LIPIDS

BIOCHEMISTRY
 OVERVIEW OF LIPIDS

• Lipids are naturally occurring compounds that are grouped together due to
their insolubility in water and other polar solvents.
- They are, however, soluble in non-polar solvents, such as:
- ether
- chloroform
- carbon tetrachloride

• They have structural diversity, meaning, there is no existing common

structural feature among them. They can be esters, amides, or alcohols.
 PHYSIOLOGICAL FUNCTIONS OF
LIPIDS

1. Storage form of energy (9 kcal/g)

2. Structural components of biomembranes
3. Metabolic regulators
4. Act as surfactants, detergents and emulsifying agents
5. Act as electric insulators in neurons
6. Provide insulation against changes in external temperature
7. Give shape and contour to the body
8. Protect internal organs by providing a cushioning effect
9. Help in absorption of fat soluble vitamins (A, D, E and K)
10. Improve taste and palatability of food
 FATTY ACIDS

• These are the commonly encountered component of lipids.

• Fatty acids considered as derived lipids because in biological
systems, they are usually incorporated in a larger lipid
molecule, and is seldom found in free form
 FATTY ACIDS

A fatty acid contains a hydrocarbon tail (hydrophobic/non- polar part) and

a carboxyl head (hydrophilic/polar part), making it amphipathic.
 CLASSIFICATIONS OF FATTY ACIDS

1. Based on hydrocarbon chain length

• a. Short chain fatty acids – contain 2–6 carbons (often referred to
as carboxylic acids)
• b. Medium chain fatty acids – contain 8–14 carbons; these fatty
acids are easily absorbed by the cell for energy consumption.
• c. Long chain fatty acids – contain 16–24 carbons
• d. Very long chain fatty acids – contain more than 24 carbons
CLASSIFICATIONS OF FATTY ACIDS
 CLASSIFICATIONS OF FATTY ACIDS

2. Based on the nature of the hydrocarbon chain.

• a. Saturated fatty acids
• - These are fatty acids that contain only carbon-carbon single bond.
 CLASSIFICATIONS OF FATTY ACIDS

2. Based on the nature of the hydrocarbon chain.

• b. Unsaturated fatty acids
• - These are fatty acids that contain at least one carbon-carbon double bond.
• - Recall that a carbon-carbon double bond inhibits free rotation of atoms around it.
 CLASSIFICATIONS OF FATTY ACIDS

• For this reason, unsaturated fatty acids exhibit geometric

isomerism (cis or trans) around the carbon-carbon double bond,
where cis conformation is present in most common fatty acids.
CLASSIFICATIONS OF FATTY ACIDS
 CLASSIFICATIONS OF FATTY ACIDS

2. Based on the nature of the hydrocarbon chain.

• b. Unsaturated fatty acids
• - Monounsaturated fatty acids (MUFA) - with only one double bond
• - Polyunsaturated fatty acids (PUFA) - with 2 or more double bonds
 CLASSIFICATIONS OF FATTY ACIDS

2. Based on the nature of the hydrocarbon chain.

• b. Unsaturated fatty acids
- The location and number of double bonds in an unsaturated fatty acids are very
important in distinguishing them from one another.
To help as remember the location and number of double bonds, we can use the shorthand
notation:
x:y Δn
x - number of carbons
y - number of double bonds
n - carbon number at which the double bond is located
CLASSIFICATIONS OF FATTY ACIDS
 PROPERTIES OF FATTY ACIDS

1. Structure
• *Saturated fatty acids have straight chain structure.
• *Unsaturated fatty acids have 30o kinks or bends at every double bond.

2. Strength of Intermolecular Force (IMF)

• *Hydrophobic interaction is the IMF present in the hydrophobic tails of fatty acids.
• *Saturated fatty acids extend and stack regularly which increases intermolecular
attraction.
• *Unsaturated fatty acids have kinks and cannot be stacked in organized manner
which decreases intermolecular attraction.
 PROPERTIES OF FATTY ACIDS

3. Melting Point
• *The melting point increases as the number of carbon atom increases.
• *Saturated fatty acids have higher melting point than unsaturated fatty acid with the
same number of carbon.
• *The more the double bond, the lower the melting point when comparing fatty acids
with same number of carbon
 TYPES OF LIPIDS

TRIACYLGLYCEROL (TAG) TRYGLCERIDES

• - Fats and oils are mixtures of lipids known as triacylglycerol
(TAG). The main function of TAG in the body is for long-term
energy storage. In humans, they are concentrated mainly in
special cells called adipocytes located in the subcutaneous layer of
the skin.
• Adipose tissue is abundant in the lower abdomen, and in
mammary gland in females.
TYPES OF LIPIDS
TYPES OF LIPIDS
 TYPES OF LIPIDS

TRIACYLGLYCEROL (TAG) TRYGLYCERIDES

• Triglycerides are a type of fat (lipid) found in your blood.
• When you eat, your body converts any calories it doesn't need to
use right away into triglycerides. The triglycerides are stored in
your fat cells. Later, hormones release triglycerides for energy
between meals.
• If you regularly eat more calories than you burn, particularly from
high-carbohydrate foods, you may have high triglycerides
(hypertriglyceridemia).
 TYPES OF LIPIDS

TRIACYLGLYCEROL (TAG) TRYGLCERIDES

• Structurally, TAG is a triester of glycerol and 3 fatty acids. The
fatty acid attached to the glycerol backbone are also referred as
acyl, hence the name triacylglycerol to denote that there are 3 fatty
acids in the structure.
• - The fatty acids are connected to the glycerol backbone through
an ester bond.
 TYPES OF LIPIDS

TRIACYLGLYCEROL (TAG) TRYGLCERIDES

 TYPES OF LIPIDS

FORMATION OF TRIACYLGLYCEROL (TAG)

TRYGLCERIDES
• Triacylglycerols are formed by esterification reaction between a glycerol molecule and
3 fatty acids.
• Esterification is a general a dehydration reaction, meaning water is produced as by-
product. In the case of reaction for the formation of TAG, for every molecule of
triacylglycerol produced, 3 water molecules are formed.
• The formation of trilaurin, a TAG abundantly found in coconut oil is illustrated on the
next slide. The atoms of the reactants directly involved in the reaction are encircled in
red. In the reaction, these atoms are removed forming water molecules.
TYPES OF LIPIDS
 TYPES OF LIPIDS

FORMATION OF TRIACYLGLYCEROL (TAG)

TRYGLCERIDES

• In simpler sense, the formation of TAG can be generalized as:

1 glycerol + 3 fatty acids  1 triacylglycerol + 3 water

• Take note that the 3 fatty acids in a TAG molecule can be the same
or different.
 TYPES OF LIPIDS

TYPES OF TRIACYLGLYCEROL (TAG) TRYGLCERIDES

TAGs can be classified based on the fatty acids present in their structures.
1. Simple triacylglycerol - all 3 fatty acids are identical
2. Mixed triacylglycerol - 1 or more of the 3 fatty acids are not
identical

When a PUFA is present in a TAG, it is usually located at the 2nd fatty acid.
 TYPES OF LIPIDS

TYPES OF TRIACYLGLYCEROL (TAG) TRYGLCERIDES

TAGs can be classified based on the fatty acids present in their structures.
1. Simple triacylglycerol - all 3 fatty acids are identical
2. Mixed triacylglycerol - 1 or more of the 3 fatty acids are not
identical

When a PUFA is present in a TAG, it is usually located at the 2nd fatty acid.
TYPES OF LIPIDS

SIMPLE TRYCYLGLYCEROL
TYPES OF LIPIDS

MIXED TRYCYLGLYCEROL
 TYPES OF LIPIDS

NOMENCLATURE OF TRIACYLGLYCEROL (TAG) TRYGLCERIDES

The TAG is taken as a derivative of glycerol; thus, glycerol is taken as the parent name.
• 2. The fatty acids are designated with locants 1, 2, and 3, where 1 is given for the fatty
acid drawn on top, 2 is given for the one in the middle, and 3 for the one at the bottom.
Since the fatty acids are connected via ester bond, the names of these fatty acids are
converted by replacing the suffix –ic acid to –oyl.
• Let us take the triacylglycerol molecule above as an example. The first fatty acid is
palmitoleic acid, thus it will be converted to 1-palmitoleoyl (1 being the locant of its
position). The second fatty acid is linolenic acid, thus it will be converted to 2-linolenoyl
(2 being the locant of its position). The third fatty acid is pamitic acid, thus it will be
converted to 3-pamitoyl (3 being the locant of its position).
 TYPES OF LIPIDS

NOMENCLATURE OF TRIACYLGLYCEROL (TAG) TRYGLCERIDES

• 3. The final name is taken by arranging the locants in increasing manner and
attaching the parent name glycerol at the end. In the sample molecule, the
name is: 1-pamitoleoyl-2-linolenoyl-3-pamitoylglycerol.
TYPES OF LIPIDS

palmitoleic acid

linolenic acid

pamitic acid

1-Pamitoleoyl-2-linolenoyl-3-pamitoylglycerol.
TYPES OF LIPIDS

Palmitic Acid

Oleic acid

Arachidonic Acid

1-Palmitoyl-2-oleoyl-3arachidonoylglycerol.
CLASSIFICATIONS OF FATTY ACIDS
CLASSIFICATIONS OF FATTY ACIDS
 TYPES OF LIPIDS

1,3-Dipalmitoyl-2-myristolglycerol
 TYPES OF LIPIDS

1-lauroyl-2-palmitoyl-3-oleoylglycerol.
 FATS AND OILS

Fats are mixture of triacylglycerols that are rich in saturated fatty acids.
These are solid or semi-solid at room temperature and are usually sourced
from animals.

- Oils are mixture of triacylglycerols that are rich in unsaturated fatty acids.
These are liquid at room temperature and are usually sourced from plants.
Fish oils from cold water fishes are exception.
 GOOD AND BAD FATS

In nutrition, the term fat is often used in replacement of triacylglycerol. Thus,

a dietary fat can be a fat or an oil.

• Saturated fats (rich in saturated FA) are bad fats. These types of fats can
increase the risk of heart diseases.

• Monounsaturated fats (rich in MUFA) are good fats. These fats can
decrease the risk of heart disease and breast cancer. MUFAs help reduce
the stickiness of platelets, which helps prevent formation of blood clots
and may dissolve clots once they form.
 CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Acrolein Test

The glycerol portion of TAGs undergoes dehydration reaction using potassium

bisulfate (KHSO4) to form acrolein (2-propenal) with black appearance and burnt fat
odor. The same substance is produced when cooking oil is used repeatedly or when grilling
pork fat for a long time. Acrolein is carcinogenic, and therefore, it is not advisable to reuse
cooking oils.
 CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Hydrogenation (Catalytic reduction)

Under high pressure and in the presence of a transition metal catalyst

(e.g. Ni, Pt, Pd), the double bonds of unsaturated fatty acids present in
triacylglycerols, undergoes addition reaction with hydrogen gas (H2). In the
process, the double bond is replaced with a single bond, and each carbon atom
involved in a double bond is added with one hydrogen atom. Unsaturated fatty
acids are converted to saturated fatty acids. Margarine and other butter
substitutes are produced using this process from vegetable oils.
CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Note: The number of molecules hydrogen gas that will be involved in the reaction is equal to the number of
double bonds present in the unsaturated fatty acid. The saturated fatty acid that will be produced will have similar
number of carbons as the unsaturated fatty acid reactant.
 CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Acid Hydrolysis

In the presence of a strong acid (H+), triacylglycerol reacts with water breaking the
ester bonds in between the glycerol backbone and the fatty acids. Consequently, 1 glycerol
molecule and 3 fatty acid molecules.
CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL
 CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Enzymatic hydrolysis

Triacylglycerol are hydrolyzed in humans by the enzyme

lipase. Hydrolysis by lipase occurs in a stepwise manner following
the order: first fatty acid —> third fatty acid —> second fatty acid.
But lipase hydrolysis rarely goes to completion. Most of the time,
the products are 2 fatty acids and 1 monoacylglycerol.
CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL
 CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL

Saponification (Basic Hydrolysis)

In the presence of strong base, such as NaOH and KOH, the ester
bonds in triacylglycerols are broken down without the action of
water. In return, a glycerol molecule is produced together with 3
fatty acid salt whose cation is from the used base. The fatty acid
salt products are commonly known as soap.
CHEMICAL REACTIONS INVOLVING
TRIACYLGLYCEROL
 TYPES OF LIPIDS

PHOSPHOLIPIDS/ MEMBRANE LIPIDS

• All cells are surrounded by a membrane that confines their contents. Up to 80% of the
mass of a cell membrane can be lipid materials; the rest is primarily protein. It is
membranes that give cells their individuality by separating them from their environment.

• The lipid component of the cell membrane is associated in a lipid bilayer, in which the
polar heads of are found in the exterior of the bilayer exposed to the aqueous
environment, while the non-polar portions are found in the interior of the bilayer.
Thus, majority of membrane lipids are amphipathic, a molecule with polar head and
non-polar tail, like fatty acids. The tails of the membrane lipids often include long-chain
unsaturated fatty acids which provides kinks (bend) in the structure resulting to
fluidity. .
 TYPES OF LIPIDS

• It is amphipathic in nature.

• It acts as a barrier to the

passage of molecules and
ions in and out of the cell.

The are different types of membrane lipids – glycerophospholipids (phosphoacylglycerol), sphingophospholipids

(sphingomyelin), and sphingoglycolipids (cerebrosides and gangliosides).
 TYPES OF MEMBRANE LIPIDS

GLYCEROPHOSPHOLIPIDS

• Glycerophospholipids are the major component of biological membranes.

• A glycerophospholipid molecule has somewhat similar structure to a TAG
molecule; it consists of a glycerol backbone, but only the first and second
carbon positions are attached with fatty acids. The third carbon position
is attached with a phosphate group, which is additionally linked to another
polar group (usually alcohol). All attachments between groups are ester
linkages. The 2 fatty acids are the non-polar tail of a glycerophospholipid,
while the phosphate and the polar group are the polar head.
 TYPES OF MEMBRANE LIPIDS

• The fatty acid at the first carbon is usually saturated C16 or C18 fatty acids, and the
fatty acid at the second carbon is often unsaturated C16 to C20 fatty acids.
 TYPES OF MEMBRANE LIPIDS

• Glycerophospholipids are differentiated from each other according to the

type of polar group present. The table below shows the different
Glycerophospholipids with their corresponding polar groups. The groups in
RED are the point of attachment to the phosphate group.
TYPES OF MEMBRANE LIPIDS
TYPES OF MEMBRANE LIPIDS
 TYPES OF MEMBRANE LIPIDS

NOMENCLATURE OF GLYCEROPHOSPHOLIPIDS
• An example of a glycerophospholipid molecule is illustrated below. The glycerol backbone is drawn in
black, the fatty acids in red, the phosphate group in blue, and the polar group in green. The fatty acids
present in the molecule below are stearic acid at 1st carbon and oleic acid at 2nd carbon. The polar
group is ethanolamine.
 TYPES OF MEMBRANE LIPIDS
NOMENCLATURE OF GLYCEROPHOSPHOLIPIDS
1. The parent name is the type of glycerophospholipid based on the polar group
present (refer to the table above) and should bear the locant number 3 as it is always
present in carbon number 3. So the parent name shall be 3-
phosphatidylethanolamine.
2. The fatty acids are treated as substituents. Since they are attached to the glycerol
via ester bond, its name is converted by replacing the suffix – ic acid to –oyl. Their
new names should bear their corresponding locants. In the case of the sample
molecule, the fatty acid in the first carbon is stearic acid, thus it should be converted
to 1-stearoyl. The fatty acid in the second carbon is oleic acid, thus it should be
converted to 2-oleoyl.
3. The name of the molecule is obtained by arranging the locants in increasing order.
 TYPES OF MEMBRANE LIPIDS
NOMENCLATURE OF GLYCEROPHOSPHOLIPIDS

1-stearoyl-2-oleoyl-3-phosphatidylethanolamine
 TYPES OF MEMBRANE LIPIDS
NOMENCLATURE OF GLYCEROPHOSPHOLIPIDS

Palmitic Acid

Linolenic Acid

Choline

1-Palmitoyl-2-linolenoyl-3-phosphatidylcholine
 TYPES OF MEMBRANE LIPIDS
USES OF SOME GLYCEROPHOSPHOLIPIDS
• - Lecithins (phosphatidylcholine) are used in food industries as emulsifiers for
mayonnaise, ice cream, and custards.
• - Dipalmitoylphosphatidylcholine (DPPC), a phosphatidylcholine (lecithin) with 2
palmitic acid residues at carbons 1 and 2, is the major lipid of lung surfactant, the
protein–lipid mixture that is essential for normal pulmonary function. The surfaces of the
cells that form the alveoli (small air spaces of the lung) are coated with surfactant, which
decreases the alveolar surface tension. Its absence from the lungs of premature infants
causes respiratory distress syndrome.
• - Cephalin (phosphatidylethanolamine) and phosphatidylserine are present in heart
and liver tissue at high concentration. They are important for blood clotting.
Phosphatidylserine also plays a role in apoptosis (programmed cell death).
 TYPES OF MEMBRANE LIPIDS

USES OF SOME GLYCEROPHOSPHOLIPIDS

• Cardiolipin is found only in mitochondria and is essential for the mitochondrial
function. Decreased cardiolipin levels or alterations in its structure or metabolism
cause mitochondrial dysfunction in aging and in pathological conditions including
heart failure, hypothyroidism, and Barth syndrome (cardioskeletal myopathy)
 TYPES OF MEMBRANE LIPIDS

SPHINGOLIPIDS
• In addition to glycerophospholipids, sphingolipids are also major
components of cell membrane. They were named after the Sphinx because
their function in cells was at first mysterious.
• Sphingolipids are derivatives of sphingosine, an amino alcohol containing
18 carbons with a double bond having a trans configuration. When the
amino group of sphingosine is attached with a fatty acid residue (acyl), it is
known as ceramide.
 TYPES OF MEMBRANE LIPIDS

SPHINGOLIPIDS
 TYPES OF MEMBRANE LIPIDS

SPHINGOLIPIDS

Ceramides are the parent compounds of the abundant sphingolipids.

 TYPES OF MEMBRANE LIPIDS
MOST ABUNDANT SPHINGOLIPIDS
Sphingophospholipids
• These are ceramides bearing phosphate group and an alcohol as polar
head like the glycerophospholipid. If the alcohol present in a
sphingophospholipids is choline or ethanolamine, they are known as
sphingomyelins. Sphingomyelins are the most common sphingolipid; they
typically make up 10-20% of membrane lipids. The membranous myelin
sheath that electrically insulates the axons is rich in sphingomyelins.
 TYPES OF MEMBRANE LIPIDS
MOST ABUNDANT SPHINGOLIPIDS
Sphingophospholipids
 TYPES OF MEMBRANE LIPIDS
MOST ABUNDANT SPHINGOLIPIDS

Sphingoglycolipids
• - These are ceramides that contain a carbohydrate component as
polar head. The carbohydrate can be a monosaccharide or
oligosaccharide, and is attached to the sphingosine at the terminal
carbon atom through glycosidic linkage.
 TYPES OF MEMBRANE LIPIDS
MOST ABUNDANT SPHINGOLIPID

Sphingoglycolipids
 TYPES OF MEMBRANE LIPIDS

• Sphingoglycolipids
having a monosaccharide
polar head is known as
cerebrosides.
Galactocerebrosides
(having galactose polar
head) and
glucocerebrosides
(having glucose polar
head) .

galactocerebroside
 TYPES OF MEMBRANE LIPIDS

• - Gangliosides are
the most complex
sphingoglycolipids.
They are ceramides
with attached
oligosaccharides
 TYPES OF MEMBRANE LIPIDS

STERIODS
• Steroids, which are eukaryotic origin, are derivatives of
cyclopentanoperhydrophenanthrene, a compound that consists
of four fused nonplanar rings (labeled A-D)
 TYPES OF MEMBRANE LIPIDS

CHOLESTEROL
• Cholesterol is a steroid, which can be further classified as a sterol due to the
presence of a hydroxyl (-OH) group. It is the major component of animal
plasma membranes.
 TYPES OF MEMBRANE LIPIDS

CHOLESTEROL
• Cholesterol is a steroid, which can be further classified as a sterol due to the
presence of a hydroxyl (-OH) group. It is the major component of animal
plasma membranes.
 TYPES OF MEMBRANE LIPIDS

CHOLESTEROL
• Most of the cholesterol in humans are biosynthesized by the liver
and (to a lesser extent) the intestine. Typically, 800-1000 mg of
cholesterol is biosynthesized each day. Ingestion of foods rich in
cholesterol decreases cholesterol biosynthesis. However, more
often, the amount ingested is much higher than the reduction. Thus,
the total body cholesterol levels increase with dietary intake of
cholesterol.
 TYPES OF MEMBRANE LIPIDS

CHOLESTEROL
Cholesterol is distributed throughout the body by a protein carrier. The
cholesterol-protein combinations are called lipoproteins. There are 2 types of
lipoproteins:
1. Low-density lipoprotein (LDL) - lipoproteins that carry cholesterol from
the liver to various tissues. This is known as the bad cholesterol because it
increases the amount of cholesterol in the blood.
2. High-density lipoprotein (HDL) - lipoproteins that carry excess
cholesterol from the tissues back to the liver. This is known as the good
cholesterol because it decreases the amount of cholesterol in the blood.
 TYPES OF MEMBRANE LIPIDS

CHOLESTEROL
• If too much cholesterol is transported by LDL or too little by
HDL, the imbalance results in increase in blood cholesterol levels.
• High cholesterol level in the blood contribute to atherosclerosis, a
cardiovascular disease caused by buildup of lipid plaques along the
inner walls of arteries.
 TYPES OF MEMBRANE LIPIDS

STEROID HORMONES
• -A hormone is a biochemical substance, produced by a ductless
gland, that has a messenger function. Hormones serve as a means
of communication between various tissues.
• - A steroid hormone is a hormone that is a cholesterol
derivative. There are two major classes of steroid hormones: (1)
sex hormones, which control reproduction and secondary sex
characteristics and (2) adrenocorticoid hormones, which regulate
numerous biochemical processes in the body.
 TYPES OF MEMBRANE LIPIDS

• The sex hormones can be classified into three major subclasses:

• 1. Estrogens—the female sex hormones
• 2. Androgens—the male sex hormones
• 3. Progestins—the pregnancy hormones
 TYPES OF MEMBRANE LIPIDS

• Estrogens are synthesized in the ovaries and adrenal cortex (the outer part
of the adrenal glands, which are located on the top of each kidney) and are
responsible for the development of female secondary sex characteristics at
the onset of puberty and for regulation of the menstrual cycle. They also
stimulate the development of the mammary glands during pregnancy and
induce estrus (heat) in animals.
• Androgens are synthesized in the testes and adrenal cortex and promote the
development of male secondary sex characteristics. They also promote
muscle growth.
 TYPES OF MEMBRANE LIPIDS

• Progestins are synthesized in the ovaries and the placenta and

prepare the lining of the uterus for implantation of the fertilized
ovum. They also suppress ovulation.
• Increased knowledge of the structures and functions of sex
hormones has led to the development of a number of synthetic
steroids whose actions often mimic those of the natural steroid
hormones. The best known types of synthetic steroids are oral
contraceptives and anabolic steroids.
 TYPES OF MEMBRANE LIPIDS

• Oral contraceptives are used to suppress ovulation as a method of birth

control. Generally, a mixture of a synthetic estrogen and a synthetic
progestin is used. The synthetic estrogen regulates the menstrual cycle, and
the synthetic progestin prevents ovulation, thus creating a false state of
pregnancy.
• Anabolic steroids include the illegal steroid drugs used by some athletes to
build up muscle strength and enhance endurance. Such steroids are now
known to have serious side effects in the user. Its structure is similar to that
of the naturally occurring testosterone.
 TYPES OF MEMBRANE LIPIDS

• The adrenocorticoid hormones are synthesized in the adrenal

cortex, and have two subclasses:
• 1. Mineralocorticoids control the balance of Na+ and K+ ions in
cells and body fluids.
• 2. Glucocorticoids control glucose metabolism and counteract
inflammation.