Chapter 8

Lipids and Proteins Are

Associated in Biological
Membranes

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Chapter Outline
Seven-structure (8-1)
(8-2)
The definition of a lipid
The chemical natures of the lipid types
(8-3) Biological membranes

objective (8-4)
(8-5)
Membrane proteins
The functions of membranes
(8-6) Lipid-soluble vitamins and their functions
1 Fatty Acids (8-7) Prostaglandins and leukotrienes

2 Triacylglycerols
3 Glycerophospholipids
4 Sphingolipids
5 Waxes
6 Terpenes
7 Steroids
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1. Fatty acids

All biological lipids are

amphipathic
• Fatty acid part
–Lauric acid (12 C)
–Myristic acid (14
C)
–Palmitic acid (16
C)
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UNSATURATED
Fatty Acids
1.Palmitoleic acid
(16:1)
2. Oleic acid (18:1)
3. Linoleic acid (18:2)
4. -Linolenic acid
(18:3)
5. -Linolenic acid
(18:3)
6. Arachidonic acid
(20:4)
Saturated vs Unsaturated
Structural consequences of unsaturation
1) Saturated chains pack tightly and form more rigid,
organized aggregates (i.e., membranes)
2) Unsaturated chains bend and pack in a less ordered
way, with greater potential for motion
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2. Triacylglycerols
Also called triglycerides
Other advantages
A major energy accrue to users of
triacylglycerols
source for
1.Insulation
many
organisms 2.Energy
without
Why?
Most reduced form of
nitrogen
carbon in nature 3. Metabolic
No solvation needed
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Figure, Page 336

Figure
10.2, The
structure
of
tristearin
,a
simple
fat
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Figure 10.4, Structure of a typical wax
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Figure 10.5c, Phospholipids and membrane structure

60A
3. Glycerophospholipids
Figure 10.6, Glycerophospholipid
structure

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4. Sphingolipids
Base structure is sphingosine
A. Sphingosine is an 18-carbon amino
alcohol
B. Ceramides are amide linkages of fatty acids
to
the nitrogen of sphingosine
C. Glycosphingolipids are ceramides with one
or more sugars in beta-glycosidic linkage at
• Glycosphingolipids
the 1-hydroxyl groupwith one sugar are
cerebrosides
• Gangliosides - ceramides with 3 or more
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Sphingosine is to Ceramide

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Figure 10.7a, Examples of
glycosphingolipids

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Figure, Page 340

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Chapter 10, Figure 10.7b, Examples of
glycosphingolipids

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5. Waxes
Esters of long-
chain alcohols
with long-chain
fatty acids
• Highly insoluble
• Animal skin and
fur are wax-
coated
• Leaves of many
plants
• Bird feathers
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6. Terpenes
Based on the isoprene structure
• Know nomenclature
• All sterols (including cholesterol) are terpene-
based molecules
• Steroid hormones are terpene-based

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7. Steroids
Based on a core structure consisting of
three 6-membered rings and one 5-
membered ring, all fused together

• Cholesterol is the most common steroid

in animals and precursor for all other steroids
in animals
• Steroid hormones serve many functions in
animals - including salt balance, metabolic
function and sexual function
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7.Steroids

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Chapter 10, Figure 10.8b, Cholesterol

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Lipid-Soluble Vitamins and Their Functions
• Lipid-soluble vitamins are hydrophobic

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 • Most active from of vitamin E is α-tocopherol
Vitamin E • Contains antioxidant properties
• Antioxidants: Strong reducing agents, which
are easily oxidized and thus prevent the
oxidation of other substances
• Traps free radicals (HOO• and ROO•)
• Highly reactive molecules that have at least
one unpaired electron
• Formed as a result of oxidation of
unsaturated hydrocarbon chains in
membrane phospholipids

Figure 8.35 - Most Active Form of Vitamin E Is

α-Tocopherol

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Vitamin K
• Plays an
important role in
the blood-clotting
process
• Bicyclic ring
system contains
two carbonyl
groups, the only
polar groups on
the molecule
• Long unsaturated
hydrocarbon side
chain consists of
repeating
isoprene units

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Figure 8.37 - Role of Vitamin K in the
Modification of Prothrombin

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Functions of Prostaglandins
• Control of blood pressure
• Stimulation of smooth-muscle contraction
• Induction of inflammation
• Aspirin, cortisone, and other steroids possess anti-
inflammatory effects
• Inhibition of the aggregation of platelets
• Possess therapeutic value by preventing formation of
blood clots

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Leukotrienes
• Compounds derived from arachidonic acid
• Found in white blood cells (leukocytes)
• Consist of three conjugated double bonds
• Help in the constriction of smooth muscle, especially
in the lungs
• May have inflammatory properties and may be
involved in rheumatoid arthritis

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Thromboxanes
• Third class of derivatives of arachidonic acid
• Structure contains cyclic ethers
• Thromboxane A2 (TxA2)
• Induces platelet aggregation and smooth-muscle
contraction

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Glycolipids
• Lipid to which a sugar moiety
is bonded
• Ceramides
• 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
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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

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Figure 8.8
-
Structures
of Several
Important
Gangliosid
es
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Figure 8.9 - Structures of Some Steroids

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Biological Membranes
• Every cell has a cell (plasma) membrane
• Eukaryotic cells also have membrane-enclosed
organelles (nuclei and mitochondria)
• Molecular basis of membrane structure lies in its lipid
and protein components
• Separate cells from the external environment and
transport specific substances into and out of cells
• Interaction between lipid bilayers and membrane
proteins determines membrane function
• Contain many important enzymes whose function
depends on the membrane environment

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Biological Membranes (continued)
• Major force
driving the
formation of lipid
bilayers is
hydrophobic
interaction
• Differ from lipid
bilayers as they
contain proteins
as well as lipids

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Lipid Bilayer (continued)
• 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 the
outer layer
• Smaller molecules
tend to occur in the
inner layer
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Table 8.3 - Lipid Composition of Membranes in Rat
Liver Cells, in Weight Percent

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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
• Unsaturated fatty acids
• Kink in the hydrocarbon
chain causes disorder in its
packing and leads to greater
fluidity

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 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
• Animal membranes are less fluid and
more rigid than plant membranes
• Plant membranes have a higher
percentage of unsaturated fatty
acids than animal membranes
• Presence of cholesterol is
characteristic of animal, rather
than plant, membranes
• Membranes of prokaryotes are the
most fluid
• Contain no appreciable amounts
of steroids
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Phase Transition in Lipid Bilayer
• Ordered bilayers become less ordered in the
presence of heat
• Cooperative transition occurs at a characteristic
temperature
• Transition temperature is higher for more rigid
membranes and is lower for less rigid membranes
• Mobility of the lipid chains increases dramatically

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Types of Membrane Proteins
• Peripheral proteins: Loosely bound to the outside of
a membrane
• Bound by polar interactions, electrostatic interactions,
or both and can be removed by raising the ionic
strength of the medium
• Example - Heterotrimeric G protein
• Integral proteins: Embedded in a membrane
• Can be removed by treatment with detergents or
extensive sonication, which may lead to denaturation
of the protein
• Example - Rhodopsin

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Figure 8.18 - Integral and Peripheral Proteins
• Proteins span across
the membrane in the
form of an α-helix or a
β-sheet
• Structures minimize
the contact of polar
parts with the
nonpolar lipids
• Proteins can be
anchored to the lipids
via covalent bonds from
cysteines or free amino
groups on the protein to
one of the several lipid
anchors

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Anchoring Proteins to Membranes (continued)
• N-myristoyl and S-palmitoyl are the anchoring motifs
• Anchors can be via N-terminal Gly
• Form a thioester linkage with Cys

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Figure 8.19 - Certain Proteins Are Anchored to
Biological Membranes by Lipid Anchors
Transport proteins

• Mediate the entry of specific substances into a

cell

Receptor proteins

• Contain specific binding sites for extracellular

substances

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 • Model in which proteins and a lipid bilayer exist side
Fluid-Mosaic Model by side without covalent bonds between them
• Basic structure of the biological membranes is that
of a lipid bilayer, with proteins embedded in the
bilayer structure
• Lipids are sorted into assemblages called rafts,
which serve as fundamental building blocks on
which membrane specificity is based
• Fluid mosaic
• Term that implies that there is lateral motion of
components in the membrane

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Membrane Transport: Passive Transport
• Process by which a substance
enters a cell without
expenditure of cell energy
• Driven by concentration
gradient
• Categories
• Simple diffusion: Process
by which a molecule or an
ion moves through an
opening or pore in a
membrane without
requirement for a carrier or
an expenditure of energy
• Facilitated diffusion:
Process by which
substances enter a cell by
binding to a carrier protein
• Does not require ©energy
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Low-Density Lipoprotein (LDL)
• Principal carrier of
cholesterol in the
bloodstream
• Consists of various
lipids and a protein
• Cholesterol portion is
used by the cell
• Protein portion binds to
the LDL receptor of a cell
• Forms a complex that is
pinched off into the cell via
endocytosis

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