Lipids Structure

- An organic compound found in living • Lipids exhibit structural diversity

organisms that is insoluble (or only sparingly
• Some are esters, some are amides, and
soluble) in water but soluble in non-polar
some are alcohols (acyclic and cyclic) and
organic solvents.
some are polycyclic.
Classification: Based on two methods
– Biochemical function
– Saponification (hydrolysis under basic
conditions)

Biochemical Function
- For purposes of simplicity of study lipids are
divided into five categories based on their
biochemical function:
– Energy-storage lipids - triacylglycerols
– Membrane lipids - phospholipids,
sphingoglycolipids, and cholesterol
– Emulsification lipids - bile acids Types of Fatty Acids

– Chemical messenger lipids - steroid Saturated and Unsaturated Fatty Acids

hormones and eicosanoids)
– Protective-coating lipids - biological
waxes
– Transport lipids – lipoproteins
Even # of Carbon atoms:
– Long chain fatty acids: C12 - C26
– Medium chain fatty acids: C6 - C11
– Short-chain fatty acids: C4 - C5

Saponification reaction
Saturated Fatty Acids
- Hydrolysis reaction that occurs in a basic
solution. • Fatty acid with a carbon chain in
which all C-C bonds are single bonds
• Based on saponification reactions lipids are
• Numbering starts from the end of -
divided into two categories:
COOH group
– Saponifiable lipids – triacylglycerols • Structural notation: it indicates
phospholipids, sphingoglycolipids, number of C atoms.
cholesterol and biological waxes
Unsaturated Fatty Acids
– Nonsaponifiable lipids - bile acids,
• A monounsaturated fatty acid is a fatty acid
steroid hormones and eicosanoids)
with a carbon chain in which one carbon –
carbon double bond is present.
Polyunsaturated Fatty Acids (PUFAs) – Ideal ratio: Omega 6 : Omega 3 (4 - 10 g:
1g)
• A polyunsaturated fatty acid is a fatty acid
with a carbon chain in which two or more
carbon–carbon double bonds are present.
Physical Properties of Fatty Acids
• Up to six double bonds are found in
biochemically important PUFAs.
• Two types of unsaturated fatty acids. Water solubility: Short chain fatty acids
have some solubility whereas long chain fatty
– Omega (ω)-3 fatty acids - An unsaturated acids are insoluble
fatty acid with its endmost double bond three
carbon atoms away from its methyl end. – Short chain fatty acids are sparingly
soluble because of carboxylic acid polar
– Omega (ω)-6 fatty acid is an unsaturated group.
fatty acid with its endmost double bond six
carbon atoms away from its methyl end.
The Melting Point

Omega Acids • Melting Point Depends Upon:

Essential Fatty Acids: Must be part of diet – Length of carbon chain

• Nutritionally important Omega-3 and – Degree of unsaturation (number of

Omega-6 fatty acids double bonds in a molecule)

– Linolenic acid – Omega-3

– Linoleic acid – Omega-6 Space-Filling Molecules

• Linoleic Acid Deficiency: • The number of bends in a fatty acid chain

increase as the number of double bonds
– Skin redness - becomes irritated increase
– Infections and dehydration • Less packing occurs
– Liver abnormalities • Melting point is lower
– Children need it the most • Tend to be liquids at room temperature
– Human milk has more than cow’s milk

Energy-Storage Lipids: Triacylglycerols

American Diet Energy-Storage Materials
• Sufficient in omega 6 fatty acids • With the notable exception of nerve cells,
human cells store small amounts of energy
• Deficient in omega 3 fatty acids
providing materials:
– Fish - good source for omega 3 fatty acids
– The most widespread energy storage
• High rate of heart disease may be due to material
imbalance in omega 3 and 6 fatty acids
- carbohydrate glycogen
– Present in small amounts
• Major Energy– Storage material is
triacylglycerols:
– Triacylglycerols are concentrated primarily
in special cells (adipocytes)
– Adipocytes are nearly filled with
triacylglycerols.
Two Types of Triacylglycerols
• Simple Triacylglycerols: Three identical
fatty acids are esterified
– Naturally occurring simple triacylglycerols
are rare
• Mixed Triacylglycerols: A triester formed
from the esterification of glycerol with more
than one kind of fatty acid
– In nature mostly mixed triacylglycerols are
found and are different even from the same
source depending on the feed, e.g., corn,
peanut and wheat -fed cows have different
triacylglycerols.
Fats and Oils
• Physical State:
– Fats
• Predominantly Saturated
• Solids or semisolids at room temperature
– Oils:
• Predominantly unsaturated
• Liquids at room temperature
• Source:
– Fats: Animal source and tasteless
– Oils: Plants and fish oil
– Pure oils and fats are colorless, odorless
“Good Fats” Versus “Bad Fats”
– Saturated fats are considered “bad fats”
– Monounsaturated fats are considered
“good fats”
– Trans-monounsaturated fats are
considered “bad fats”
– Polyunsaturated fats can be both “good
fats” and “bad fats”
• Omega 3 and 6 are important “good fats”
Essential Fatty Acids
Two most important essential fatty acids
are:
– Linoleic acid (18:2) - omega 6
– Linolenic acid (18:3) - omega 3
• Both are needed for:
– Proper membrane structure
– Serve as starting materials for the
production of several nutritionally important
longer-chain omega-6 and omega-3 fatty
acids
• Deficiencies of above two acids may result
in skin redness, infections and dehydration
likely and liver abnormalities may develop.
Chemical Reactions of Triacylglycerols
Partial Hydrolysis
Chemical Properties due to two functional – To avoid this unwanted oxidation process
groups: esters and alkenes antioxidants are added as preservatives, e.g.,
Vitamin C and vitamin E are good antioxidant
– Hydrolysis: Partial hydrolysis of
preservatives.
triacylglycerols
– Breaking of 1-2 ester bonds to give rise to
mono- or diacylglycerol and fatty acid(s)
– Carried out by enzymes produced by the
pancreas

Saponification
• Hydrolysis in basic solution: Produce salt of Glycerophospholipids
fatty acid and glycerol
• A glycerophospholipid is a lipid that
contains two fatty acids and a phosphate
group esterified to a glycerol molecule and
Hydrogenation an alcohol esterified to the phosphate group.
– Addition of hydrogen across double (=)
bond - increases degree of saturation
– a test for unsaturation
– the amount of halogen absorbed by a lipid
can be used as an index of the degree of
unsaturation; the index value is called iodine
number, the number of grams of iodine that
will add to 100 g of fat or oil
– the rule is: high I2 number indicates a high
• Structurally glycerophospholipids are
degree of unsaturation
although similar to triacylglycerols, they
have different biochemical functions.

Oxidation – Triacylglycerols serve as energy storage

molecules
• Double bonds in triacylglycerols are
subject to oxidation with oxygen in air (an – Glycerophospholipids function as
oxidizing agent )-Leads to C=C breakage components of cell membranes

• Remember that oxidation of alkenes may
result into two short chain molecules – an
aldehydes or a carboxylic acid:
– The aldehydes and/or carboxylic acids so
produced often have objectionable odors -
fats and oils are said to be rancid
• A major structural difference between the
two types of lipids is that of their “polarity”
Responsible for the their differing
biochemical functions.
– Triacylglycerols are a non-polar
– Glycerophospholipids are polar.
Sphingophospholipids 3. Leukotrienes: C20-fatty-acid derivative
containing three conjugated double bonds
• Structures based on the 18-carbon
and hydroxyl groups – Promote
monounsaturated aminodialcohol
inflammatory and hypersensitivity (allergy)
sphingosine
responses
• Contains one fatty acid and one
phosphate group attached to a
sphingosine molecule and an
Transport Lipids: Lipoproteins
alcohol attached to the phosphate
group • responsible for the transport of other lipids
• Sphingophospholipids in which in the body; lipids are only sparingly soluble
the alcohol esterified to the in water, and the movement of lipids from
phosphate group is choline are one organ to another through the blood
called sphingomyelins. stream requires a transport system that
• Sphingoglycolipids: Contains both operates via plasma lipoproteins
a fatty acid and carbohydrate
• Simple sphingoglycolipids are called Four major classes:
cerebrosides: contains a single 1. Chylomicrons – transport dietary TAG
monosaccharide unit - either from the intestine to the liver and to adipose
glucose or galactose tissue
Gangliosides 2. Very-low-density lipoprotein (VLDL) –
• Complex sphingoglycolipids are called transport TAG synthesized in the liver to
Gangliosides: contain a branched chain of adipose tissue
up to seven monosaccharide residues. 3. Low-density lipoprotein (LDL) –
• Occur in the gray matter of the brain as transport cholesterol synthesized in the liver
well as in the myelin sheath. to cells throughout the body
4. High-density lipoprotein (HDL) – collect
excess cholesterol from body tissues and
Messenger Lipids: Eicosanoids transport it back to the liver for degradation
to bile acids
Principal Types of Eicosanoids
1. Prostoglandins: C20 -fatty -acid
derivative containing cyclopentane ring and
oxygen -containing functional groups
– Involved in raising body temperature,
– Inhibiting the secretion of gastric juices,
– Increasing the secretion of a protective
mucus layer into the stomach
2. Thromboxanes: C20-fatty-acid derivative
containing a cyclic ether ring and oxygen- Saponifiable and Nonsaponifiable Lipids
containing functional groups
̶ Promote platelet aggregation.
• Saponifiable Lipid: A lipid that undergoes
hydrolysis in a basic solution to yield 2 or
more small molecules.
• Saponification is possible in molecules that
contain the following linkages (bonds): ̶
Ester ̶ Amide ̶ Glycosidic
Saponifiable Lipids and Linkages:
̶ Triacylglycerols – 3 ester bonds
̶ Glycerophospholipids – 4 ester bonds
̶ Sphingophospholipids – 1 amide and 2
ester bonds
̶ Sphingoglycolipids: 1 amide, 1 ester
and 1 glycosidic bond
̶ Biological waxes – 1 ester bond