Carbohydrates

Carbohydrates

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Publishing as Benjamin Cummings

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Carbohydrates
Carbohydrates are
 A major source of energy
from our diet.
 Composed of the elements
C, H, and O.
 Also called saccharides,
which means “sugars.”

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 Origin of “Carbohydrate”
Sugar general formula = CnH2nOn = Cn(H2O)n = “carbon hydrate”
= carbohydrate
Confirmation
sucrose + H2SO4 C + H2O (steam)

dehydrating agent

steam

carbon
sucrose
H2SO4
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 Importance of the topic
Why is this topic important?

•All organisms utilize carbohydrates  important biomolecules

•Nutrition: “carbos” are more than just starch and sugar

•Application of previous concepts:

functional groups
stereochemistry
other structural features
} control biological properties

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 Carbohydrates
 Widely distributed in nature
 Function
 Structural
 Source of energy
 Storage of energy
 Chemical structure
 Polyhydroxyaldehydes - aldoses
 Polyhydroxyketones - ketoses

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Carbohydrates
Carbohydrates
 Are produced by photosynthesis
in plants.
 Such as glucose are synthesized
in plants from CO2, H2O, and
energy from the sun.
 Are oxidized in living cells
(respiration) to produce CO2,
H2O, and energy.
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Types of Carbohydrates
The types of carbohydrates are
 Monosaccharides, the simplest carbohydrates.
 Disaccharides, which consist of two monosaccharides.
 Polysaccharides, which contain many
monosaccharides.

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Monosaccharides
Monosaccharides consist of
 3 to 6 carbon atoms, typically.
 A carbonyl group (aldehyde or ketone).
 Several hydroxyl groups.

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Aldoses
Aldoses are monosaccharides O
 With an aldehyde group. ║
 With many hydroxyl (─OH) C─H aldose
groups. │
triose (3 C atoms) H─ C─OH
tetrose (4 C atoms) │
pentose (5 C atoms) H─ C─OH
hexose (6 C atoms) │
CH2OH

Erythose, an aldotetrose
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Ketoses
Ketoses are monosaccharides CH2OH
 With a ketone group. │
 With many hydroxyl (─OH) C=O ketose
groups. │
H─ C─OH
triose (3 C atoms)
│
tetrose (4 C atoms) H─ C─OH
pentose (5 C atoms) │
hexose (6 C atoms) H─C─OH
│
CH2OH

Fructose, a ketohexose 10
Learning Check
Identify these carbohydrates based on their number of C
atom and carbonyl group !

O
C H CH2OH
H C OH C O
H C OH HO C H
H C OH
H C OH
H C OH
CH2OH
CH
A 2OH B

Solution
A. Aldohexose B. Ketopentose 11
Structures of Monosaccharides

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Fischer Projections
A Fischer projection
 Is used to represent carbohydrates.
 Places the most oxidized group at the top.
 Shows chiral carbons as the intersection of vertical
and horizontal lines.

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D and L Notations
In a Fischer projection, the −OH group on the
 Chiral carbon farthest from the carbonyl group
determines an L or D isomer.
 Left is assigned the letter L for the L-isomer.
 Right is assigned the letter D for the D-isomer.
O
O
C H
C H O
HO H
H OH C H
H OH
HO H H OH
H OH
H OH H OH
H OH HO H
H OH
CH2OH CH2OH
CH2OH
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Chiral carbon farthest from the carbonyl groupChiral carbon farthest from the carbonyl group
Examples of D and L Isomers of
Monosaccharides
O
O
C H
C H O
HO H
H OH C H
H OH
HO H H OH
H OH
H OH H OH
H OH HO H
H OH
CH2OH CH2OH
CH2OH
D-glucose D-ribose L-galactose

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Learning Check
Identify each as the D or L isomer.
A. B. C.
O CH2OH

C H O O

HO H C H HO H

HO H H OH H OH

HO H HO H H OH

CH2OH CH2OH CH2OH

_L_-ribose _L_- threose _D_ - fructose 16

D-Glucose
D-glucose is
 Found in fruits, corn
syrup, and honey.
 An aldohexose with
the formula C6H12O6.
 Known as blood sugar
in the body.
 The monosaccharide
in polymers of starch,
cellulose, and
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Blood Glucose Level
In the body,
 Glucose has a
normal blood
level of 70-90
mg/dL.
 A glucose
tolerance test
measures blood
glucose for
several hours Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin
Cummings

after ingesting
glucose.
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D-Fructose
D-fructose
 Is a ketohexose CH2OH
C6H12O6. C O
 Is the sweetest HO C H
carbohydrate.
H C OH
 Is found in fruit
juices and honey. H C OH
 Converts to CH2OH
glucose in the
body. Copyright © 2007 by Pearson Education, Inc D-Fructose
Publishing as Benjamin Cummings

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D-Galactose
D-galactose is O
 An aldohexose C6H12O6. C H
 Not found free in nature. H C OH
 Obtained from lactose, a HO C H
disaccharide.
HO C H
 A similar structure to
glucose except for the H C OH
–OH on C4. CH2OH
D-Galactose

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Learning Check

Draw the structure and Fischer projection of D-fructose.

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Solution

CH2OH CH2OH
│
C O C=O
HO C H HO H
H C OH
H OH
H C OH
CH2OH H OH

CH2OH
D-Fructose
Fischer projection 22
Cyclic Structures of
Monosaccharides

CH2OH
O

OH
OH OH

OH

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Glucose can exist in both a straight-chain and
ring form.
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Cyclic Structures
Cyclic structures
 Are the prevalent form of monosaccharides with 5 or
6 carbon atoms.
O O

 Form when the hydroxyl group on C-5 reacts with the

aldehyde group or ketone group.

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Cyclic Haworth Structures
Stable cyclic hemiacetals form
 When the C=O group and the
—OH are part of the same
molecule. CH2OH
 For hexoses, the hydroxyl group O
on C-5 reacts with the aldehyde
group or ketone group.
 The cyclic structure of a D-isomer
has the last CH2OH group located
above the ring.

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Drawing the Cyclic Structure for
Glucose
STEP 1 Number the carbon chain and turn clockwise to
form a linear open chain.
H O
C
1
H C OH H OH H
2 H O
HO C H
3 HOCH2 C C C C C
H 4 C OH 6 5 4 3 2 1 H
H 5 C OH OH OH H OH

6 CH2OH
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Cyclic Structure for Glucose
STEP 2 Bend the chain to
make a hexagon
 Bond the C5 –O– to C1. CH2OH
6
 Place the C6 group above O
5
the ring.
 Write the –OH groups on 4 1

C2 and C4 below the ring.

OH
OH 3 2 OH
 Write the –OH group on C3
above the ring. OH
 Write a new –OH on C1.

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Cyclic Structure for Glucose (cont)
STEP 3 The new –OH on C1 is drawn
 Down for the  anomer.
 Up for the  anomer.

CH2OH CH2OH 
O O
OH
OH OH
OH OH OH
OH  OH

-D-glucose -D-glucose
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 Summary of the Formation of Cyclic
Glucose

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-D-Glucose and β-D-Glucose in
Solution
When placed in solution,
 Cyclic structures open and close.
 -D-glucose converts to β-D-glucose and back.
 There is only a small amount of open chain.
CH2OH CH2OH CH2OH
H
O O O
O OH
OH C
OH OH H OH
OH OH OH
OH
OH OH
-D-glucose D-glucose (open) β-D-glucose
(36%) (trace) (64%) 31
 Cyclic Structure of Fructose
Fructose
 Is a ketohexose.
 Forms a cyclic structure.
 Reacts the —OH on C-5 with the C=O on C-2.
CH2OH
CH2OH CH2OH CH2OH OH
C O O O
HO C H OH OH
H C OH OH CH2OH
H C OH OH OH
CH2OH
D-fructose α-D-fructose -D-fructose
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Learning Check
Write the cyclic form of -D-galactose
O
C H
H C OH
HO C H
HO C H
H C OH
CH2OH

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Solution

CH2OH
O
OH

OH
OH

OH

-D-galactose

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Chemical Properties of
Monosaccharides

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 Reducing Sugars
Reducing sugars
 Are monosaccharides with a carbonyl group that
oxidizes to give a carboxylic acid.
 Undergo reaction with Benedict’s reagent (Cu2+) to
give the corresponding carboxylic acid.
 Include the monosaccharides glucose, galactose,
and fructose.

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 Oxidation of D-Glucose

O O
Glucose is oxidized
H to a carboxylic acid
C Benedicts C OH
reagent
H C OH H C OH
HO C H [O] HO C H
+ Cu 2+ + Cu2O(s)
H C OH H C OH
H C OH H C OH
Cu+ (reduced
CH2OH CH2OH form)

D-glucose D-gluconic acid

Glucose is a reducing
sugar 37
Reduction of Monosaccharides
D-Glucitol
The reduction of
monosaccharides
 Involves the carbonyl
group.
 Produces sugar
alcohols called alditols.
 Such as D-glucose
gives D-glucitol also
called sorbitol.
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Learning Check
Write the products of the oxidation and reduction of
D-mannose.
O
C H
HO H
HO H
H OH
H OH
CH2OH
D-mannose
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Solution
Write the products of the oxidation and reduction of
D-mannose.
O O
CH2OH C H C OH
HO H HO H HO H
Reduction Oxidation
HO H HO H HO H
H OH H OH H OH
H OH H OH H OH
CH2OH CH2OH CH2OH

D-mannitol D-mannose D-mannonic acid

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Disaccharides

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 Building Disaccharides
 Dehydration Synthesis (aka Condensation) is used to link
two monosaccharides together.
Important Disaccharides
A disaccharide
 Consists of two monosaccharides.
Monosaccharides Disaccharide
Glucose + glucose maltose + H2O
Glucose + galactose lactose + H2O
Glucose + fructose sucrose + H2O

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Disaccharides - two sugar molecules
 Maltose = glucose + glucose
 Cellobiose = glucose + glucose
 Sucrose = glucose + fructose
 Lactose = glucose + galactose
Maltose

Maltose is
 A disaccharide also known as malt sugar.
 Composed of two D-glucose molecules.
 Obtained from the hydrolysis of starch.
 Linked by an -1,4-glycosidic bond formed from the
 −OH on C1 of the first glucose and −OH on C4 of
the second glucose.
 Used in cereals, candies, and brewing.
 Found in both the - and β - forms.

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Formation of Maltose

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Lactose
Lactose
 Is a disaccharide of β-
D-galactose and α- or
β-D-glucose.
 Contains a β -1,4-
glycosidic bond.
 Is found in milk and
milk products.
α-form

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Sucrose
Sucrose or table sugar
 Is obtained from sugar cane and sugar beets.
 Consists of α-D-glucose and β-D-fructose..
 Has an α,β-1,2-glycosidic bond.

α-D-glucose

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β-D-fructose 48
Learning Check
Write the structures and names of the two
monosaccharides that form when sucrose is
hydrolyzed.

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Solution

α-D-glucose

β-D-fructose

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Sweeteners
Sugars and artificial TABLE 15.2

sweeteners
 Differ in
sweetness.
 Are compared to
sucrose (table
sugar), which is
assigned a value
of 100.
60 000

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Learning Check

Identify the monosaccharides in each of the following:

A. lactose
(1) α-D-glucose (2) β-D-fructose (3) β-D-galactose

B. maltose
(1) α-D-glucose (2) β-D-fructose (3) β-D-galactose

C. sucrose
(1) α-D-glucose (2) β-D-fructose (3) β-D-galactose

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Solution
Identify the monosaccharides in each of the following:
A. lactose
(1) α-D-glucose (3) β-D-galactose

B. maltose
(1) α-D-glucose

C. sucrose
(1) α-D-glucose (2) β-D-fructose

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Polysaccharides

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Polysaccharides
Polysaccharides CH2OH
 Are polymers of D-glucose. O
 Include amylose and
amylopectin, starches made of OH
α-D-glucose. OH OH
 Include glycogen (animal starch
in muscle), which is made of α- OH
D-glucose.
 Include cellulose (plants and α-D-glucose
wood), which is made of
β-D-glucose.
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Polysaccharides - polymers of sugar molecules

- Starch - polymer of glucose (plants)

o Alpha 1- 4 linkages, branch at alpha 1-6
o Amylose (unbranched) 20 to 30% of starch in
grain
o Amylopectin (branched) 70 to 80% of starch in
grain

- Cellulose - polymer of glucose (plants)

o Beta 1- 4 linkages
Starch
Starch: A polymer of α-D-glucose in α-1, 4 linkages.

Starch consists of two types of molecules, amylose and

amylopectin.

Amylose is a single chain of glucose units whereas in

amylopectin at about every twenty glucose units there is a branch
with an α-1, 6 linkage.

The relative proportions of amylose to amylopectin depend on the

source of the starch, e.g. normal corn contains over 50% amylose
whereas 'waxy' corn has almost none (~3%).

Amylose has lower molecular weight with a relatively extended

shape, whereas amylopectin has large but compact molecules.
 Partial structure of amylopectin

Partial structure of amylose

Amylose molecules consist of single mostly-unbranched chains
with 500-20,000 α-(1, 4)-D-glucose units with a few α-1, 6 branches.
Amylose can form an extended shape. Hydrogen bonding occurs
between aligned chains. The aligned chains may form double
stranded crystallites that are resistant to amylases.

Amylopectin is formed by non-random α-1, 6 branching of the

amylose-type α-(1, 4)-D-glucose structure. This branching is
determined by branching enzymes that leave each chain with up to
30 glucose residues. Each amylopectin molecule contains one to
two million residues, about 5% of which form the branch points, in
a compact structure forming granules. The molecules are oriented
radially in the starch granule and as the radius increases so does
the number of branches required to fill the space, resulting in
concentric regions of alternating amorphous and crystalline
structure.
 Structures of Amylose and
Amylopectin

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Amylose
Amylose is
 A polymer of α-D-
glucose molecules.
 Linked by -1,4
glycosidic bonds.
 A continuous
(unbranched)
chain.

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Amylopectin
Amylopectin
 Is a polymer of α-D-
glucose molecules.
 Is a branched-chain
polysaccharide.
 Has α-1,4-glycosidic
bonds between the
glucose units.
 Has α-1,6 bonds to
branches.


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Cellulose

Cellulose:
A polymer of glucose units in β – 1,4 linkages.
Cellulose is a linear molecule consisting of 1,000 to
10,000 β-D-glucose residues with no branching.
Neighboring cellulose chains may form hydrogen
bonds leading to the formation of microfibrils with
partially crystalline parts.
Hydrogen bonding among microfibrils can form
microfibers and microfibers react to form cellulose
fibers.
Cellulose fibers usually consist of over 500,000
cellulose molecules.
Cellulose
 Is a polysaccharide
of glucose units in
unbranched chains.
 Has β-1,4-glycosidic
bonds.
 Cannot be digested
by humans because
humans cannot
break down β-1,4-
glycosidic bonds.
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β-1,4 linkage
Lignin

• Not a carbohydrate – does not contain sugars

• Large phenolic three-dimensional polymers in secondary
cell walls
• The monomers are polymerized phenylpropane units,
predominantly coumaryl alcohol [with an OH-group in
position 4 of the phenyl ring], coniferyl alcohol (OH-group
in position 4, -OCH3 in position 3) and sinapyl alcohol (OH-
group in position 4, -OCH3 group in positions 3 and 5).
• The side groups of the monomers are reactive forming
poorly defined structures that are heavily cross linked.
• Attach with hemicellulose and pectins
• Not digested in the rumen
Lignin Monomers
 Interaction of Lignin with
Polysaccharides
Core lignin

Non core lignin

Glycogen

Glycogen
 Is the polysaccharide
that stores α-D-glucose
in muscle.
 Is similar to
amylopectin, but is
more highly branched.

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69
Learning Check
Identify the polysaccharides and types of glycosidic
bonds in each of the following:

A. B. C.

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Solution

A. Cellulose -1,4-glycosidic bonds

B. Amylose -1,4-glycosidic bonds

Amylopectin -1,4-and -1,6-glycosidic bonds

C. Glycogen -1,4-and -1,6-glycosidic bonds

(more branched than amylopectin)

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Glycosaminoglycans

Glycosaminoglycans (mucopolysaccharides) are

linear polymers of repeating disaccharides.
The constituent monosaccharides tend to be
modified, with acidic groups, amino groups, sulfated
hydroxyl and amino groups, etc.
Glycosaminoglycans tend to be negatively charged,
because of the prevalence of acidic groups.

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 CH 2 O H
D -glucuronate 6
 H 5 O
6 COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NH COCH 3
3 2 O
H OH N -acetyl- D -glucosam ine
hyaluronate
Hyaluronate (hyaluronan) is a glycosaminoglycan
with a repeating disaccharide consisting of 2 glucose
derivatives, glucuronate (glucuronic acid) & N-acetyl-
glucosamine. The glycosidic linkages are (13) &
(14). Form ground substance of connective tissue.

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 Inulin :Plant polysaccharide of fructose
.residues connected by 2-1 linkage
 Chitin: Polymer of N-acetylglucosamine
linked through β-1,4 glycosidic bond. Found in
fungal cell wall and arthropod cuticle
 Mannan: Polymer of mannose linked by α-1,4
and α-1,3 glycosidic bonds. Found in cell wall of
bacteria yeast and some plants.
 Heparin: Consists of glucosamine N-sulphate and
sulphate esters of glucuronic acid. Found in
granules of mast cells has anticoagulant
properties.

h
Physical propreties of
carbohydrates
 Monosaccharides are colorless crystalline solids, very
soluble in water, but only slightly soluble in ethanol, low
molecular weight, sweet tasting
 Disaccharides are low molecular weight, sweet,crystalline,
less soluble in water than monosaccharides
 Polysaccharides are high molecular weight, not sweet, not
soluble and not crystalline.

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Complex Carbohydrates
 Carbohydrates can be attached by glycosidic bonds
to non-carbohydrate structures :
(a)Nitrogen bases (in nucleic acids)
(b)Aromatic ring (in steroid and bilirubin)
(c)Proteins (in glycoproteins and glucosaminoglycans)
(d) Lipids (in glycolipids)

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