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Chapter 17
Lipids and Their Functions in
Biochemical Systems

Denniston
Topping
Caret
5th Edition
17.1 Biological Functions of Lipids
• As an energy source, lipids provide 9 kcal of
energy per gram
• Triglycerides provide energy storage in
adipocytes
• Phosphoglycerides, sphingolipids, and steroids
are structural components of cell membranes
• Steroid hormones are critical intercellular
messengers
• Lipid-soluble vitamins (A, E, D, K)
• Dietary fat acts as a carrier of lipid-soluble
vitamins into cells of small intestine
• Provide shock absorption and insulation
17.1 Biological Functions Classification of Lipids
Based on groups of two’s
• Saponifiable lipids have two subclasses
– Simple saponifable has two sub-categories
of Lipids

• Waxes
• Triglycerides
– Complex saponifable has two sub-categories
• Phosphoglycerides
• Sphingolipids
• Nonsaponifiable have two subclasses
– Steroids
– Prostaglandins
17.1 Biological Functions Lipid Classification
of Lipids Lipids

Nonsaponifiable
Saponifiable

Steroids Prostaglandins

Simple Complex

Sphingolipids Phosphoglycerides

Waxes Triglycerides
17.1 Biological Functions Second Classification of Lipids
Four Main Groups
• Fatty Acids
– Saturated
of Lipids

– Unsaturated
• Glycerides glycerol-containing lipids
• Nonglyceride lipids
– Sphingolipids
– Steroids
– Waxes
• Complex lipids lipoproteins
17.1 Biological Functions
of Lipids A Scheme to Classify Lipids
17.1 Biological Functions Simple and Complex Lipids
• Simple: an ester-containing lipid with just
two types of components
– An alcohol
of Lipids

– One or more fatty acids

• Complex: an ester-containing lipid with
more than two components
– An alcohol
– Fatty acids
– Plus others
 17.2 Fatty Acids
• Long straight-chain carboxylic acids
– no branching
• Most common chains range from 10–20
carbons in length
• Usually, an even number of carbons in the
chain, including the carboxyl carbon
• Can be saturated or unsaturated, but usually
no other functional groups present
– Any fatty acid that cannot be synthesized by the
body is called an essential fatty acid
– E.g. linolenic and linoleic acid
 Structure
• Stearic acid: a typical
17.2 Fatty Acids
saturated fatty acid with
18 carbons in the chain

• Oleic acid: a typical

unsaturated fatty acid with
18 carbons in the chain
 Saturated and Unsaturated
17.2 Fatty Acids Fatty Acids
• Saturated fatty acids have no double bonds
• Unsaturated fatty acids do contain double bonds
• The double bond is normally in a cis
configuration
• Double bonds lower the melting temperature
– The cis configuration produces kinks in the
chain and doesn’t allow fatty acids to pack as
close together
 Fatty Acids
• An unsaturated fatty acid has one or more
17.2 Fatty Acids
carbon-carbon double bonds in the chain
• The first double bond is usually at the ninth
carbon
• The double bonds are not conjugated and are
usually cis
• cis double bonds result in a bent chain and
lower melting point H H O
C C CH2 CH2 CH2 C
O
CH2 CH CH2 CH2 CH2
2
CH2
CH2
CH2 Palmitoleic
CH2 acid
CH3
 Fatty Acid Properties
• Melting point increases with increasing carbon
17.2 Fatty Acids

number
• Melting point of a saturated fatty acid is higher than
an unsaturated fatty acid with the same number of
carbons
• Typical saturated fatty acids are tightly packed
together
• cis double bonds prevent good alignment of
molecules in unsaturated fatty acids leading to poor
packing
• Double bonds lower melting point relative to
saturated acid
17.2 Fatty Acids Common Fatty Acids
 Melting Points of Fatty Acids
17.2 Fatty Acids
 Chemical Reactions of
Fatty Acids
17.2 Fatty Acids

Esterification reacts fatty acids with

alcohols to form esters and water
 Fatty Acid Hydrolysis
17.2 Fatty Acids

• Acid Hydrolysis reverses esterification

– Fatty acids are produced from esters
 Saponification
• Saponification is the base-catalyzed hydrolysis
17.2 Fatty Acids

of an ester
• Products of the reaction are
– An alcohol
– An ionized salt which is a soap
• Soaps have a long uncharged hydrocarbon tail
• Also have a negatively charged carboxylate group
at end
• Form micelles that dissolve oil and dirt particles
 Reaction at the Double Bond
• Hydrogenation is an addition reaction
17.2 Fatty Acids

• Unsaturated fatty acids can be converted to

saturated fatty acids
• Hydrogenation is used in the food industry
– Margarine is made from hydrogenation of
unsaturated fatty acid
O
CH3 CH2 4CH CH CH2CH CH CH2 7 C OH
2 H2, Ni
O
CH3 CH2 16 C OH
 17.3 Glycerides
• Glycerides are lipid esters
– Alcohol group of glycerol form an ester with a
fatty acid
– Esterification may occur at one, two, or all three
alcohol positions producing:
• Monoglyceride
• Diglyceride
• Triglyceride
– A neutral triacylglycerol or a triglyceride
– Triglycerides are nonionic and nonpolar
– Triglycerides serve as energy storage in adipose
cells
 Triglycerides
• Glycerides are lipid esters
17.3 Glycerides

• A triglyceride places fatty acid chains at each

alcohol group of the glycerol

O
CH2O C R1
Glycerol O
part CH O C R2 Fatty acid
O chains
CH2O C R3
 Chemical Properties
Triglycerides have typical ester and alkene
17.3 Glycerides

chemical properties as they are composed of

these two groups:
– Hydrolysis: produces the fatty acids and
glycerol, a reverse of formation
– Saponification: replace H with salt from a
strong base
– Hydrogenation: saturates the double bonds
 Triglyceride Reactions
• Triglycerides undergo three basic reactions
17.3 Glycerides

• These reactions are identical to those studied in

carboxylic acids

Triglyceride
H2O, H+ H2, Ni
NaOH
Glycerol More saturated
Fatty Acids triglyceride
Glycerol
Fatty Acid Salts
 Fats and Oils
• Triglycerides or triacylglycerols
17.3 Glycerides
– Fats are a combination of glycerol and the
fatty acids
• Fats mainly come from animals, unless
from fish, and are solid at room
temperature
• Oils mainly come from plants, and are
liquid at room temperature
– High degree of unsaturation
 Phosphoglycerides
• Phospholipid is a more general
17.3 Glycerides

term G
– Any lipid containing phosphorus l
Fatty Acid
• Phosphoglycerides contain: y
– Glycerol c
Fatty Acid
– Fatty acid e
r
– Phosphoric acid with an amino Phosphoric Acid
alcohol o
l
• Replace an end fatty acid of a Alcohol
triglyceride with a phosphoric
acid linked to an amino
alcohol
 Phosphoglycerides
• Have hydrophobic and hydrophilic
17.3 Glycerides

domains
• Structural components of membranes
• Emulsifying agents
• Suspended in water, they spontaneously
rearrange into ordered structures
– Hydrophobic group to center
– Hydrophilic group to water
– Basis of membrane structure
• Micelles and bilayer
17.3 Glycerides Types of Phosphoglycerides
• The phospho-amino-alcohol is highly hydrophilic
• They are used in:
– Cell membranes
– Emulsifying
– Micelle-forming agents in the blood
• Two types
– Ones made with choline are called lecithin
– Those made with either ethanolamine or serine are
called cephalins
17.3 Glycerides Types of Phosphoglycerides
 17.4 Nonglyceride Lipids
Sphingolipids
• These lipids are based on sphingosine
– Long-chain
– Nitrogen-containing
– Alcohol
• Amphipathic, like phospholipids
– Polar head group
– Two nonpolar fatty acid tail
• Structural component of cellular membranes
• Major categories
– Sphingomyelins
– Glycosphingolipids
17.4 Nonglyceride Lipids Types of Sphingolipids
• Sphingomyelins
– Structural lipid of
nerve cell membranes
– Myelin sheath feature
• Glycosphingolipids
– Built on a ceramide
– Cerebrosides have a
single monosaccharide
head group
• Glucocerebroside
• Galactocerebroside
 Waxes
• Waxes are also esters like fats
17.2 Fatty Acids
• Use one alcohol instead of glycerol
• Esters of:
– Long-chain fatty acid
– Long-chain alcohol
• The longer the chains, the higher the melting
point
• Protects the skin of plants and fur of animals
• Examples of waxes include:
– Carnuba, from Brasilian wax palm
– Beeswax
17.6 The Structure of Biological
Membranes

• Each type of cell has a unique membrane

composition with varying percentages of
lipids, proteins, and some carbohydrates
• The currently accepted model of the
membrane is the fluid mosaic model of a
lipid bilayer
17.6 The Structure of
Biological Membranes
 Membrane Proteins
Biological Membranes
17.6 The Structure of

• Most membranes require proteins to carry out

their functions
• Integral proteins are embedded in and/or
extend through the membrane
• Peripheral proteins are bound to membranes
primarily through interactions with integral
proteins
17.6 The Structure of
Biological Membranes
Membrane Structure
Fluid Mosaic Model of