Section 19.

1 Chapter 19
Structure and Classification of Lipids Chapter Outline

19.1 Structure and classification of lipids

19.2 Types of fatty acids
19.3 Physical properties of fatty acids
19.4 Energy-storage lipids: Triacylglycerols
Chapter 2 19.5 Dietary considerations and triacylglycerols
19.6 Chemical reactions of triacylglycerols
19.7 Membrane lipids: Phospholipids
19.8 Membrane lipids: Sphingoglycolipids
19.9 Membrane lipids: Cholesterol
19.10 Cell membranes
19.11 Emulsification lipids: Bile acids
19.12 Messenger lipids: Steroid hormones
19.13 Messenger lipids: Eicosanoids
19.14 Protective-coating lipids: Biological waxes
19.15 Saponifiable and nonsaponifiable lipids

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols
Chemical properties of triacylglycerols are typical of the Hydrolysis
functional groups esters and alkenes
• Reverse of esterification
Four Important Reactions: • In human body  digestion
• Hydrolysis • Carried out by enzymes produced by the
pancreas in a stepwise manner
• Saponification – Breaking of outer fatty acids produces diacylglycerol
and monoacylglycerol
• Complete hydrolysis - When all three fatty acids
• Hydrogenation
are removed
• Partial hydrolysis - When one or more fatty acid
• Oxidation residue remains
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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

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 Section 19.6 Section 19.6
Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols
Hydrolysis

• In the lab, requires the presence of acid or base

• Acidic  glycerol and fatty acids
• Basic  glycerols and fatty acid salts

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

Saponification Saponification

• Hydrolysis reaction carried out in basic solution • Hydrolysis reaction carried out in basic solution
• Products: glycerol and Fatty acid salts • Products: glycerol and Fatty acid salts
Recall: Fat or oil + 3H 2 O 
 3 fatty acids + glycerol

3 fatty acids + 3 NaOH 

 3 fatty acid salts + 3 H2O
• Soapmaking – (old method) heating animal fat +
lye (wood ashes); (new method) hydrolyzing fats
and oils under high pressure and temp. +
Na2CO3
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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols
Soap Synthesis
Soap Synthesis
Soaps are metal salts of fatty acids prepared by
basic hydrolysis (saponification) of a
triacylglycerol.

(top): ©Image Source/Getty Images RF; (b ottom): ©David Buffington/Getty Images RF

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Section 19.6 Section 19.6
Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols
Soap Synthesis Hydrogenation
The nonpolar tails dissolve grease and oil and the • Addition of hydrogen across C–C multiple
polar head makes it soluble in water. bonds, which increases degree of saturation
• Multiple bonds converted into single bonds
Soaps are made from lard (from hogs), tallow (from
cows or sheep), coconut oil, or palm oil. • Many food products are produced by partial
hydrogenation of oils and fats
All soaps work in the same way, but have different – Peanut oil  Peanut butter
properties depending on the lipid source, length of – Liquid plant oil  Margarine
C chain, and degree of unsaturation.

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols
Focus on Health and Medicine

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© The McGraw-Hill Companies, Inc./Jill Braaten, photographer

Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

Focus on Health and Medicine Oxidation

• Double bonds in triacylglycerols are subject to

oxidation with oxygen from air (an oxidizing
agent)
• Leads to C=C breakage that produces both
aldehyde and carboxylic acid products
– Products often have objectionable odors, and fats
and oils are said to be rancid
© The McGraw-Hill Companies, Inc./Jill Braaten, photographer
• To avoid this unwanted oxidation process,
antioxidants are added as preservatives
– Example: Vitamin C and vitamin E are naturally
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 Section 19.6 Section 19.6
Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

What are the important triacylglycerol reactions?

a.Hydrolysis, hydrogenation, and oxidation

b.Hydrogenation, saponification, and hydrolysis
c.Hydrolysis, saponification, hydrogenation, and oxidation
d.Hydrolysis, saponification, oxidation, and
hydrohalogenation

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

What are the important triacylglycerol reactions? Partial triacylglycerol hydrolysis occurs during the
process of digestion in the human body, and it
a.Hydrolysis, hydrogenation, and oxidation produces a _____ and _____.
b.Hydrogenation, saponification, and hydrolysis
c.Hydrolysis, saponification, hydrogenation, and oxidation a.glycerol; three fatty acids
d.Hydrolysis, saponification, oxidation, and b.diacylglycerol; two fatty acids
hydrohalogenation c.monoacylglycerol; one fatty acid
d.monoacylglycerol; two fatty acids

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

Partial triacylglycerol hydrolysis occurs during the Which of the following statements regarding
process of digestion in the human body, and it saponification of triacylglycerols is correct?
produces a _____ and _____.
a.Saponification is a hydrolysis reaction carried out in an
a.glycerol; three fatty acids alkaline (basic) solution.
b.diacylglycerol; two fatty acids b.Saponification of animal fats is the process by which
c.monoacylglycerol; one fatty acid soaps were made in pioneer times.
d.monoacylglycerol; two fatty acids c.Saponification is a hydrolysis reaction resulting in the
formation of carboxylate ions.
d.All the above.
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 Section 19.6 Section 19.6
Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

Which of the following statements regarding What process is utilized to convert liquid plant oils
saponification of triacylglycerols is correct? into semi-solid materials that, when ingested, play
a role in raising blood cholesterol levels?
a.Saponification is a hydrolysis reaction carried out in an
alkaline (basic) solution. a.Halogenation
b.Saponification of animal fats is the process by which b.Hydrohalogenation
soaps were made in pioneer times. c.Hydrogenation
c.Saponification is a hydrolysis reaction resulting in the d.Hydrolysis
formation of carboxylate ions.
d.All the above.
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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

What process is utilized to convert liquid plant oils What process results in breaking the carbon–
into semi-solid materials that, when ingested, play carbon double bonds producing both short chain
a role in raising blood cholesterol levels? aldehyde and carboxylic acid products causing the
fats and oils to become rancid?
a.Halogenation
b.Hydrohalogenation a.Oxidation
c.Hydrogenation b.Hydrolysis
d.Hydrolysis c.Saponification
d.Hydrogenation

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Section 19.6 Section 19.6

Chemical Reactions of Triacylglycerols Chemical Reactions of Triacylglycerols

What process results in breaking the carbon–

carbon double bonds producing both short chain
aldehyde and carboxylic acid products causing the
fats and oils to become rancid?

a.Oxidation
b.Hydrolysis
c.Saponification
d.Hydrogenation

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 Section 19.7 Section 19.7
Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

An Introduction
Phospholipids are lipids that contain a P atom.
• All cells are surrounded by a membrane that Two common types of phospholipids are
confines their contents phosphoacylglycerols or glycerophospholipids
• Up to 80% of the mass of a cell membrane can and sphingomyelins or sphingophospholipid.
be lipid materials dominated by phospholipids
• Phospholipid: Lipid that contains one or more
fatty acids, a phosphate group, a platform
molecule to which the fatty acid(s) and the
phosphate group are attached, and an alcohol
that is attached to the phosphate group

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

Types of Phospholipids Based on Platform Molecule Glycerophospholipids or phosphoacylglycerol

• Lipids that contain two fatty acids and a

phosphate group esterified to a glycerol
molecule and an alcohol esterified to the
phosphate group
• All attachments (bonds) between groups are
ester linkages
– Contain four ester linkages when contrasted to three
ester linkages in triacylglycerols

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids
Similar Ester Linkage

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Section 19.7 Section 19.7
Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

Glycerophospholipids or phosphoacylglycerol

• Undergo hydrolysis and saponification reactions

in a manner similar to that for triacylglycerols
• The alcohol attached to the phosphate group in
a glycophospholipid is usually one of three
amino alcohols:
– Choline - Phosphatidylcholines
– Ethanolamine - Phosphatidylethanolamines
– Serine - Phosphatidylserines

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids
Example 2-5

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

Glycerophospholipids or phosphoacylglycerol

Phosphoacylglycerols are the main component of

most cell membranes.

Structurally, they resemble a triacylglycerol with a

phosphodiester bonded to an alcohol replacing
the third fatty acid.

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Section 19.7 Section 19.7
Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

Glycerophospholipids or phosphoacylglycerol Phosphoacylglycerols or Glycerophospholipid

One of the main types of phosphoacylglycerols is The second of the main types of phosphoacylglycerols
cephalin (or phosphatidylethanolamine): is lecithin (or phosphatidylcholine):

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

The two fatty acid side chains form two nonpolar

“tails” that lie parallel to each other.

The phosphodiester end of the molecule is a

charged or polar “head”.

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

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 Section 19.7 Section 19.7
Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids
Glycerophospholipids or phosphoacylglycerol Sphingophospholipids

• Structurally glycerophospholipids are similar to • Structures based on the 18-carbon

triacylglycerols, but they have different monounsaturated aminodialcohol sphingosine
biochemical functions • Contains one fatty acid and one phosphate
– Triacylglycerols serve as energy-storage molecules group attached to a sphingosine molecule, and
– Glycerophospholipids function as components of cell an alcohol attached to the phosphate group
membranes
– A major structural difference between the two types of
lipids is that of their “polarity”, which is responsible for
their differing biochemical functions
• Triacylglycerols are a nonpolar
• Glycerophospholipids are polar
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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids
Sphingophospholipids
do not contain a glycerol backbone, they have a
sphingosine backbone instead.

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids
Sphingophospholipids Sphingophospholipids
do not contain an ester; their single fatty acid is • Amide bond
bonded to the backbone by an amide bond.

Ethanolamine
Choline

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 Section 19.7 Section 19.7
Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

Sphingophospholipids Sphingophospholipids
Sphingomyelin:
• Participate in hydrolysis and saponification
reaction
• Sphingophospholipids in which the alcohol
esterified to the phosphate group is choline are
called sphingomyelins
– Found in all cell membranes and are important
structural components of the myelin sheath of
neurons

The myelin sheath, the coating that surrounds

nerve cells, is rich in sphingomyelins.
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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

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Section 19.7 Section 19.7

Membrane Lipids: Phospholipids Membrane Lipids: Phospholipids

What is the most abundant type of membrane What is the most abundant type of membrane
lipid? lipid?

a.Cholesterol a.Cholesterol
b.Sphingoglycolipids b.Sphingoglycolipids
c.Phospholipids c.Phospholipids
d.Eicosanoids d.Eicosanoids

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 Section 19.8 Section 19.8
Membrane Lipids: Sphingoglycolipids Membrane Lipids: Sphingoglycolipids

Sphingoglycolipids Cerebrosides

• 2nd type of membrane • Simplest sphingoglycolipids

• Contains both a fatty acid • Contain a single monosaccharide unit–either
and a carbohydrate glucose or galactose
component attached to a • Occur primarily in brain (7% of dry mass)
sphingosine molecule
• Head and 2 tails structure
• Head - carbohydrate

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Section 19.8 Section 19.8

Membrane Lipids: Sphingoglycolipids Membrane Lipids: Sphingoglycolipids

Gangliosides

• Complex sphingoglycolipids
• Contain a branched chain of up to seven
monosaccharide residues
• Occur in the gray matter of the brain as well as
in the myelin sheath

Gray matter consists primarily of

neuronal cell bodies, or soma. This a
spherical structure that houses the
neuron’s nucleus.

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Section 19.8 Section 19.8

Membrane Lipids: Sphingoglycolipids Membrane Lipids: Sphingoglycolipids

What is the membrane lipid, sphingoglycolipid, What is the membrane lipid, sphingoglycolipid,
made up of? made up of?

• sphingosine; fatty acid; monosaccharide • sphingosine; fatty acid; monosaccharide

• sphingosine; fatty acid; oligosaccharide • sphingosine; fatty acid; oligosaccharide
• sphingosine; glycerol; fatty acid • sphingosine; glycerol; fatty acid
• Both (a) and (b) • Both (a) and (b)

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 Section 19.9 Section 19.9
Membrane Lipids: Cholesterol Membrane Lipids: Cholesterol

Cholesterol - Third Major Type of Membrane Lipid

• Is a steroid Steroids are a group of lipids whose carbon

skeletons contain several fused rings:
– Lipid whose structure is based on a fused-ring
system of three 6-membered rings and one 5-
membered ring
• Cholesterol: C27 steroid molecule and
precursor for other steroid-based lipids
– Important in human cell membranes, nerve tissue,
and brain tissue
– Important in chemical synthesis of various hormones
and vitamins essential for life

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Section 19.9 Section 19.9

Membrane Lipids: Cholesterol Membrane Lipids: Cholesterol

Cholesterol, the most prominent steroid, is Elevated levels of cholesterol in the bloodstream
synthesized in the liver and found in almost all lead to coronary artery disease, heart attack, etc.
body tissues.
Cholesterol is insoluble in the aqueous medium
of blood.
It is transported through the bloodstream by
lipoproteins, aggregates of phospholipids and
proteins.
Low-density lipoproteins (LDLs) transport
cholesterol from the liver to the tissues.

It is obtained in the diet from many sources, High-density lipoproteins (HDLs) transport
including meat, cheese, butter, and eggs. 69
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cholesterol from tissues back to the liver. 70
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Section 19.9 Section 19.9

Membrane Lipids: Cholesterol Membrane Lipids: Cholesterol

LDLs deposit cholesterol on the walls of arteries

when they carry more than is needed to form cell
membranes.

This forms plaque, which restricts blood flow; LDL

cholesterol is called “bad” cholesterol.
The surface of the lipoprotein particle
contains polar or ionic groups.
HDLs reduce the level of cholesterol in the
Cholesterol is embedded in the
phospholipid surface, with the nonpolar
bloodstream by bringing excess back to the liver;
carbon skeleton in the interior and the
polar OH group pointing outward.
The interior of the lipoprotein
particle is hydrophobic
HDL cholesterol is called “good” cholesterol.

Recommended levels are: 𝐇𝐃𝐋 > 𝟒𝟎 𝐦𝐠/𝐝𝐋,

𝐋𝐃𝐋 < 𝟏𝟎𝟎 𝐦𝐠/𝐝𝐋, total serum cholesterol <
71
𝟐𝟎𝟎 𝐦𝐠/𝐝𝐋. 72
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 Section 19.9 Section 19.9
Membrane Lipids: Cholesterol Membrane Lipids: Cholesterol

Drugs called statins reduce the level of cholesterol

in the bloodstream.

They act by blocking the synthesis of cholesterol

at its early stages.

© Ed Reschke
© Ed Reschke

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Section 19.9 Section 19.9

Membrane Lipids: Cholesterol Membrane Lipids: Cholesterol

Cholesterol in Food

• Liver synthesizes almost 1g of cholesterol The membrane lipid cholesterol is a steroid whose
everyday structure is based on a fused-ring system that
– Not necessary to consume in the form of diet involves _____ six-membered ring(s) and _____
• Cholesterol ingestion decreases biosynthetic five-membered ring(s).
cholesterol production
• Animal food contains lots of cholesterol a.2, 2
• Plant food contains negligible amounts of b.3, 2
cholesterol c.3, 1
d.1, 3

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Section 19.9
Membrane Lipids: Cholesterol

The membrane lipid cholesterol is a steroid whose

structure is based on a fused-ring system that
involves _____ six-membered ring(s) and _____
five-membered ring(s).

a.2, 2
b.3, 2
c.3, 1
d.1, 3

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