LIPIDS Fats. Oils. Energy.

DEFINITION
 Organic compounds that are found in living organisms that are soluble in non-polar
organic solvents.
Oily, greasy materials that have a glistening appearance.
 Formed of long-chain hydrocarbon groups (carbon and hydrogen) but
may also contain oxygen, phosphorus, nitrogen and sulfur
 Insolubility or immiscibility with water but soluble in organic nonpolar
solvents such as chloroform, ether, benzene and acetone, due to fat’s non-
polar nature.
When lipids are hydrolyzed, they form GLYCEROL and FATTY ACIDS.
BIOLOGICAL FUNCTIONS
Fuel molecules
Highly concentrated energy stores
Signal molecules
Components of membranes:
Phospholipids
Sphingolipids
Cholesterol
CLASSIFICATION
Lipids can be divided into five categories, on the basis of lipid function:
1. Energy-storage lipids (triacylglycerol)
2. Membrane lipids (e.g. phospholipids)
3. Emulsification lipids (bile acids)
4. Messenger lipids (e.g. steroid hormones)
5. Protective-coating lipids (biological waxes)
FATTY ACIDS
Are the “building blocks” of functional lipids
Made up of a methyl (omega) end and a carboxyl end.
Fatty acids are structural components of all the lipids except cholesterol, bile acids and
steroid hormones.
They are naturally occurring monocarboxylic acids that tend to have even numbers of carbon
atoms, and may be classified as:
long-chain (C12 to C26)
medium-chain (C8 and C10)
short-chain (C4 and C6)
Do not generally exist free in large quantity but are complex to other molecules depending
on their function
Fatty acids are often conjugated to other molecules to change their chemical properties
Fatty acids are not like most lipids in that they may be recognized
distinctly by the presence of a COOH group on a carbon chain.
TYPES OF FATTY ACIDS
Fatty acids may also be categorized with regards to the presence (and
number) of unsaturated units (double bonds).
1. SATURATED FATTY ACIDS - contain no double bonds – all C-C
single bonds in the carbon chain component.
With high molecular weight and made of single bonds
These are fatty acids which contain the maximum possible
number of hydrogen atoms.
TYPES OF FATTY ACIDS
2. UNSATURATED FATTY ACIDS - With low Molecular Weight and with the
occurrence of double or triple bonds. Therefore, since a carbon atom can have
only 4 covalent bonds, there is one less bond available for hydrogen, thus,
there is one less hydrogen. (The carbons are NOT "saturated" with hydrogen
atoms.)
TYPES OF FATTY ACIDS
2.1. Monounsaturated fats (MUFAs) possess one C-C double bond in
a monocarboxylic acid structure, and nearly all naturally occurring MUFAs
have cis- stereochemistry.
TYPES OF FATTY ACIDS
2.2. Polyunsaturated fatty acids (PUFAs) possess more than
one double bond in the carbon chain component of the fatty
acid. Up to six double bonds may be found in biochemically
important PUFAs.
TYPES OF FATTY ACIDS
Unsaturated fatty acids are chemically more active and unstable than
saturated fatty acids.
A system exists for describing unsaturated fatty acids in terms of the
number of carbon atoms in the acid and in terms of double bond
position(s):
16:0
Fatty acid with 16 C-atoms and no double
bonds

18:1 D9
Fatty acid with 18 C-atoms and one double
bond at C-9

18:3 D9,12,15
Fatty acid with 18 C-atoms and three double
bonds at C-9, C-12, and C-15
TYPES OF FATTY ACIDS
Several families of unsaturated fats may be recognized by the number of
saturated carbon atoms that follow the last double bond (the placement of the
methyl end of the chain with respect to the double bond).
The term "Omega", being the end letter of the Greek alphabet, indicates
that the count starts from the end of the chain (the CH3 side).
The location of the carbon double bond determines the type of Omega fatty
acid.
Omega 3 means a double bond occurs at the third carbon from the end
carbon of the chain. Omega 9 means a double bond occurs at the 9th carbon
from the end carbon.
TYPES OF FATTY ACIDS
1 3

2 w-3 (omega-3 fatty acid)

2 4 6

1 3 5
w-6 (omega-6 fatty acid)
Omega-3 and Omega-6 fatty acids
Omega-3 (ω3) and omega-6 (ω6) fatty acids are unsaturated "Essential
Fatty Acids" (EFAs) that need to be included in the diet because the human
metabolism cannot create them from other fatty acids.
 Since these fatty acids are polyunsaturated, the terms n-3 PUFAs and n-6
PUFAs are applied to omega-3 and omega-6 fatty acids, respectively. These
fatty acids use the Greek alphabet (α,β,γ,...,ω) to identify the location of the
double bonds.
Polyunsaturated Fatty Acids
Metabolism of natural 20-
carbon polyunsaturated fatty
acids like arachidonic acid
results in the biosynthesis of
mediators with potent
physiological effects such as
prostaglandins, prostacyclins,
thromboxanes, leucotrienes,
and lipoxins.
These substances are known
collectively as eicosanoids.
Metabolism of natural C20
Cis-fatty acids produces
powerful eicosanoids.
Thromboxane is a member of the family of lipids known as
eicosanoids. It is produced in platelets by thromboxane
synthetase, which is produced from the endoperoxides by the
cyclooxygenase (COX) enzyme from arachidonic acid.
Thromboxane is a vasoconstrictor, potent hypertensive agent, and
facilitates the clumping of platelets. It is in homeostatic balance in
the circulatory system with prostacyclin, a related compound. The
widely-used drug aspirin acts by inhibiting the ability of the COX
enzyme to synthesize the precursors of thromboxane within
platelets.
Prostaglandins are a group of lipids made at sites of tissue
damage or infection that are involved in dealing with injury and
illness. They control processes such as inflammation, blood flow,
the formation of blood clots and the induction of labour.
They are derived enzymatically from the fatty acid arachidonic
acid.
Problems with prostaglandins can limit the healing process, cause
increased inflammation and pain, and impact your overall health.
Prostaglandins are hormones created during a chemical reaction
at the site where an injury or other issue occurs.
Leukotrienes are a family of eicosanoid inflammatory mediators
produced in leukocytes by the oxidation of arachidonic acid and
the essential fatty acid eicosapentaenoic acid by the enzyme
arachidonate 5-lipoxygenase.

Acute asthma attacks are often triggered by allergens or

exercise. Leukotrienes, classified as inflammatory molecules are
one of several substances which are released by mast cells
during an asthma attack, and it is leukotrienes which are
primarily responsible for the bronchoconstriction.
Hydroxy Fatty Acids are glycosides resulting from the reaction of
the alcoholic hydroxy group of any hydroxy fatty amide with
alpha -ascarylopyranose or its derivatives.
These are found in plants (chain from 12 up to 24 carbon
atoms) and in animal wool waxes, skin lipids and specialized
tissues, mainly in brain.
It has been postulated that these lipids play a role in
reproduction. It was also found to have potent anti-cancer
activities in vitro and in animal models.

Castor oil is the only commercial source of hydroxyl fatty acid

that has industrial value.
PROPERTIES OF FATTY ACIDS
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.
PROPERTIES OF FATTY ACIDS
Melting points of fatty acids
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).
ENERGY-STORAGE LIPIDS
Fats store energy in the form of triacylglycerol.

Older term for triacylglycerol: triglycerides

Triacylglycerol is a lipid formed by the esterification of three fatty acids to a glycerol molecule.
ENERGY-STORAGE LIPIDS
Simple triacylglycerol has three identical fatty acid molecules.
Mixed triacylglycerol has different fatty acid molecules incorporated in them.
ENERGY STORAGE LIPIDS
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
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
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.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
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.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
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).
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
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.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
Oxidation of the C-C double bonds can also occur.
In this process, both bonds in the double bond are broken and two C=O groups are made:

oxidation oxidation

O2 from air O2 from air

short-chain short-chain
unsaturated fatty aldehydes carboxylic acids
acid chain

This kind of reaction occurs when fats become rancid (decompose in air), producing compounds
that have bad smells (short-chain aldehydes and carboxylic acids).
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
Hydrogenation of a triacylglycerol can happen if the triacylglycerol has unsaturated fatty acid chains.
Hydrogenation of the double bonds (adding H2 across the C-C double bond) converts C-C double bonds
to C-C single bonds.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
Hydrogenation is a commercial chemical process to add more hydrogen to natural unsaturated
fats to decrease the number of double bonds and retard or eliminate the potential for rancidity.

Unsaturated oils, such as soybean oil, which

contain unsaturated fatty acids like oleic and
linoleic acids, are heated with metal catalysts
in the presence of pressurized hydrogen gas.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
Hydrogen is incorporated into the fatty acid molecules and they become saturated with
hydrogen. Oleic acid (C18:1) and linoleic acid (C18:2) are both converted to stearic acid (C18:0)
when fully saturated.
The liquid vegetable oil becomes a solid saturated fat (shortening with a large percentage of
tristearin).
By comparison, animal fats have more than 70% saturated fatty acid radicals.
Fully saturated fats are too waxy and solid to use as food additives, so manufacturers use
partially hydrogenated oils.
These oils are also produced at high temperatures with metal catalysts and pressurized hydrogen,
but the process is stopped when the oil has the proper consistency for its application.
CHEMICAL REACTIONS OF TRIACYLGLYCEROL
The high temperatures and catalysts used for this chemical reaction weaken the double bonds
and, as a side effect, cause a large percentage of the natural Cis double bonds to change to
Trans double bonds.
This reaction is used in the food industry to make margarine, peanut butter, and other partially
hydrogenated products.
TRANS FAT
Double bonds bind carbon atoms tightly and prevent rotation of the carbon atoms along the
bond axis.
This gives rise to configurational isomers which are arrangements of atoms that can only be
changed by breaking the bonds.
The Latin prefixes Cis and Trans describe the orientation of the hydrogen atoms with respect to
the double bond.
Cis means "on the same side" and Trans means "across" or "on the other side".
TRANS FAT
Trans fatty acids are present mainly
in partially hydrogenated fats, but
they are also present in
hydrogenated fats because chemical
reactions never achieve 100%
efficiency.
TRANS FAT
When large amounts of
Trans fatty acids are
incorporated into the cells,
the cell membranes and
other cellular structures
become malformed and do
not function properly.
TRANS FAT
Trans fats are bad for your heart. Dietary trans fats raise the
level of low-density lipoproteins (LDL or "bad cholesterol")
increasing the risk of coronary heart disease.
Trans fats also reduce high-density lipoproteins (HDL or "good
cholesterol"), and raise levels of triglycerides in the blood. Both
of these conditions are associated with insulin resistance which is
linked to diabetes, hypertension, and cardiovascular disease.
TRANS FAT
Harvard University researchers have reported that people who ate partially hydrogenated oils,
which are high in Trans fats, had nearly twice the risk of heart attacks compared with those who did
not consume hydrogenated oils.
Trans fats are bad for your brain. Trans fats also have a detrimental effect on the brain and nervous
system.
Neural tissue consists mainly of lipids and fats. Myelin, the protective sheath that covers
communicating neurons, is composed of 30% protein and 70% fat. Oleic acid and DHA are two of
the principal fatty acids in myelin.
Studies show that trans fatty acids in the diet get incorporated into brain cell membranes, including
the myelin sheath that insulates neurons. These synthetic fats replace the natural DHA in the
membrane, which affects the electrical activity of the neuron.
TRANS FAT
Trans fatty acid molecules alter the ability of neurons to communicate and may cause neural
degeneration and diminished mental performance.
Neurodegenerative disorders such as Multiple Sclerosis (MS), Parkinson's Disease, and Alzheimer's
Disease appear to exhibit membrane loss of fatty acids.
TRANS FAT
Unfortunately, our ingestion of trans fatty acids
starts in infancy.
A Canadian study showed that an average of
7.2% of the total fatty acids of human breast
milk consisted of trans fatty acids which
originated from the consumption of partially
hydrogenated vegetable oils by the mothers.
CLASSES OF LIPIDS
The other lipid classes generally contain fatty acids conjugated to other molecules.
A. Glycerol-derived lipids
Fatty acids conjugated to sugar alcohol with 3 carbons (typically connected by single
bonds to 2 or 3 FAs)
including the fats (saturated, mono- and poly-unsaturated) and oils (liquid fats) and
the phospholipids
PHOSPHOLIPID
These molecules are structurally similar to the triglycerides.
Triglycerides have 3 fatty acid chains, but the phospholipids have only 2 fatty acid chains and one
phosphate (-) group.
The negatively charged phosphate group (and its various end groups) cause this end of the
molecule to form a "polar" covalent bond with glycerol.
That is this end of the phospholipid molecule is "polar" while the fatty acid chain is "non-polar".
Therefore one end of the molecule is charged (-), i.e. polar and the other end of the molecule is
not charged (neutral), i.e. non-polar.
Since water is also a polar molecule the polar end of the phospholipid is "attracted" to the + ends
of the water molecules. It is said to be "hydrophilic" (or water loving).
While the neutral end of the phospholipid molecule is non-polar, i.e. is repelled by the "polar"
water molecules, it is said to be "hydrophobic" (water fearing).
CLASSES OF LIPIDS
The other lipid classes generally contain fatty acids conjugated to other molecules.
B. Sphingosine-derived lipids
includes the ceramides, cerebrosides, gangliosides, and sphingomyelins
Sphingosine backbone - 3-C core plus long hydrocarbon chain

 Functionally analogous to glycolipids and are found in cell

membranes.
 Animal sphingosine lipids can also contain sugars =
glycolipids.
CLASSES OF LIPIDS
The other lipid classes generally contain fatty acids conjugated to other molecules.
C. Steroids and their derivatives
Basic skeleton consisting of four interconnected carbon rings; different structure than
long chain FAs
These molecules bind to specific protein receptors, precipitating a signal transduction
chain (e.g. Cholesterol)
CLASSES OF LIPIDS
The other lipid classes generally contain fatty acids conjugated to other molecules.
D. Terpenes and their derivatives
Built from same 5-carbon precursor as cholesterol (isopentenyl pyrophosphate)
Compounds also called isoprenoids
CLASSES OF LIPIDS
Certain aromatic compounds with a wide range of functions also made of isoprenyl C5 subunits