The «building blocks» of life

o They represent one of the four main classes

of organic compounds of biological interest,
together with glucides, proteins and nucleic
acids.

o Lipids are mainly made up of C and H atoms.

They are hydrophobic while they are soluble
in organic solvents.

o Some lipids have polar groups (e.g. phospholipids) in a narrow region of their molecule.
 they are amphipathic molecules (soluble both in water and in apolar solvents).

o Lipids are very different from each other in terms of chemical structure, as they
include esters and hydrocarbons and can be acyclic, cyclic or polycyclic.
 Classes of Lipids
 Fatty acids: long chain carboxylic acids (membranes, intra-intercellular
signalling, energy metabolism).

 Triglycerides: made by three fatty acids esterified to a glycerol

molecule. They are the main energy storage.

 Phosphoolipids: has a hydrophilic "head" containing a phosphate group

and two hydrophobic "tails" derived from fatty acids, joined by an
alcohol residue, usually a glycerol molecule. (membranes, intra-
intercellular signalling).

 Cholesterol: membranes, intra-intercellular signalling, other functions

(bile salts, Vitamin D synthesis.
 Lipids are a heterogeneous class of organic compounds
that play several different role in cell biology.

 Energy Storage
(Triacylglycerols)

 Structure and function

of biological membranes
(Phospholipids)

 Biosignalling
Sphingosine
(Steroids)
 Classes of Lipids

o Fatty acids
oTriacylglycerols (or triglycerides)
o Phospholipids
o Steroids
 Fatty acids
 Aliphatic monocarboxylic acids containing between
4 to 36 carbons. They are very reduced compounds.

 They can be saturated or unsaturated.

 They are the constituent ingredients of almost all

complex lipids and vegetable and animal fats.

 Free fatty acids represent the circulating fraction and energy reserve of
lipids in the body, metabolized by the liver and muscles.

 Due to their insolubility, they require serum lipoproteins (albumin) to

circulate in the blood.
Phospholipids Triacylglycerol
 Saturated Fatty Acid

All single bonds between carbons

Monounsaturated Fatty Acid (MUFA)

One carbon-carbon double bond

Polyunsaturated Fatty Acid (PUFA)

More than one carbon-carbon double bond

In PUFAs, double bonds are never conjugated but
separated by a methylenic group.
 PUFA - Location of Double Bonds
OMEGA (ω) NUMBER

PUFA are identified by position of the double bond

nearest the methyl end (CH3) of the carbon chain;
this is described as the OMEGA NUMBER

Two families:
omega-3 (ω-3) and
omega-6 (ω-6).
First double bond 3 carbons away from the methyl end = omega 3 FA

First double bond 6 carbons away from the methyl end = omega 6 FA
 Essential fatty acids (EFA)

 Essential fatty acids (EFA) are those polyunsaturated fatty acids (PUFA)
that must be provided by foods because they cannot be synthesized in
the body.

 The main ones are: linoleic acid

(ω-6), linolenic acid (ω-3), and
arachidonic acid.
Nomenclature
of Fatty Acid
 Nomenclature of Fatty Acid

ω−3 fatty acids:

C 20:5, ω-3 or C 20:5 Δ 5,8,11,14,17

(eicosapentaenoic acid)

 indicates the distance of double bonds from the carboxylic group

Nomenclature of Fatty Acid

ω−6 fatty acids

C 18:2, ω-6 or C 18:2 cis Δ 9,12

(linoleic acid)
Essential fatty acids

Linoleic acid
C18:2 Δ9,12 or C18:2 ω6

a-linolenic acid
C18:3 Δ9,12,15 or C18:3 ω3
 Fatty acids
chemical and
physical properties

The chemical and physical

properties of fatty acids are
determined by their
• chemical structure
• the length of the aliphatic chain,
• the presence of double bonds
and isomers (cis or trans).
 SATURATED
Stearic acod
(found in butter)

Cis double bond

UNSATURATED (CIS)
Linoleic acid
(found in vegetable oil)

Bent chain - reduced

conformational freedom

Trans double bond

UNSATURATED (TRANS)
Trans-linoleic acis
(found in some margarine)

Extended conformation
 Cis configuration
 In nature, unsaturated fatty acids
generally have cis-configurations
which kinks the chain.

 The conformational freedom of

the fatty acid is reduced.

 Cis bonds limit the ability of fatty

acids to be closely packed.
The more double bonds the chain has in
the cis configuration, the less flexibility
it has.

Oleic acid with one double bond, has a "kink" in it;

Linoleic acid, with two double bonds, has a more

pronounced bend;

Alpha-linolenic acid, with three double bonds,

favors a hooked shape.
 Trans configuration
• Trans fats, naturally occur in small amounts
in meat and milk fat.

• Artificial trans fatty acids form by partial

hydrogenation (reduction) of unsaturated
fatty acids.

• A trans double bond allows a given fatty

acid to adopt an extended conformation.

• Trans fatty acids can pack more regularly

and show higher melting points than cis
forms.
Structural
consequences
of unsaturation

SATURATED CHAINS pack

tightly and form more rigid,
organized aggregates (i.e.,
membranes).

UNSATURATED CHAINS (CIS

FORMS) bend and pack in a less
ordered way, with greater
potential for motion.
Saturated vs Unsaturated
Fatty Acids
Hardening of fats Hydrogenation of
cis-unsaturated fats

by hydrogenation (partial)

• Rancidity consists of a series of hydrolysis and/or oxidation reactions of unsaturated fatty acids.
This alteration is responsible for the formation of compounds that give the food unpleasant smells and
tastes (rancidity).

• In food production, in order to extend the shelf life of food, cis-unsaturated

fats are hydrogenated to produce saturated fats (hardening of fats).

• Partial hydrogenation converts some of the cis double bonds into trans double
bonds (isomerization reaction).

• Hydrogenated fats are used in stick margarine, fast foods, commercial baked
goods (donuts, cookies, crackers), and fried foods.
 ‘Bad Fats’
 Digestion breaks fats down to produce fatty acids and glycerol which pass into the
blood stream. LIPASE catalyses fatty acid metabolism, acting only on the cis-form.

 Saturated fatty acids have no reactive group susceptible to attack by oxidative

reactants (for further use by the body).

 Since they pack together easily they

form plaques which clog up the vessels

 They may be particularly dangerous for

heart health and may pose a risk for
certain cancers.
Trans Fats and Cholesterol

While both saturated and trans fats

increase levels of LDL, trans fats also
lower levels of HDL thus increasing the
risk of coronary heart disease.
 Soaps are soluble salts of long chain
fatty acids with alkali metals.

When oils and fats are mixed with a strong base

(sodium or potassium hydroxide), soap is made! Micelles are aggregates of surfactant
molecules dispersed in a liquid, forming
a colloidal suspension.

A soap contains a nonpolar end that dissolves

in nonpolar fats and oils, and a polar end that
dissolves in water.
Cleaning Action of Soap

In water a micelle forms an aggregate with

the hydrophilic "head" regions in contact with
surrounding solvent and hydrophobic single-tail
regions sequestered in the micelle centre.

Groups of micelles dissolve in water and are

washed away.
 Salts of Carboxylic Acids

• Sodium hydroxide removes a proton to form the salt.

• Adding a strong acid, like HCl, regenerates the carboxylic acid.
Salts of Carboxylic Acids

First name the cation, then name the

anion by replacing the –IC acid with –ATE.
 Classes of Lipids

oFatty acids
oTriacylglycerols (or triglycerides)
oPhospholipids
oSteroids
 Triacylglycerols
(Tri)(acyl)(glycerols): they are made by three fatty acids that are esterified to a glycerol
molecule - it is a condensation reaction.

They are highly hydrophobic, in that the only polar/charged groups are esterified together.

Ester linkage
 Fats and oils
Fats and oils are triglycerols with different physical properties.
• Fats have higher melting points; they are solids at room temperature.
• Oils have lower melting points; they are liquids at room temperature.

The identity of the three fatty acids in the triacylglycerol

determines whether it is a fat or an oil.
SOLID or Semisolid Fats
 Consist of fatty acids having few
or no double bonds.
 Typically obtained from animal
sources.

LIQUID fats (oils)

 Consist of fatty acids having a
large number of double bonds.
 Common in vegetable sources.
 Triacylglycerols
Source of energy

• They represent our main energy storage;

they are localised into fat tissue adipocytes
in the form of a big lipid droplet that occupy
almost the entire cell volume.

• When cells need to use them as energy

source, a lipase is activated (it’s regulated
by hormon axes) that hydrolyzes the fatty
acids from the glycerol, in order to release
them in the bloodstream to fuel other
peripheral tissue metabolism.
 Triglycerides represent an energy source
way more efficient of carbohydrates

o They possess higher energy density, in respect with carbohydrates

(9 Kcal/g vs 4 Kcal/g), in that they are more reduced, and their oxydation
yields more energy.

o They are hydrophobic and can be stored in a smaller volume which is

devoid of water. By comparison, carbohydrate storages – i.e. glycogen– is
stored as 2g of water per g of glycogen.
 Classes of Lipids

o Fatty acids
oTriacylglycerols (or triglycerides)
o Phospholipids
o Steroids
 Phospholipids

Phospholipids are lipids containing:

• Alcohol (glycerol or sphingosine)
• Fatty acids
• Phosphate
• Base (e.g. choline, ethanolamine or serine).
Glycerophospholipids
 Phospholipids are classified according to
alcohol content into:

1- Glycerophospholipids: alcohol is glycerol

2- Sphingophospholipids: alcohol is sphingosine

Glycerophospholipids

Sphingophospholipids
 The most common
glycero-phospholipids
Phosphatidylcholine: it is formed of glycerol, two fatty acids,
phosphate, and choline which is a nitrogenous base.

Phosphatidyl choline is the most abundant phospholipid in biological

membranes.
Glycerophospholipids
in intracellular signalling
Membrane phospholipids are involved in the
transduction of ligand-receptor-based signals.

The engaging of a ligand to its receptors

triggers the activity of phospholipase C (PLC),
that separates the polar head of the
phospholipid from the rest of the molecule.

The polar head, and the remaining backbone,

often act as second messengers that regulate
several processes in the cell and in its ability to
react to external stimuli.
 Classes of Lipids

o Fatty acids

oTriacylglycerols (or triglycerides)

o Phospholipids
o Steroids
 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.
Cholesterol
 Precursor of all steroids.

 Component of animal cell membranes

 Is an aliphatic polycyclic alcohol

which consists of 27 C atoms assembled
into 4 conjugated cycloalkanes.

 -OH group, the only polar group in an apolar

molecule. Thanks to it, cholesterol can be
esterified.
Cholesterol – Essential biological functions
Cholesterol helps make the membrane
impermeable to small water-soluble molecules
and keeps the membrane flexible over a wide
temperature range.