Chapter 15 Lipids

15.1
Lipids

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

1
 Lipids
Lipids are
• Biomolecules that contain fatty acids
• Soluble in organic solvents but not in
water.
• Named from the Greek word lipos,
which means “fat.”

2
 Types of Lipids
• Lipids with fatty acids
Waxes
Fats and oils (trigycerides)
Phospholipids
Sphingolipids

• Lipids without fatty acids

Steroids
3
 Structures of Lipids

4
Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
 Fatty Acids
• Long-chain carboxylic acids
• Insoluble in water
• Typically 12-18 carbon atoms (even number)
• Some contain double bonds

corn oil contains 86%

unsaturated fatty acids and
14% saturated fatty acids
5
 Fatty Acid Formulas
The formulas for fatty acids are written as
• Condensed formulas.
• Line-bond formulas.
• For example caprylic acid with 8 carbon atoms.
CH3—(CH2)6—COOH

CH3—CH2—CH2—CH2—CH2—CH2—CH2—COOH

OH
6
 Saturated and Unsaturated
Fatty Acids
Saturated = C–C bonds
Unsaturated = one or more C=C bonds

COOH
palmitic acid, a saturated acid
COOH

palmitoleic acid, an unsaturated fatty acid

7
 Structures
Saturated fatty acids
• Fit closely in regular pattern
COOH
COOH
COOH

Unsaturated fatty acids

H H
• Cis double bonds C C

cis double bond COOH

8
 Properties of Saturated
Fatty Acids
• Contain only single C–C bonds
• Closely packed
• Strong attractions between chains
• High melting points
• Solids at room temperature

9
 Saturated Fatty Acids
Saturated fatty acids have
• Single C–C bonds.
• Molecules that fit closely together
in a regular pattern.
• Strong attractions between fatty
acid chains.
• High melting points that make
them solids at room temperature.

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

10
Some Saturated Fatty Acids

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

11
 Properties of Unsaturated
Fatty Acids
• Contain one or more double C=C bonds
• Nonlinear chains do not allow molecules
to pack closely
• Few interactions between chains
• Low melting points
• Liquids at room temperature

12
Properties of Unsaturated Fatty Acids

Unsaturated fatty acids “kinks”

• Have “kinks” in the in
fatty acid chains. chain
• Do not pack closely.
• Have few attractions
between chains.
• Have low melting
points.
• Are liquids at room
temperature.
Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings 13
 Unsaturated Fatty Acids

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

14
 Learning Check L1
How would the melting point of stearic
acid compare to the melting points of oleic
acid and linoleic acid? Assign the melting
points of –17°C, 13°C, and 69°C to the
correct fatty acid. Explain.
stearic acid (18 C) saturated
oleic acid (18 C) one double bond
linoleic acid (18 C) two double bonds

15
 Solution L1

Stearic acid is saturated and would have a

higher melting point than the unsaturated
fatty acids. Because linoleic has two
double bonds, it would have a lower mp
than oleic acid, which has one double
bond.
stearic acid mp 69°C
oleic acid mp 13°C
linoleic acid mp -17°C 16
 Fats and Oils: Triacylglycerols

Fats and oils are

• Also called triacylglycerols.
• Esters of glycerol.
• Produced by esterification.
• Formed when the hydroxyl
groups of glycerol react
with the carboxyl groups of
fatty acids.
Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings

17
 Triacylglycerols
In a triacylglycerol,
• Glycerol forms ester bonds with three fatty acids.

Copyright © 2007 by Pearson Education, Inc. Publishing as Benjamin Cummings

18
 Formation of a
Triacylglycerol
glycerol + three fatty acids triacylglycerol

O
CH2 OH HO C (CH2)14CH3
O
CH OH HO C (CH2)14CH3
+ O
O
CH2 OH HO C (CH2)14CH3 CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3 +
3H2O
O
CH2 O C (CH2)14CH3
19
 Fats and Oils
Formed from glycerol and fatty acids
O
CH2 OH HO C (CH2)14CH3
O
CH OH + HO C (CH2)14CH3
O
CH2 OH HO C (CH2)14CH3
glycerol palmitic acid (a fatty acid)
20
 Triglycerides (triacylglcerols)
Esters of glycerol and fatty acids
ester bonds
O
CH2 O C (CH2)14CH3 + H2O
O
CH O C (CH2)14CH3 + H 2O
O
CH2 O C (CH2)14CH3 + H 2O
21
 Learning Check L2
What are the fatty acids in the following
triglyceride?
O
CH2 O C (CH2)16CH3
O
CH O C (CH2)7CH CH(CH2)7CH3
O
CH2 O C (CH2)12CH3
22
 Solutions L2
What are the fatty acids in the following
triglyceride?
O Stearic acid
CH2 O C (CH2)16CH3
O Oleic acid
CH O C (CH2)7CH CH(CH2)7CH3
O
Myristic acid
CH2 O C (CH2)12CH3
23
 Properties of Triglycerides

Hydrogenation
• Unsaturated compounds react with H2
• Ni or Pt catalyst
• C=C bonds C–C bonds

Hydrolysis
• Split by water and acid or enzyme catalyst
• Produce glycerol and 3 fatty acids
24
 Chemical Properties of
Triacylglycerols
The chemical reactions of
triacylglycerols are similar
to those of alkenes and esters.
• In hydrogenation, double bonds in
unsaturated fatty acids react with H2
in the presence of a Ni or Pt catalyst.
• In hydrolysis, ester bonds are split by
water in the presence of an acid, a
base, or an enzyme. 25
 Hydrogenation

O
CH2 O C (CH2)5CH CH(CH2)7CH3
O
Ni
CH O C (CH2)5CH CH(CH2)7CH3 + 3 H2
O
CH2 O C (CH2)5CH CH(CH2)7CH3

26
 Product of Hydrogenation
O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3
O
CH2 O C (CH2)14CH3

Hydrogenation converts double bonds in oils

to single bonds. The solid products are used
to make margarine and other hydrogenated
items. 27
 Hydrogenation of Oils
The hydrogenation of oils
• Adds hydrogen (H2) to the carbon atoms of double bonds.
• Converts double bonds to single bonds.
• Increases the melting point.
• Produces solids such as margarine and shortening.

28
Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings
 Hydrolysis
Triglycerides split into glycerol and three
fatty acids (H+ or enzyme catalyst)
O
CH2 O C (CH2)14CH3
O
H+
CH O C (CH2)14CH3 +3 H2O
O
CH2 O C (CH2)14CH3
CH2 OH O
CH OH + 3 HO C (CH2)14CH3

CH2 OH 29
 Saponification and Soap
• Hydrolysis with a strong base
• Triglycerides split into glycerol and the
salts of fatty acids
• The salts of fatty acids are “soaps”
• KOH gives softer soaps

30
 Saponification

O
CH2 O C (CH2)16CH3
O
CH O C (CH2)16CH3 + 3 NaOH
O
CH2 O C (CH2)16CH3
CH2 OH O
+-
CH OH + 3 Na O C (CH2)14CH3
salts of fatty acids (soaps)
CH2 OH

31
 Learning Check L3
What are the products obtained from the
complete hydrogenation of glyceryl
trioleate?

(1) Glycerol and 3 oleic acids

(2) Glyceryltristearate
(3) Glycerol and 3 stearic acids

32
 Solution L3
What are the products obtained from the
complete hydrogenation of glyceryl
trioleate?

2. Glyceryltristearate

33
 Learning Check
What products are obtained from the
complete hydrolysis of glyceryl
trioleate?
1. Glycerol and 3 oleic acids
2. Glyceryl tristearate
3. Glycerol and 3 stearic acids

34
 Solution
What products are obtained from
the complete hydrolysis of glyceryl
trioleate?
1. Glycerol and 3 oleic acids

35
 Learning Check
Write the product of the following
reaction.
O
CH2 O C (CH2)5CH CH(CH2)7CH3
O
Ni
CH O C (CH2)5CH CH(CH2)7CH3 + 3 H2
O
CH2 O C (CH2)5CH CH(CH2)7CH3

36
 Solution
O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3
O
CH2 O C (CH2)14CH3

37
 Glycerophospholipids
Glycerophospholipids are
• The most abundant lipids in cell membranes.
• Composed of glycerol, two fatty acids,
phosphate and an amino alcohol.
Fatty acid

Fatty acid
Glycerol

Amino
PO4
alcohol
38
 Lecithin and Cephalin
Lecithin and cephalin are glycerophospholipids
• Abundant in brain and nerve tissues.
• Found in egg yolk, wheat germ, and yeast.

Copyright © 2007 by Pearson Education, Inc Publishing as Benjamin Cummings 39

 Learning Check
Identify each as a
A. fatty acid B. triacylglycerol
C. amino alcohol D. glycerophospholipid

1. glyceryl trioleate
2. cephalin
3. choline
4. palmitic acid

40
 Solution
Identify each as a
A. fatty acid B. triacylglycerol
C. amino alcohol D. glycerophospholipid

1. glyceryl trioleate B. triacylglycerol

2. cephalin D. glycerophospholipid
3. choline C. amino alcohol
4. palmitic acid A. fatty acid

41
 Learning Check
Identify the components and type of glycerophospholipid
O
║
CH2−O −C −(CH2)16 −CH3
O
║
CH2−O −C −(CH2)16 −CH3
+
O NH3
║ │
CH2−O −P −O − CH2−CH−COO-
│
O-
42
 Solution
Identify the components and type of glycerophospholipid
O
║
CH2−O −C −(CH2)16 −CH3
O 2 stearic acids
║
CH2−O −C −(CH2)16 −CH3
+
O NH3
║ │ type = cephalin
CH2−O −P −O − CH2−CH−COO-
│ serine
O-
phosphate amino alcohol
43
Sphingolipids

Copyright © 2007 by Pearson Education, Inc.

Publishing as Benjamin Cummings

44
 Sphingolipids
Sphingolipids
• Are similar to phospholipids.
• Contain sphingosine (a long-chain amino alcohol), a
fatty acid, phosphate, and a small amino alcohol.
• Have polar and nonpolar regions.
fatty acid

sphingosine

amino
PO4
alcohol 45
 Sphingosine

Sphingosine is a long-chain unsaturated amino

alcohol.

CH3−(CH2)12 −CH=CH−CH−OH
│
CH−NH2
│
CH2−OH 46
Steroids: Cholesterol, Bile Salts,
and Steroid Hormones

CH3 CH3
CH3
CH3
CH3

HO
Copyright © 2007 by Pearson Education, Inc.
Publishing as Benjamin Cummings
47
 Steroid Nucleus
A steroid nucleus
consists of
• 3 cyclohexane
rings.
• 1 cyclopentane
ring.
• No fatty acids.
steroid nucleus

48
 Cholesterol
Cholesterol
• Is the most abundant steroid in the body.
• Has methyl CH3- groups, alkyl chain, and -OH
attached to the steroid nucleus.
CH3 CH3
CH3
CH3
CH3

HO
49
 Learning Check

Match the components of the cholesterol molecule with

the following:
___ carbon chain ___hydroxyl group
___ steroid nucleus ___methyl group

D
CH3 CH3
CH3
B CH3
CH3

A
C
HO 50
 Solution
Match the components of the cholesterol molecule with
the following:
D carbon chain A hydroxyl group
C steroid nucleus B methyl group

D
CH3 CH3
CH3
B CH3
CH3

A
C
HO 51