Chapter 8 – Part 1

Lipids and Proteins Are

Associated in Biological
Membranes

© 2018 Cengage Learning. All Rights Reserved.

Lipids
 Lipids
• Heterogeneous class of naturally occurring organic
compounds classified together on the basis of
common solubility properties
• Examples - Fats and oils
• Insoluble in water but soluble in aprotic organic
solvents including chloroform and acetone
• Amphipathic in nature
• Amphipathic: Molecule that has one end with a polar,
water-soluble group and another end with a nonpolar
hydrocarbon group that is insoluble in water
 Classification of Lipids

Open-chain Fused-ring
compounds compounds
1. • Fatty acids 6. • Cholesterol
2. • Triacylglycerols • Steroid hormones
3. • Sphingolipids • Bile acids
4. • Phosphoacylglycerols
5. • Glycolipids
 1. Fatty Acids
• Unbranched chain carboxylic acids
• 12–20 carbons long
• Derived from hydrolysis of animal fats, vegetable oils,
or phosphodiacylglycerols of biological membranes
• Rarely found free in nature; form parts of many
commonly occurring lipids
• Amphipathic compounds – carboxyl group is
hydrophilic and hydrocarbon tail is hydrophobic
• Types
• Unsaturated fatty acids - Contain carbon–carbon
double bonds
• Saturated fatty acids - Contain only single bonds
1. Structures of Some Typical Fatty Acids

Most naturally occurring fatty acids contain:

• even number of carbon atoms
• hydrocarbon chain usually unbranched

If there are carbon-carbon double bonds in the chain,

usually:
• cis
• unconjugated
 1. Structures of Some Typical Fatty Acids

Saturated Saturated Unsaturated

16 C 18 C 16 C

Polyunsaturated Polyunsaturated
Omega-3 fatty acid
18 C 20 C
1. Typical Naturally Occurring Saturated
Fatty Acids

Even Melting point increases

w/ increasing # of
carbons
1. Typical Naturally Occurring Unsaturated
Fatty Acids

Delta System of Notation: indicates # of carbon atoms and # of

double bonds; D12 refers to a double bond at the twelfth carbon
atom from the carboxyl end.

Unsat’d Fatty Acids have lower melting points than sat’d Fatty
Acids
 1. Unsaturated Fatty Acids
• cis isomer predominates and the trans isomer is rare
• cis double bond puts a kink in the long-chain
hydrocarbon tail
• Shape of a trans fatty acid is like that of a saturated
fatty acid in its fully extended conformation
• Double bonds are isolated by several singly bonded
carbons
• Have lower melting points than their saturated
counterparts
• Greater the degree of unsaturation, lower the melting
point
 1. Fatty Acid Notation
• Indicates the number of carbon atoms and the
number of double bonds separated by a colon
• Examples
• 18:0 denotes an 18-carbon saturated fatty acid with no
double bonds
• 18:1 denotes an 18-carbon fatty acid with one double
bond
 2. Triacylglycerols (Triglycerides)
• Lipids formed by the esterification of three fatty acids
to glycerol
• Ester groups form the polar part of the molecule, and
the tails are nonpolar
• Accumulated in adipose tissues and provide a means
of storing fatty acids
• Ester linkages are hydrolyzed by lipases when fatty
acids are used by organisms
• Serve as concentrated stores of metabolic energy
 2. Triacylglycerols

Electron micrograph
of an adipocyte

Small band of
cytoplasm surrounds
large deposit of
triacylglycerols

From Tymoczko et al. 2015

2. Triacylglycerols – storage form of Fatty Acids
• Triacylglycerols -
energy rich
• Hydrophobic and
reduced (one gram
of anhydrous fat
stores more than six
times the energy of
one gram of
hydrated glycogen)

• Migratory birds use fat stores to power long

non-stop flights across Gulf of Mexico
From Tymoczko et al. 2015
2. Triacylglycerols - Formed from Glycerol
and Fatty Acids
2. Saponification – Hydrolysis of Triacylglycerols
• Reaction of glyceryl
ester with NaOH or KOH
to produce glycerol and
respective Na or K salts
(soaps)
• Soaps form water-
insoluble salts when used
in hard water, which
contains Ca(II), Mg(II),
and Fe(III) ions
• Glycerol is used in
creams and in
manufacture of
nitroglycerin (used to
treat heart failure)
 3. Waxes
• Complex mixtures of esters of long-chain carboxylic
acids and long-chain alcohols
• Serve as protective coatings for plants and animals

Cetyl palmitate found in spermaceti from sperm whales

Image from:
https://www.smithsonianmag.com/science-nature/the-sperm-wha
les-deadly-call-94653/
 3. Sphingolipids

• Sphingolipids contain
sphingosine, a long-chain
amino alcohol
• Found in plants and
animals
 3. Sphingolipids
Sphingomyelin
• Primary alcohol of
sphingosine is esterified to
phosphoric acid, which is
esterified to choline
• Occurs in cell membranes
of nervous system

Ex. Schwann cell wraps its plasma

membrane concentrically around the
axon to form a segment of myelin
sheath about 1 mm long
• membrane layers shown less
compacted than are in reality
4. Phosphoacylglycerols: Phosphatidic Acid
• Compound in which two fatty acids and phosphoric
acid are esterified to three hydroxyl groups of glycerol
• Phosphoric acid is triprotic in nature
• One molecule can form ester bonds to glycerol and to
some other alcohol to create phosphatidyl esters
nxt slide
4. Phosphoacylglycerols: Phosphatidyl Esters
• Classed as phosphoacylglycerols
• Classification depends on nature of the second alcohol
that is esterified to the phosphoric acid
• Nature of fatty acids in a molecule varies widely
• Structure
• Long, nonpolar, hydrophobic tails
• Polar, highly hydrophilic head groups
• Amphipathic in nature
 4. Phosphoacylglycerols
• Polar head group is
charged
• Phosphate group is
ionized at neutral
pH
• Positively charged
amino group is
contributed by an
amino alcohol
esterified to the
phosphoric acid
 4. Phosphoacylglycerols

Glycerol + 2 FA chains + Phosphate + Choline

 5. Glycolipids
• Lipid to which a sugar moiety
is bonded
• Ceramides (slide 19)
• Parent compounds for
glycolipids
• Glycosidic bond is formed
between the primary alcohol
group of the ceramide and a
sugar residue (glucose or
galactose)
• Resulting compound is
called a cerebroside
 5. Example of Glycolipids:
Gangliosides
• Glycolipids with a
complex carbohydrate
moiety that contains
more than three sugars
• One is always a sialic
acid
• Called acidic
glycosphingolipids
because of their net
negative charge at
neutral pH
 5. Glycolipids- Structures of Several Important
Gangliosides (glycolipids with a complex carbohydrate
moiety)

Sialic acid
 6. Steroids - fused-ring compounds
(not open-chain compounds)
• Lipids with characteristic fused-ring structure
• Three six-membered rings (A, B, and C rings)
• One five-membered ring (D ring)
• Important steroids include sex hormones and
cholesterol
• Cholesterol:
-Occurs in cell membranes
-Highly hydrophobic
-Precursor of other steroids
-Plays role in development of atherosclerosis, narrowing
of arteries because of plaque build-up
 6. Structures of Some Steroids
• Three six-membered rings (the A, B, and C
rings)
• One five-membered ring (the D ring)

One polar Cholesterol

group on
cholesterol

Steroid Sex Hormones

Membranes
 Biological Membranes
• Every cell has a cell (plasma) membrane
• Eukaryotic cells also have membrane-enclosed organelles
• Molecular basis of membrane structure lies in its lipid and
protein components
 Biological Membranes

Functions:

1. Separate cells from external environment

2. Transport specific substances into and out of cells
3. Receptors – binding sites for extracellular
substances
4. Contain many important enzymes whose function
depends on the membrane environment

Chapter 8 focuses on these two functions:

transport proteins and receptor proteins
 Lipid Bilayer
• Aggregate of a lipid molecule in
which polar head groups are in
contact with water and the
hydrophobic parts are not
• Polar surface contains
charged groups
• Hydrocarbon interior
consists of saturated and
unsaturated fatty acid chains
and fused-ring system of
cholesterol
 Biological Membranes
• Major force driving the formation of lipid bilayers is
hydrophobic interaction
• Differ from lipid bilayers as they contain proteins as
well as lipids
 Lipid Bilayer
• Arrangement is held
together by noncovalent
interactions
• van der Waals and
hydrophobic interactions
• Both inner and outer
layers contain mixtures
of lipids
• Bulkier molecules tend to
occur in outer layer
• Smaller molecules tend
to occur in inner layer
 Lipid Composition of Membranes in Rat Liver Cells, in
Weight Percent

Phosphatidylcholine (a phosphoacylglycerol) – highest % (~27% - 49%) in membranes

Phosphatidylcholine
most common
phospholipid in cell
membranes

Essential Cell Biology, Fifth Edition

Copyright © 2019 W. W. Norton & Company
 Membrane Fluidity
• Arrangement of hydrocarbon interior of the bilayer
can be ordered and rigid or disordered and fluid
• Depends on composition of the bilayer
• Saturated fatty acids
• Linear arrangement of hydrocarbon chains leads to
rigidity (increases vdW interactions)
• Unsaturated fatty acids
• Kink in the hydrocarbon chain causes disorder in its
packing and leads to greater fluidity
Effect of Double Bonds on the Conformations of
Hydrocarbon Tails of Fatty Acids
 Membrane Fluidity and Cholesterol
• Presence of cholesterol can enhance order and
rigidity
• Fused-ring structure of cholesterol is rigid
• Stabilizes extended straight-chain arrangement of
saturated fatty acids by van der Waals interactions
 Membrane Fluidity in Plants and Animals
• Animal membranes - less fluid
and more rigid than plant
membranes
• Plant membranes - higher
percentage of unsaturated
fatty acids
• Presence of cholesterol-
characteristic of animal, not
plant, membranes

Membranes of prokaryotes
- Most fluid
- Contain no appreciable
amounts of steroids
Phospholipids and glycolipids distributed asymmetrically in lipid bilayer
of an animal cell plasma membrane

Phospholipids:
• Phosphatidylcholine (red ) and sphingomyelin (brown)
concentrated in noncytosolic monolayer
• Phosphatidylserine (light green) and phosphatidylethanolamine
(yellow) found mainly on cytosolic side
Glycolipids: blue head groups - found exclusively in noncytosolic
monolayer of membrane
Cholesterol (green) - distributed almost equally in both monolayers