OH
CHOH C= O
CH2 OH CH2 OH
Glyceraldehyde D ihydroxyacetone
(an aldotriose) (a ketotriose)

 aldo- and keto- are often omitted and these compounds are
referred to simply as trioses; although this designation does
not tell the nature of the carbonyl group, it at least tells the
number of carbons
● Glyceraldehyde (aldose with three C) contains a
chiral carbon and exists as a pair of enantiomers

*Enantiomer = each of a pair of molecules that are mirror images of each other.
 Fischer Projections
● Fischer projection: a two dimensional
representation for showing the configuration of
tetrahedral stereocenters.
 horizontal lines represent bonds projecting forward
 vertical lines represent bonds projecting to the rear
 the carbon atom at the intersection of the horizontal
and vertical lines is not shown
convert to
CHO a Fischer CHO
projection
H C OH H OH

CH2 OH CH2 OH
D-Glyceraldehyde D-Glyceraldehyde
 D,L Monosaccharides
● According to the
conventions proposed by
Fischer
 D-monosaccharide: a
monosaccharide that, when
written as a Fischer projection,
has the -OH on the right of the
highest-numbered chiral
carbon
 L-monosaccharide: a
monosaccharide that, when
written as a Fischer projection,
has the -OH on the left of the
highest-numbered chiral
carbon
 The four aldotetroses
●Enantiomers: stereoisomers that are mirror
images
 example: D-erythrose and L-erythrose
●Diastereomers: stereoisomers that are not
mirror images
 example: D-erythrose and D-threose
Mirror Mirror
plane plane

CHO CHO CHO CHO

H OH HO H HO H H OH
H OH HO H H OH HO H
CH2 OH CH 2 OH CH2 OH CH2 OH
D-Erythrose L-Erythrose D-Threose L-Threos e
 D,L Monosaccharides

● Following are the two most common D-

aldotetroses and the two most common D-
aldopentoses
CHO CHO
CHO CHO H OH H H
H OH HO H H OH H OH
H OH H OH H OH H OH
CH2 OH CH 2 OH CH 2 OH CH2 OH
D-Erythrose D-Threose D-Ribose 2-Deoxy-D-
ribose
 What if sugar form cyclic molecule?
• Sugars especially with five or six carbon atoms
normally exist as cyclic molecule
– This is due to interaction between the functional
groups on distant carbons
– e.g. C-1 and C-5 to form hemiacetal
 What if sugar form cyclic molecule?
• Cyclic sugar can take either of two different forms (α
or β) and are called anomers of each other
• Free carbonyl (C=O) group can readily form either
α- or β-anomer
• Anomers can be converted from one form to
another through the free carbonyl species
• Fischer projection formulas do not give a
realistic picture of the bonding situation in the
cyclic forms
• Thus Haworth projection formulas are more
useful for this purpose.
– five and six-membered hemiacetals are
represented as planar pentagons or hexagons, as
the case may be, viewed through the edge.
– most commonly written with the anomeric carbon
on the right and the hemiacetal oxygen to the
back right
 Haworth Projections
CH= O CH2 OH
H OH H5 OH
HO H redraw H O
H OH OH H C
5 HO H
H OH anomeric
CH2 OH H OH carbon
D-Glucose CH OH CH2 OH
2
H5 O OH( ) H5 O
H
H + H
OH H OH H
HO H HO OH( )
H OH H OH
-D-Glucopyranos e -D-Glucopyranos e
(-D-Glucose) (-D-Glucose)
 Haworth Projections

 a six-membered hemiacetal ring is shown by the

infix -pyran
 a five-membered hemiacetal ring is shown by the
infix -furan

O O
Furan Pyran
 Conformational Formulas
 five-membered rings are so close to being planar
that Haworth projections are adequate to represent
furanoses

HOCH2 OH( ) HOCH2 H

O O
H H H H
H H H OH( )
HO OH HO OH
-D-Ribofuranose -D-Ribofuranose
(-D-Ribose) (-D-Ribose)
 Conformational Formulas
 for pyranoses, the six-membered ring is more
accurately represented as a strain-free chair
conformation

CH2 OH
HO O
HO
OH( )
OH
 - D-Glucopyranose
(chair conformation)
 Conformational Formulas
 if you compare the orientations of groups on carbons
1, 2, 3, 4, and 5 in the Haworth and chair projections
of β-D-glucopyranose, you will see that in each case
they are up-down-up-down-up respectively

CH2 OH
5
H O OH( ) 4 CH2 OH
H HO 5 O
4 OH
H 1 HO
HO H 2 1 OH( )
3 2 3
OH
H OH
-D-Glucopyranos e -D-Glucopyranos e
(Haworth projection) (chair conformation)
 Ascorbic Acid (Vitamin C)
L-Ascorbic acid (vitamin C) is synthesized both
biochemically and industrially from D-glucose

CHO
H OH both biochemial CH2 OH
and industrial
HO H syntheses H OH O
H OH O
H OH H
HO OH
CH2 OH
L-Ascorbic acid
D-Glucose (Vitamin C)
 Ascorbic Acid (Vitamin C)
L-Ascorbic acid is very easily oxidized to L-
dehydroascorbic acid
 both are physiologically active and are found in most
body fluids

CH2 OH CH2 OH
H OH O H OH O
oxidation
O O
H reduction H
HO OH O O
L-Ascorbic acid L-Dehydroascorbic acid
(Vitamin C)
 Reactions of monosaccharide
• Oxidation and reduction reactions of sugars
play an important role in biochemistry
– Oxidation of sugars  energy for organisms to
carry out life processes
– Highest yield of energy from complete oxidation
of sugar to CO2 and H2O in aerobic process
– The reverse of this reaction takes place in
photosynthesis where sugar is formed as end
product

Oxidation means the addition of oxygen to a molecule or the removal of hydrogen from a molecule.
Reduction means the addition of hydrogen to a molecule or the removal of oxygen from a molecule.
 Oxidation
●Reducing sugar: one that reduces an oxidizing
agent
 oxidation of a cyclic hemiacetal form gives a
lactone
 when the oxidizing agent is Tollens’ solution, silver
(Ag) precipitates as a silver mirror
CH2 OH CH2 OH
H OH H O
H H
OH H + A g( N H3 ) 2 + OH- O
OH H + Ag
HO OH HO
H OH H OH
A cyclic A lactone
hemiacetal (a cyclic ester)
 Disaccharides
●Sucrose
 table sugar; obtained from the juice of sugar
cane and sugar beet
 one unit of D-glucose and one unit of D-fructose
joined by an a-1,2-glycosidic bond
CH2 OH CH2 OH
D-Glucose O O
HO
OH 1 HO 1
HO -1,2-glycosidic OH
OH bond O
HOCH2 O HOCH 2 O
O
HO 2 HO 2

CH2 OH CH2 OH
D-Fructose 1 1
OH OH
 Disaccharides
●Lactose
 about 5% - 8% in human milk, 4% - 5% in cow’s milk
 one unit of D-galactose and one unit of D-glucose
joined by a β-1,4-glycosidic bond

D-glucose

D-galactose CH2 OH -1,4-glycosidic bond

O OH
4 HO CH OH
2
CH2 OH OH O CH2 OH
HO O O 4
HO O 1 O
OH 1 OH OH HO OH
OH
HO -1,4-glycosidic bond
 Disaccharides
●Maltose
 two units of D-glucose joined by an α-1,4-glycosidic
bond

-1,4-glycosidic bond

1 4 CH2 OH CH2 OH
O
HOCH2 O O OH HO 1
O OH HO
OH OH 4 CH2 OH
HO O O
HO HO OH
OH OH
 Common disaccharides
Disaccharide Unit 1 Unit 2 Bond

Sucrose (table
sugar, cane
Glucose Fructose α(1→2)β
sugar, beet sugar,
or saccharose)

Lactulose Galactose Fructose β(1→4)

Lactose (milk sugar) Galactose Glucose β(1→4)
Maltose Glucose Glucose α(1→4)
Trehalose Glucose Glucose α(1→1)α
Cellobiose Glucose Glucose β(1→4)
Structural and Functions of
Polysaccharides
 Polysaccharides
● Cellulose: the major structural component of plants,
especially wood and plant fibers
 a linear polymer of approximately 2800 D-glucose
units per molecule joined by β-1,4-glycosidic bonds
 fully extended conformation with alternating
180° flips of glucose units
 extensive intra- and intermolecular hydrogen
bonding between chains
HO- CH 2 OH 1 HO- CH 2
4 4 O
O HO O
O O 4
HO 1 O HO 1
OH HO- CH 2 OH
 Polysaccharides
● Starch: is used for energy storage in plants
 a polymers of a-D-glucose units
 amylose: continuous, unbranched chains of up to 4000 a-
D-glucose units joined by α-1,4-glycosidic bonds
 amylopectin: a highly branched polymer consisting of 24-
30 units of D-glucose joined by α-1,4-glycosidic bonds
and branches created by α-1,6-glycosidic bonds
 Polysaccharides
● Glycogen is a branced-chain polymer of α-D-glucose
like amylopectin
● It also consist of a chain of α-1,4-glycosidic bonds
and branches created by α-1,6-glycosidic bonds
● The difference is that glycogen is more branched
than amylopectins
Polysaccharides
 Polysaccharides
● Chitin: the major structural component of the
exoskeletons of invertebrates, such as insects and
crustaceans; also occurs in cell walls of algae, fungi,
and yeasts
 composed of units of N-acetyl-β-D-glucosamine
joined by β-1,4-glycosidic bonds
 Polysaccharides
● Bacterial cell walls: prokaryotic cell walls are
constructed on the framework of the repeating unit
NAM-NAG joined by β-1,4-glycosidic bonds
 Plant Cell Walls
 consist largely of cellulose
 also contain pectin which
functions as an
intercellular cementing
material
 pectin is a polymer of D-
galacturonic acid joined by
α-1,4-glycosidic bonds
 the major
nonpolysaccharide of cell
walls, especially in woody
plants, is lignin
 Polysaccharides
● Glycosaminoglycans: polysaccharides based on a
repeating disaccharide where one of the monomers is
an amino sugar and the other has a negative charge
due to a sulfate or carboxylate group
 heparin: natural anticoagulant
 hyaluronic acid: a component of the vitreous humor
of the eye and the lubricating fluid of joints
 chondroitin sulfate and keratan sulfate: components
of connective tissue
 Glycoproteins

●Glycoproteins contain carbohydrate units

covalently bonded to a polypeptide chain
antibodies are glycoproteins
carbohydrates play a role as antigenic
determinants, the portions of the antigenic
molecule that antibodies recognize and to
which they bind
 Blood Group Substances
● Membranes of animal plasma cells have large
numbers of relatively small carbohydrates bound to
them
 these membrane-bound carbohydrates act as
antigenic determinants
 among the first antigenic determinants discovered
were the blood group substances
 in the ABO system, individuals are classified
according to four blood types: A, B, AB, and O
The Generation of ATP from Glucose
• The breakdown of carbohydrates, particularly
glucose, is a major source of cellular energy. The
complete oxidative breakdown of glucose to CO2 and
H2O can be written as follows:

• The reaction yields a large amount of free energy:

ΔG°′= -686 kcal/mol. To harness this free energy in
usable form, glucose is oxidized within cells in a
series of steps coupled to the synthesis of ATP.
The Generation of ATP from Glucose
• Aerobic respiration is the oxygen-requiring
degradation of food molecules and production of
ATP, and is the one we shall be concerned with in
carbohydrate metabolism.

• There are three basic steps involved with

carbohydrate metabolism:
1. Glycolysis
2. Citric Acid Cycle (Kreb's Cycle)
3. Electron Transport Chain/Oxidative Phosphorylation
The Generation of ATP from Glucose
• Typically, a breakdown of one molecule of
glucose by aerobic respiration (i.e. involving
both glycolysis and Krebs cycle) is about 33-35
ATP. This is categorized as:

• Anaerobic breakdown by glycolysis - yielding 8-10 ATP

• Aerobic respiration by Krebs cycle - yielding 25 ATP
Thank you