Lipids: Fats & Oils

Important for the assignment

This lecture will cover LO1:
Discuss how the structural features of
proteins and phospholipids are
determined by their chemical
structures
Fatty Acids

• Fatty acids contain a carboxylic acid group

• This should make them quite polar
• However, they also contain a long hydrocarbon tail
• Which overall, makes them nonpolar.
• Fatty acids typically contain between 12 and 20 carbons
• The number is usually always even.
• The nonpolar tails interact with London forces.

nonpolar polar

4
Fatty Acids
Melting points for saturated fatty acids
•Increases with increasing chain length
•Greater VdW contacts
Melting Temperature {°C}

No. of Carbons
5
Fatty Acids
• Some fatty acids contain double bonds

• Saturated

• monounsaturated

• polyunsaturated

• polyunsaturated

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Fatty Acids

• The common fatty acids found in biological systems

Linolenic acid is one of the omega-3 fatty acids.

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Fatty Acids

• Normally the double bonds are cis

• This lowers the melting points for fatty acids containing double bonds.
Melting Temperature {°C}

No. of Double Bonds

8
Fatty Acids

• The cis double bonds produce kinks, which disrupt the London forces
(part of the van der Waals forces) by preventing the tails from
packing close to one another.
•
• Zero double bonds (Source-lard) VS Two double bonds (source-safflower)

9
Fatty Acids
• As acids, the carboxylic acid group in fatty acids can react with a base
to produce a carboxylate ion
• By donating its proton (H+) to the base the fatty acid becomes negatively
charged.

The negative charge makes the polar head portion of the the fatty acid
even more polar and hydrophilic.
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Fatty Acids

• The salts of fatty acids are also called soaps, and are considered
amphipathic, meaning they have a part that is very hydrophobic
along with a part that is very hydrophilic.

When placed in water, amphipathic

molecules, form structures, such as
micelles, which attempt to address the
conflict.

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Phospholipids and Glycolipids

• Phospholipids and Glycolipids are what biological membranes are

made of.
• Like the soaps, these molecules are highly aphipathic, and when mixed with
water spontaneously form membranes that are described as lipid bilayers.

Soaps form Phospholipids form

Micelles Lipid Bilayers
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Phospholipids and Glycolipids

• Phosphospholipids
• There are two types of phospholipids
• Sphingolipids

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Phospholipids and Glycolipids

• Phosphospholipids
• There are two types of phospholipids
• Glycerophospholipids

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Phospholipids and Glycolipids

• Phosphospholipids
• The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

There is usually
an additional
alcohol attached
to the other side
of the phosphate

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Phospholipids and Glycolipids

• Phosphospholipids
• The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

phosphoester
phosphoester
17 bonds
bonds
 Phospholipids and Glycolipids

• Phospholipids
• The Glycerophospholipids have a structure similar to triglycerides, with one
of the fatty acids replaced with a phosphate.

“Phosphotidyl-”
refers to everything
but the X

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Phospholipids and Glycolipids

• Phosphospholipids
• Phospholipids are used commercially as emulsifying agents.
• An emulsifying agent stabilizes an emulsion.
• An emulsion is a colloidal suspension of one liquid in another.
• An example is mayonnaise, which is a colloidal suspension of oil and water.

• Lecithin, which is another name for the phospholipid phosphotidylcholine, is

used as an emulsifying agent in mayonnaise and other prepared foods.

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Phospholipids and Glycolipids

• Phosphospholipids
• The sphingolipids function similarly to the glycerophospholipids, but
structurally they are different.
• There is not glycerol core
• The glycerol and one of the fatty acids found in glycerophospholipids is replaced with a
molecule called sphingosine.

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Phospholipids and Glycolipids

• Phosphospholipids
• The sphingolipids are found in the myelin membranes that insulate the nerve
cells.
• Some sphingolipids use sugars for the alcohol portion of the molecule
• These are called glycolipids.

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Lipoproteins
• Lipoproteins are used to transport the
water insoluble lipids such as triglycerides,
phospholipids and cholesterol, in the blood.

• Lipoproteins contain lipids and proteins.

• They include:
• Chylomicrons transport primarily triglycerides from the
digestive track.
• LDLs (low density lipoproteins) transport cholesterol,
triglycerides and phospholipids from the liver to other
tissues.
• HDLs (high density lipoproteins) transport cholesterol
and phospholipids back to the liver.

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Lipoproteins

• The HDL and LDL levels in the blood can be used to assess ones risk
for atherosclerosis.
• High levels of HDL is considered good
• This is why HDL is sometimes referred to as “good cholesterol”

• > 40 mg/dL is good.

• High levels of LDL is considered bad

• This is why LDL is sometimes referred to as “bad cholesterol”

• > 100 mg/dL is bad.

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24
Saturated/Unsaturated fatty
acids
Structure of Triglycerides
• The structure of triglycerides is varied due to the variety of fatty
acids. These molecules may be two types which give rise to lipids
with different properties:-
• Saturated – these have no double C - C bonds e.g. palmitic acid and
stearic acid. Triglycerides containing saturated fatty acids are very
straight in structure and pack closely together.
• Unsaturated – have one or more double C - C bonds e.g. oleic acid
or linoleic acid. Lipids containing unsaturated fatty acids are ‘kinked’
in structure and cannot pack so closely together.
SATURATED & UNSATURATED?
 • Saturated
• Unsaturated

• Differ in terms of melting

point even if very nearly
identical chemical formulae

• Not apparent why in the

linear diagram (left)

• Saturated
• Saturated with hydrogen
• No double/triple bonds
• LINEAR

• Unsaturated
• Unsaturated with hydrogen
• One or more double/triple bonds
• KINKED
Saturated FAs can stack Unsaturated FAs cannot stack
VdW contacts Less VdW due to lack of contact
Large surface areas Lower melting temperatures
Large RFMs/# electrons
• Once we introduce
the double bond in
unsaturated fatty
acids, we also
introduce isomerism

• The unsaturated
fatty acids can be
either cis or trans
fatty acids

• This also affects their

properties
 Cis/trans isomerism

• Cis main groups same side of double bond

• Trans main groups opposite sides of double bond

• Caused by lack of rotation about a double bond

• Single bonds can freely rotate around the sigma • Double bond requires an energy barrier to be overcome
bond • To interconvert one to another, you must break the pi
• Groups can be drawn anyway, up or down, as they bond, move the atoms, then reform the pi bond
can rotate freely so they are interchangeable • Locks into one of two conformations
• As with sat/unsat, cis and
trans isomers have
different stacking potentials

• Trans fats you may have

heard of as being worse for
you. This is because
• Can stack more easily
• So more energy is therefore
required to melt them
• So they have a higher melting
point
• So harder to burn off
essentially
Remember this is due
to VdW and the
hydrophobic
interaction
Summary
Membrane fluidity
Biological uses of lipids
PHOSPHOLIPIDS

• Phospholipids are also

built around a molecule
of glycerol.

• There are only two fatty

tails and a phosphate
group forms the
hydrophilic “head”.
Phospholipid Example
• They do not all have choline attached to the phosphate
• This phospholipid, common in membranes, is called lecithin
• Instead of having to draw this

• Biochemists are lazy and do everything as a “representative” diagram

PHOSPHOLIPIDS &
MEMBRANES
The POLAR nature
of the phospholipid
molecule keeps the
structure of
membranes intact.
Plasma Membrane
Plasma Membrane
Membrane is composed of:

A. Lipids
 Phospholipids
 Sterols
B. Proteins
 Integral
 Peripheral
C. Carbohydrates
 Glycolipids
 Glycoproteins
Plasma Membrane

Variable components in different membrane types

Membrane Lipids

Amphiphilic lipids

Major types: sphingosine

phospholipids,
glycolipids, sterols

Glycolipid

glycerophospholipid sphingophospholipid
Lipid Components of Membranes

Lipid
composition
varies across
different
membranes.

Fig 11-2
Lipid Components of Membranes

Lipid composition
varies across the two
leaflets of the same
membrane.
Turnover of Membrane Lipids

Fig 10-16
Defects in Membrane Turnover

Deposits of
gangliosides in Tay
Sachs brain
Lipid Aggregates

 Lipids spontaneously
aggregate in water as
a result of the
Hydrophobic Effect.
Lipid Aggregates
Amphiphilic lipids form
structures that solvate
their head groups and
keep their hydrophobic
tails away from water.

Above the critical

micelle concentration,
single-tailed lipids form
micelles. Fig 11-4
 Lipid Aggregates
Fig 11-4
Double-tailed lipids
form bilayers, the basis
of cell membranes.

 Bilayers can form vesicles

enclosing an aqueous cavity
(liposomes). Fig 11-4
Membranes

• Fluid mosaic model

56
Membranes
• Transport across membranes

57
 Membrane Proteins
Integral proteins
(includes lipid-linked):
need detergents to
remove

Peripheral proteins:
removed by salt, pH
changes

Amphitropic proteins:
sometimes attached,
sometimes not
Single Transmembrane Segment Proteins

Usually alpha-helical,
~20-25 residues, mostly
nonpolar.

Example: glycophorin of
the erythrocyte.
Multiple Transmembrane Segment Proteins

7 alpha-helix
motif is very
common.

Example:
bacteriorhodopsin
Beta Barrel Transmembrane Proteins

 Multiple
transmembrane
segments form β
sheets that line
a cylinder.

 Example: porins.
Lipid-Linked Membrane Proteins

 Attached lipid
provides a
hydrophobic
anchor. Fig. 11-14

 An important lipid
anchor is GPI
(glycosylated
phosphatidylinositol.
Membrane Carbohydrates

 On exoplasmic face
only
Membrane Carbohydrates

 On exoplasmic face
only

 An example is the blood

group antigens

glycosphingolipids
Membrane Dynamics

At its transition

temperature (TM), the
bilayer goes from an
ordered crystalline state
to an a disordered fluid
one.

Fig 11-16
Membrane Dynamics
Phospholipids in a bilayer have free lateral diffusion.
Membrane Dynamics
Phospholipids in a bilayer have restricted movement
between the two faces.
Membrane Dynamics
Flippases, floppases, and scramblases catalyze
movement between the two faces.
Fluid Mosaic
Fluorescent Recovery
After Photobleaching

Fluorescent tag is attached

to a membrane component
(lipid, protein, or
carbohydrate).
Fluorescence is bleached
with a laser.
Recovery is monitored over
time.
Fluorescent Recovery
After Photobleaching

FRAP Movie
Protein Mobility in the Membrane

Some membrane
proteins have
restricted
movement.

May be anchored
to internal
structures (e.g.,
glycophorin is
tethered to
spectrin).
Protein Mobility in the Membrane
Lipid rafts are
membrane
microdomains
enriched in
sphingolipids,
cholesterol, and
certain lipid-linked
proteins.

Thicker and less

fluid than neighboring
domains.
Protein Mobility in the Membrane
Lipid rafts are
membrane
microdomains
enriched in
sphingolipids,
cholesterol, and
certain lipid-linked
proteins.

Thicker and less

Lipid Rafts fluid than neighboring
domains.
 Nature Reviews Molecular Cell
Biology 4, 414-418 (May 2003)

Domains of gel/fluid lipid segregation in a model membrane vesicle, which is a mixture of

fluid dilaurylphosphatidylcholine phospholipids with short, disordered chains and gel
dipalmitoylphosphatidylcholine phospholipids with long, ordered chains. A red fluorescent
lipid analogue (DiIC18) partitions into the more ordered lipids, whereas a green fluorescent
lipid analogue (BODIY PC) partitions into domains of more fluid lipids. These domains in a
model membrane are much larger than the domains of cell membranes.
cell membrane
Structure of the Plasma Membrane
 The Plasma Membrane (PM)
• PM surrounds every cell on earth
• Protein-studded thin film that separates a cell from its surroundings.
• Enables the molecular composition of a cell to different from that of its
environment.
• Eukaryotic cells also have internal membranes surrounding organelles.
Functions of the Plasma Membrane

1. Regulates the passage of materials into and out

of the cell (whilst maintaining separation
between the intra- and extra-cellular
environments.
2. Receives chemical signals from other cells, e.g.
hormones, growth factors, neurotransmitters.
3. Maintains structural and chemical relationships
with other cells.
4. Protects the cell, helps in cell movement,
secretion, and in transmitting impulses (as in
nerve cells).
Membrane Structure & Function

The plasma membrane consists of a phospholipid

bilayer and associated proteins

Phospholipid structure

• 2 long, hydrophobic fatty acids (“tails”)

• hydrophilic glycerol/phosphate area (“head”)

Membrane Structure
Outside Cell

Hydrophilic

M
E
M Hydrophobic
B Region
R
A
N
E

Hydrophilic

Inside Cell
 Overview of Plasma Membrane functions
The plasma membrane is involved in cell
communication, import and export of
molecules, and cell growth and motility.
Receptor proteins in the plasma membrane
enable the cell to receive signals from the
environment
channels and transporters in the
membrane enable the import and export of
small molecules
The flexibility of the membrane and its
capacity for expansion allow the cell to
grow, change shape, and move.
Overview of Membrane Structure

A cell membrane consists of a lipid bilayer in which proteins are embedded.

Phospholipid

Hydrophilic head
- water loving

Hydrophobic tail
- water hating

4.
6
The polar hydrophilic heads are water soluble
and the hydrophobic heads are water
insoluble
Hydrophobic (water-hating) tail
air

aqueous solution

Hydrophilic (water-loving) head

Phospholipids form
micelles when
submerged in water
 Fluid Mosaic Model of the Plasma
Membrane
Carbohydrate
chain

Glycoprotein

Intrinsic
Protein

Non-polar hydrophobic Phospholipids

fatty acid
Biochemical Composition of the Plasma
Membrane
Side view

Surface view
Biochemical Composition of the Plasma Membrane

The main components are protein and phospholipid:

Protein
Phospholipid

Side view
4.
6
 This model is referred to as the ‘fluid mosaic
model’ because the components are free to
Surface view move independently of each other.

4.
6
 Membrane Lipids

• Membrane lipids have a hydrophilic

‘head’ and hydrophobic ‘tail’

• Molecules with both hydrophobic

and hydrophilic parts are termed
AMPHIPATHIC

• Phospholipids are the most

abundant class of membrane lipids
Phosphatidylcholine is the most common phospholipid in cell
membranes.
Different types of membrane lipids are all amphipathic
A hydrophilic molecule
attracts water molecules.
Both acetone and water are
polar molecules: thus
acetone readily dissolves in
water.
A hydrophobic molecule tends to
avoid water.
2-methylpropane molecule is
entirely hydrophobic, thus cannot
form favorable interactions with
water - water molecules to
reorganize into a cagelike
structure around it, to maximize
their hydrogen bonds with each
other.
 The Lipid Bilayer
• Because cells are filled with and surrounded by water, the structure of
cell membranes is determined by the way membrane lipids behave in an
aqueous environment.
• Amphipathic membrane lipids form ‘bilayers’ in water
Phospholipid bilayers spontaneously close in on
themselves to form sealed compartments.
•Avoids exposure of the hydrophobic tails to water,
which would be energetically unfavorable.
•Allows:
• Separation of a cell from it’s environment
• Vesicles to pinch off and form from membranes
• Tears to repair quickly
THE LIPID BILAYER IS A FLEXIBLE 2-D FLUID

•FLEXIBLE and can bend – important for

forming vesicles

•Aqueous environment inside and outside

a cell prevents membrane lipids from
escaping from the bilayer but they can
move about within the bilayer

•FLUID - Consistency of olive oil at body

temperature.
THE FLUIDITY OF A LIPID BILAYER DEPENDS ON ITS
COMPOSITION

• Fluidity is important for membrane function & has to be maintained within

certain limits.

• Dependent on phospholipid composition – (nature of the hydrocarbon

tails).
• The closer and more regular the packing of the tails, the less fluid it is.

• More unsaturated fatty acids (containing C=C) : more fluid.

• More saturated fatty acids (containing only C-C) : less fluid.

IN ANIMAL CELLS MEMBRANE FLUIDITY IS MODULATED BY INCLUSION
OF CHOLESTEROL
•Cholesterol stiffens and strengthens the membrane, helping to regulate
fluidity (fits into gaps between phospholipids).
•Constitutes ~ 20% of the lipids in the plasma membrane.
 Carbohydrates
• Found on the outer surface of all eukaryotic cell
membranes
• are attached to the membrane proteins or
sometimes to the phospholipids.
• Proteins with carbohydrates attached are called
glycoproteins (protein modified by the ER)
• phospholipids with carbohydrates attached are
called glycolipids.
• Both Glycolipids and Glycoproteins can act as Cell Receptor
Sites.
• Hormones may bind to them, as may drugs, to instigate a
response within the cell. They may also be involved in Cell
Signalling in the Immune System.
• The carbohydrates are short
polysaccharides composed of a variety of
different monosaccharides, and form a
cell coat or glycocalyx outside the cell
membrane.
• The glycocalyx is involved in protection
and cell recognition
• antigens such as the ABO antigens on
blood cells are usually cell-surface
glycoproteins.
Eukaryotic cells are coated with sugars.
•Note that all the carbohydrate is on the external (noncytosolic) surface of the
plasma membrane.
CERTAIN PHOSPHOLIPIDS ARE CONFINED TO ONE SIDE OF THE
MEMBRANE

The 2 sides of the lipid bilayer differ in composition with glycolipids only
occurring on the non-cytosolic layer of the membrane where they are
involved in cell recognition and communication.
 Membrane Proteins
• Although the lipid bilayer provides the basic structure of the cell membrane, most
membrane functions are carried out by membrane proteins.
• Plasma membrane proteins have a variety of funtions
Inside the cell membrane (amoeba sisters) – 9m

https://www.youtube.com/watch?v=qBCVVszQQNs&feature=youtu.be

Cell membrane (TED-Ed) – 5m

https://www.youtube.com/watch?v=nsklF1w4eok
Membrane Proteins
Membrane proteins can associate with the lipid bilayer in different
ways.
A transmembrane polypeptide chain
usually crosses the lipid bilayer as an α
helix

•Hydrophobic side chains on exterior of

helix in contact with hydrocarbon tails of
phospholipids

•Hydrophilic side chains form hydrogen

bonds with one another along interior of
the helix.
A transmembrane hydrophilic pore can
be formed by multiple amphipathic α
helices.

•‘CHANNEL PROTEIN’

•Forms a water-filled channel across the

lipid bilayer

•Hydrophilic molecules / ions to pass

through

•Facilitated diffusion
Porin proteins form channels for
water to pass through the
plasma membrane

•Consists of a 16-stranded β sheet

curved around on itself to form a
transmembrane water-filled channel.
 Membrane Proteins
Membrane Proteins Can Be Solubilized in
Detergents
•SDS and Triton X-100 are two commonly used
detergents.
•Sodium dodecyl sulfate (SDS) is a strong ionic
detergent
• Displace lipid molecules from proteins &
unfold the proteins
•Triton X-100 is a mild non-ionic detergent
Detergent molecules aggregate to
form micelles in water.
•Detergent disrupts the lipid bilayer and
interacts with the membrane-spanning
hydrophobic portion of the protein
•Brings the proteins into solution as protein–
detergent complexes
•Phospholipids are also solubilized forming
lipid–detergent micelles
The Plasma Membrane Is Reinforced by the Underlying Cell Cortex
(A)Scanning EM showing human red blood cells, which have a flattened, biconcave shape.

(B)In the cortex of a red blood cell, a network of spectrin and actin are linked together to
form a mesh. This is attached to the PM by the binding of at least two types of attachment
proteins (yellow and blue) to two kinds of transmembrane proteins.
A Cell Can Restrict the Movement of Its
Membrane Proteins
Proteins can be tethered to:
(A)The cell cortex inside the cell,
(B)Extracellular matrix molecules outside the cell, or
(C)Proteins on the surface of another cell.
(D)Diffusion barriers (shown as black bars) can restrict proteins to a particular membrane domain.
Specialized membrane transport proteins facilitate the
passage of selected small, water-soluble molecules.
.

•Can facilitate the passive diffusion of specific molecules

or ions across the membrane (blue circles) / active
pumping of specific substances either out of (purple
triangles) or into (green bars) the cell.
•For some molecules, the membrane is impermeable (red
squares).
•Allows a specific set of solutes to build up inside a
membrane-enclosed compartment, such as the cytosol or
an organelle.