Lipids are non-polar (hydrophobic) compounds,

soluble in organic solvents.

Lipids: Most membrane lipids are amphipathic, having a
non-polar end and a polar end.
Complex Lipids & Membranes Fatty acids consist of a hydrocarbon chain with a
carboxylic acid at one end.
A 16-C fatty acid: CH3(CH2)14-COO-
Non-polar polar

A 16-C fatty acid with one cis double bond between

C atoms 9-10 may be represented as 16:1 cis D9.

O
Double bonds in fatty O
a C

acids usually have the 3 1 O a C
4 2 3 1 O
cis configuration. 4 2

Most naturally fatty acid with a cis-D9

occurring fatty acids fatty acid with a cis-D9
double bond
have an even number double bond
of carbon atoms.
Some fatty acids and their common names:
There is free rotation about C-C bonds in the fatty acid
14:0 myristic acid; 16:0 palmitic acid; 18:0 stearic acid;
hydrocarbon, except where there is a double bond.
18:1 cisD9 oleic acid
18:2 cisD9,12 linoleic acid Each cis double bond causes a kink/twist in the chain.
18:3 cisD9,12,15 a-linonenic acid Rotation about other C-C bonds would permit a more
20:4 cisD5,8,11,14 arachidonic acid linear structure than shown, but there would be a twist.
20:5 cisD5,8,11,14,17 eicosapentaenoic acid (an omega-3)

Physical properties of fatty acids 2. Melting points of fatty acids

1. Water-solubility of fatty acids
The length of the carbon chain in a fatty acid is important
in determining things like water-solubility and
melting/boiling points.
Long carbon chains are non-polar, and things with long
carbon chains on them do not dissolve in water.
Short chain fatty acids are slightly water-soluble, because
the carboxyl group (-COOH) is polar.
Melting points also increase with increasing molar mass
(London forces), so the longer the carbon chain, the higher
the melting point of the fatty acid.
The presence of double bonds (all cis-stereochemistry)
lowers the melting point (makes it easier for the fatty acid
to melt) because these double bonds cause the molecule to
become bent (less attractions between chains).

1
 Type of Lipids Lipids
Insoluble in water (think oil & water)
5 types of lipids:
triglycerides (fats & oils): long-term energy storage,
insulation.
phospholipids (cell membranes)
bile acids (emulsification lipids)
steroids (cell signaling, messenger): cholesterol
molecules modified to form sex hormones. (e.g.
testosterone, estrogen, etc.)
waxes (protection, prevents water loss): used mainly by
plants, but also bees, some furry animals and humans.

Triglycerides Phospholipids

Steroids
Waxes

2
 Triglycerides: energy storage lipids
Fats and oils
Triacylglycerols/triglycerides are lipids formed by the
.
esterification of three fatty acids to a glycerol molecule.
Fats store energy in the form of triacylglycerols
Both fats and oils are complex mixtures in which many
different kinds of triacylglycerols are present
fats are solids or semi-solids at room temperature
oils are liquids at room temperature
Generally, fats are obtained from animal sources, while
oils are obtained from plants.
Fats involve triacylglycerols that contain mainly saturated
fatty acid components, while oils have more unsaturated
fatty acids components
Hydrolysis: since triacylglycerols are tri-esters, the
ester groups can undergo hydrolysis to yield
carboxylic acids and glycerol (1,2,3-Propanetriol).
This kind of reaction is important in digestion.
Simple triacylglycerols have three identical fatty acid
molecules.
Mixed triacylglycerols have different fatty acid
molecules incorporated in them.
Chemical reactions of triacylglycerols
Triacylglycerols have ester groups and (sometimes) double
bonds, so the reactions that can happen with triacylglycerols
involve those functional groups (hydrolysis, addition
reactions)
They can also undergo oxidation (enzyme-mediated) at the
double bond to produce two carbonyl groups (aldehyde and
then carboxylic acid).
Enzymes catalyze the hydrolysis of triacylglycerols in a
stepwise fashion. The outside ester groups are hydrolyzed first
before the middle group.
In certain cases, triacylglycerols are only partially hydrolyzed
(partial hydrolysis) this happens when only one or two of the
fatty acid groups are removed from the triacylglycerol by
hydrolysis.
3

Saponification: as before, the hydrolysis of an ester carried
out under basic conditions is called saponification. The
base causes de-protonation of the carboxylic acid to form a
carboxylic acid salt (called fatty acid salts).
Saponification of a triacylglycerol yields fatty acid salts.
The anions (negative ions) in these salts have long carbon
chains and they have both polar and non-polar
components.
In the body (and other aqueous environments), these
anions form ball-shaped structures called micelles.
Micelles are able to interact with both polar and non-polar
molecules, and serve as soaps/detergents.

Hydrogenation of a triacylglycerol can happen if When hydrogenation occurs, the

physical properties of a
the triacylglycerol has unsaturated fatty acid triacylglycerol will change. For
chains. example, more saturated chains
will lower the melting point of
Hydrogenation of the double bonds (adding H2 the triacylglycerol, perhaps
across the C-C double bond) converts C-C double causing it to become a
semisolid/solid at room
bonds to C-C single bonds. temperature.
This reaction is used in the food
industry to make margarine,
peanut butter, and other partially
hydrogenated products; however,
partial hydrogenation also results
in the conversion of cis-double
bonds to trans-double bonds
(trans-fats).

Oxidation of the C-C double bonds can also occur. Phospholipids

In this process, both bonds in the double bond are broken
and two C=O groups are made:
Glycerophospholipids (phosphoglycerides), CH2OH
are common constituents of cellular
oxidation oxidation
membranes. H C OH
O2 from air O2 from air They have a glycerol backbone.
short-chain short-chain CH2OH
unsaturated fatty
acid chain
aldehydes carboxylic acids
Hydroxyls at C1 & C2 are esterified to fatty
glycerol
acids.

This kind of reaction occurs when fats become rancid An ester forms
(decompose in air), producing compounds that have bad when a hydroxyl Formation of an ester:
smells (short-chain aldehydes and carboxylic acids). reacts with a O O
carboxylic acid,
R'OH + HO-C-R" R'-O-C-R'' + H2O
with loss of H2O.

4
 O

O H2C O C R2

R1 C O CH
1 O

H22C O P O

3 O
phosphatidate

In most glycerophospholipids (phosphoglycerides),

In phosphatidate: Pi is in turn esterified to OH of a polar head group (X):
fatty acids are esterified to hydroxyls on C1 & C2 e.g., serine, choline, ethanolamine, glycerol, or inositol.
the C3 hydroxyl is esterified to Pi. The 2 fatty acids (R1 and R2) tend to be non-identical.
They may differ in length and/or the presence/absence of
double bonds.

O
Phosphatidylcholine, with O
O H2C O C R2 choline as polar head group, is O H2C O C R2

R1 C O CH O another glycerophospholipid. R1 C O CH O CH3

+
H2C O P O CH2 CH2 N CH3
H2C O P O It is a common membrane lipid O CH3

O H (e.g. lecithin) phosphatidylcholine

OH OH
H OH
OH H
phosphatidyl- H H
inositol H OH

Phosphatidylinositol, with inositol as polar head group,

is one glycerophospholipid.
In addition to being a membrane lipid,
- Lecithin -
phosphatidylinositol has roles in cell signaling.

OH OH
Sphingolipids are derivatives of
H
O the lipid sphingosine, which has a H2 C C CH
long hydrocarbon tail, and a polar
O H2C O C R2 H3N+ CH
Each glycerophospholipid domain that includes an amino group.
R1 C O CH O HC
includes O
a polar region: H2C O P O X

O P O
(CH2 )12

glycerol, carbonyl O O sphingosine CH3

of fatty acids, Pi, & the glycerophospholipid O OH
H
polar head group (X) H2C C CH Sphingosine may be reversibly
polar phosphorylated to produce the signal
non-polar hydrocarbon H3N+ CH
tails of fatty acids (R1, R2). "kink" due to molecule sphingosine-1-phosphate.
double bond non-polar HC
Other derivatives of sphingosine are
(CH2 )12 commonly found as constituents of
sphingosine-1-P
CH3
biological membranes.

5
 OH OH
H CH3 O
H2 C C CH H2 H2
H3C N+ C C O P O
The amino group of sphingosine can H3N+ CH
Sphingomyelin has CH3 O OH
form an amide bond with a fatty acid HC a phosphocholine or phosphocholine H
carboxyl, to yield a ceramide. phosphethanolamine
H2C C CH
(CH2 )12 sphingosine
OH OH
head group. NH CH
sphingosine CH3
H Sphingomyelins are O C HC
H2 C C CH
common constituent fatty acid R (CH2 )12
NH CH
In the more complex sphingolipids, of plasma membranes
Sphingomyelin CH3
O C HC a polar head group" is esterified
to the terminal hydroxyl of the Sphingomyelin, with a phosphocholine head group, is
R (CH2 )12
sphingosine moiety of the ceramide. similar in size and shape to the glycerophospholipid
ceramide CH3 phosphatidyl choline.

CH2OH
A cerebroside is a O
OH Amphipathic lipids in
sphingolipid H OH
OH H O association with water form
(ceramide) with a H
H H H2C C CH complexes in which polar
monosaccharide
H OH NH CH
regions are in contact with
such as glucose or
water and hydrophobic Bilayer Spherical Micelle
galactose as polar O C HC
regions away from water.
head group. R (CH2 )12
A ganglioside is a cerebroside with Depending on the lipid, possible molecular arrangements:
-galactose head group CH3
ceramide with a polar Various micelle structures. e.g., a spherical micelle is
head group that is a complex oligosaccharide, including a stable configuration for amphipathic lipids with a
the acidic sugar derivative sialic acid. conical shape, such as fatty acids.
Cerebrosides and gangliosides, collectively called
A bilayer. This is the most stable configuration for
glycosphingolipids, are commonly found in the outer
amphipathic lipids with a cylindrical shape, such as
leaflet of the plasma membrane bilayer, with their sugar
phospholipids.
chains extending out from the cell surface.

Membrane fluidity: Steroids

The interior of a lipid bilayer
is normally highly fluid. liquid crystal
In the liquid crystal state, hydrocarbon chains of
phospholipids are disordered and in constant motion.
At lower temperature, a membrane containing a single
phospholipid type undergoes transition to a crystalline
state in which fatty acid tails are fully extended, packing
is highly ordered, & van der Waals interactions between
adjacent chains are maximal.
Kinks in fatty acid chains, due to cis double bonds,
interfere with packing in the crystalline state, and lower
the phase transition temperature.
Steroids are a family of lipids found in plants and
crystal animal
A steroid contains four fused carbon ring: 17
carbon atoms make the structural unit of steroids
known as steroid nucleus.
Steroid nucleus is found in a number of extremely
important biological molecules: cholesterol,
adrenocorticoid hormones, the sex hormone and
bile acids.

6
Cholesterol, an
important constituent of
cell membranes, has a
rigid ring system and a
short branched
hydrocarbon tail.

Cholesterol is largely
hydrophobic.
Cholesterol inserts into bilayer membranes with its hydroxyl
But it has one polar group, group oriented toward the aqueous phase & its hydrophobic ring
a hydroxyl, making it system adjacent to fatty acid chains of phospholipids.
amphipathic. The OH group of cholesterol forms hydrogen bonds with polar
phospholipid head groups.

Interaction with the relatively rigid cholesterol

decreases the mobility of hydrocarbon tails of
phospholipids.
But the presence of cholesterol in a phospholipid
membrane interferes with close packing of fatty acid
tails in the crystalline state, and thus inhibits transition
to the crystal state.

Phospholipid membranes with a high concentration of

cholesterol have a fluidity intermediate between the
liquid crystal and crystal states.

Steroid Hormones Made from Cholesterol

Two strategies by which phase changes of membrane

lipids are avoided:
Cholesterol is abundant in membranes, such as
plasma membranes, that include many lipids with
long-chain saturated fatty acids.
In the absence of cholesterol, such membranes would Multistep

crystallize at physiological temperatures. Glucose Metabolism Salt Excretion

Cholesterol
The inner mitochondrial membrane lacks cholesterol,
but includes many phospholipids whose fatty acids
have one or more double bonds, which lower the
melting point to below physiological temperature.

Anti-inflammatory

7
 Synthesis of Vitamin-D A child who began life in a closet

Regulate Calcium
Metabolism

Retinal Comes from Carotene Isoprene Vitamins

Mitochondrial and Chloroplast Membrane

Carotenoids
Electron Carriers

8
 - Waxes are found in many plants and animals (or
Waxes humans).
Waxes are carboxylic acid esters, RCOOR ,with long, straight - In plants, they help prevent loss of water and
hydrocarbon chains in both R groups. damage from pests.
Waxes are secreted by sebaceous glands in the skin of animals - In humans and animals, provide waterproof
and perform mostly external protective functions. coating on skin and fur.

Ear Wax (Cerumen) is Not Wax Chemistry of Bile Acids

The primary components of ear wax are shed layers of
skin: 17

- 60% of the earwax consisting of keratin 27

- 1220% saturated and unsaturated long-chain fatty acids, 3

alcohols and squalene,

Cholesterol
- 69% cholesterol

12 24

3 7

Bile acid

(Cholic acid)

Amphipathic Nature of Bile Acids Amphipathic Molecules

Exist in micelles when concentration is greater than the CMC (Critical Micellar
Concentration)

9
 Mixed Micelle
cholesterol lecithin

bile

salt

Emulsification of Fat by Bile

10