1

LIPIDS • It is amphipathic where the hydroxyl group in the A-

INTRODUCTION
• Lipids are commonly referred to as fats and composed
mostly of carbon-hydrogen bonds.
• They are insoluble in blood and water but soluble in
organic solvents (chloroform and ether).
• A lipid is an organic compound found in living organisms
that is insoluble (or only sparingly soluble) in water but
soluble in non-polar organic solvents.
• Unlike other biomolecules, lipids do not have a common
structural features that serves as the basis for defining
such compounds.
Classification: They are classified based on
solubility, not on any functional groups
 Insoluble or sparingly soluble in water
 Soluble in non-polar organic solvents
ring is the hydrophilic part of cholesterol.
• It is not catabolized by most cells; does not serve as a
source of fuel/energy.
• Liver synthesizes cholesterol: ~ 1g everyday; so it is not
necessary to consume in the form of diet
• Cholesterol synthesis decrease if it is ingested but
reduction is not sufficient: Leads to cardiovascular
disease
Animal Food: Lots of cholesterol
Plant Food: No cholesterol
Cells are surrounded by plasma membranes:
• Separates aqueous interior of a cell from the aqueous
environment surrounding the cell
• Up to 80% of plasma membrane is lipid material

• Lipids exhibit structural diversity- Some are esters, some • The membranes are lipid bilayer made up of
are amides, and some are alcohols (acyclic and cyclic) phospholipids
and some are polycyclic. Bilayer: Nonpolar tails of phospholipids in the middle and
FUNCTIONS OF LIPIDS polar heads are on the surface

• Source of fuel Cholesterol molecules are also components of plasma

membranes:
• Provides stability to cell membranes
• Cholesterol helps regulate membrane fluidity – The
• Source of hormones fused ring system does not allow rotation of fatty acid
tails in the vicinity
FIVE CATEGORIES OF LIPIDS
• Fits between fatty acid chains of the lipid bilayer: Make
For purposes of simplicity of study lipids are divided into five it rigid
categories based on their function:
• Cholesterol thus acts a membrane plasticizer
1. Energy-storage lipids: triacylglycerols
2. Membrane lipids: phospholipids, sphingoglycolipids, and
cholesterol
3. Emulsification lipids: bile acids PROTEINS
4. Chemical messenger lipids: steroid hormones and The membranes also contain proteins:
eicosanoids)
5. Protective-coating lipids: biological waxes • Responsible for moving substances such as nutrients
and electrolytes across the membrane
Based upon whether or not saponification occurs when a lipid
is placed in basic aqueous solution, lipids are divided into two • Receptors for hormones and neurotransmitters
categories:
The membrane proteins and some lipids are further reacted
Saponifiable lipids (triacylglycerols, phospholipids, with carbohydrates molecules:
sphingoglycolipids, and biological waxes
Act as markers: process by which different cells recognize
Nonsaponifiable lipids (cholesterol, steroid hormones, bile each other
acids, and eicosanoids)
TRIGLYCERIDES
• Formally defined, triacylglycerol is a lipid formed by
Major Lipids in plasma esterification of three fatty acids to a glycerol molecule
1. Phospholipids • A simple triacylglycerol is a triester formed from the
esterification of glycerol with three identical fatty acid
2. Cholesterol molecules
3. Triglycerides • A mixed triacylglycerol is a triester formed from the
4. Fatty acids esterification of glycerol with more than one kind of
fatty acid molecule.
5. Fat soluble vitamins (ADEK)
• It contains three molecules of fatty acid and one molecule
PHOSPHOLIPIDS of glycerol by ester bonds.

• It is the most abundant lipid derived from phosphatidic • It does not contain charged or hydrophilic groups; very
acid. hydrophobic and water-insoluble.

• It originates in the liver and intestine. It is produced from
the conjugation of two fatty acids and a phosphorylated
glycerol.
• It is an amphipathic lipid
CHOLESTEROL
• It is synthesized in the liver and it is found on the
surface layer of lipoproteins.
• It is the main storage lipid in humans (adipose tissue)
• Lipids known as triacylglycerols also function within the
body as energy-storage materials. Rather than being
widespread, triacylglycerols are concentrated primarily
in special cells (adipocytes) that are nearly filled with the
material.
• Adipose tissue containing these cells is found in various
parts of the body: under the skin, in the abdominal
 2

cavity, in the mammary glands, and around various • It transports exogenous/dietary TAG to liver, muscles,
organs and fat depot.
• Triacylglycerols are much more efficient at storing energy • It is produced in the intestine from dietary fat.
than is glycogen because large quantities of them can be
packed into a very small volume. These energy- storage VERY LOW DENSITY LIPOPROTEIN (VLDL)
lipids are the most abundant type of lipid present in the • It is secreted in the liver.
human body.
• It transports endogenous TAG from the liver to muscle,
fat depots, and peripheral tissues.
Difference of fats and oils HIGH DENSITY LIPOPROTEIN (HDL)
• Fats are naturally occurring mixtures of triacylglycerol • is the smallest lipoprotein but the most dense (5-12 nm).
molecules in which many different kinds of
triacylglycerol molecules are present. • It is produced in the liver and intestine (nascent disk-
shaped particles).
• A fat is a triacylglycerol mixture that is a solid or a semi-
solid at room temperature (25C). LOW DENSITY LIPOPROTEIN (LDL)
• Oils are also naturally occurring mixtures of • It is synthesized in the liver.
triacylglycerol molecules in which there are many
different kinds of triacylglycerol molecules present. • It is the major end product from the catabolism of
VLDL.
• An oil is a triacylglycerol mixture that is a liquid at
room temperature (25C)
*usual ref temp(4C)
*Freezer temp(-120C- -65C)
Physical State:
Fats
Predominantly Saturated
Solids or semisolids at room temperature MINOR LIPOPROTEINS

Oils: INTERMEDIATE DENSITY LIPOPROTEIN (IDL)

Predominantly unsaturated • It is product of VLDL catabolism - "VLDL remnant."

Liquids at room temperature • It is converted to LDL - "subclass of LDL."

Source: LIPOPROTEIN (A)

Fats: Animal source and tasteless • It is synthesized in the liver

Oils: Plants and fish oil • it is known as the "sinking pre-B lipoprotein due to
electrophoretic mobility same as VLDL but density
Pure oils and fats are colorless, odorless like LDL.
ABNORMAL LIPOPROTEINS
LIPOPROTEINS LIPOPROTEIN X
These are large macromolecular complexes of lipids with • It is an abnormal lipoprotein found in obstructive
specialized proteins known as apolipoproteins jaundice and LC AT deficiency.
Main purpose: To transport TAG and cholesterol to sites of • It is a specific and sensitive indicator of cholestasis.
energy and storage
BETA VLDL (B-VLDL)
APOLIPOPROTEINS
• It is known as "abnormally migrating B-VLDL'; has
• It helps to keep the lipids in solution (solubility) the density of VLDL by ultracentrifugation but
during blood circulation migrates with LDL in the B region during
electrophoresis. It is also known as the "VLDL rich
• It facilitates uptake of LPPs into cells through their
in cholesterol" due to defective catabolism of VLDL.
recognition by specific cell surface receptors.
There is an accumulation of IDL because of failure to
MAJOR LIPOPROTEINS fully convert VLDL to LDL.
OXIDIZED HDL
• It is commonly considered as a dysfunctional HDL
because native HDL is protective to atherosclerosis.
SATURATED AND UNSATURATED FATTY ACIDS
• A fatty acid is a naturally occurring monocarboxylic
acid. Because of the pathway are biosynthesized fatty
acids nearly always contain an even number of
carbon atoms and have a carbon chain that is
unbranched
• Long chain fatty acids: C12 - C26
CHYLOMICRONS • Medium chain fatty acids: C6 - C11
• Short-chain fatty acids: C4 - C5

Two Types:
Saturated - all C-C bonds are single bonds
Unsaturated
Monounsaturated: one C=C bond
Polyunsaturated: 2 or more C=C bonds present - up to six
double bonds are present in fatty acids
Unsaturated Fatty Acids
 A monounsaturated fatty acid is a fatty acid with a
carbon chain in which one carbon–carbon double bond
is present.
Polyunsaturated fatty acids
 A polyunsaturated fatty acid is a fatty acid with a carbon
chain in which two or more carbon–carbon double
bonds are present.
 Up to six double bonds are found in biochemically
important PUFAs.
Two types of unsaturated fatty acids
• Omega (ω)-3 fatty acids - An unsaturated fatty acid
with its endmost double bond three carbon atoms
away from its methyl end.
• Omega(ω)-6 fatty acid is an unsaturated fatty acid
with its endmost double bond six carbon atoms away
from its methyl end.
Unsaturated Fatty Acids and Double-Bond Position
• The notation 18:0 denotes a C18 fatty acid with no
double bonds
• 18:2:
Selected Unsaturated Fatty Acids of Biological Importance
• Numbering starts from the other end of COOH
• See structural notation: it indicates number of C
atoms
• E.g., 18:2 – 18 carbons, 2 double bonds
3
Types of fatty acids
An essential fatty acid is a fatty acid needed in the human
body that must be obtained from dietary sources because it
cannot be synthesized within the body, in adequate amounts,
from other substances. There are two essential fatty acids:
linoleic acid and linolenic acid. Linoleic acid (18:2) is the
primary member of the omega-6 acid family, and linolenic
acid (18:3) is the primary member of the omega-3 acid family.
Linoleic Acid Deficiency:
 Skin redness - becomes irritated
 Infections and dehydration
 Liver abnormalities
 Children need it the most
 Human milk has more than cow’s milk
Types of fatty acids
Linoleic acid is the starting material for the biosynthesis of
arachidonic acid.
Arachidonic acid is the major starting material for eicosanoids,
substances that help regulate blood pressure, clotting, and
several other important body functions.
Linolenic acid is the starting material for the biosynthesis of
two additional omega-3 fatty acids.
EPA (eicosapentaenoic acid) and DHA (docosahexaenoic
acid) are important constituents of the communication
membranes of the brain and are necessary for normal brain
development. EPA and DHA are also active in the retina of the
eye
Physical properties of fatty acids
The physical properties of fatty acids, and of lipids that
contain them, are largely determined by the length and
degree of unsaturation of the fatty acid carbon chain.
Water solubility for fatty acids is a direct function of carbon
chain length; solubility decreases as carbon chain length
increases.
• Short-chain fatty acids have a slight solubility in
water.
• Long-chain fatty acids are essentially insoluble in
water. The slight solubility of short-chain fatty acids
is related to the polarity of the carboxyl group
present.
Melting points for fatty acids are strongly influenced by both
carbon chain length and degree of unsaturation (number of
double bonds present).
• As carbon chain length increases, melting point
increases.
Space filling molecules - The number of bends in a fatty acid
chain increase as the number of double bonds increase
• Less packing occurs
• Melting point is lower
• Tend to be liquids at room temperature
Good fats vs. bad fats
Studies indicate that type of dietary fat and amount of dietary
fat are important for balanced diet:
Current recommended amounts are: total fat intake in calories:
 15% - Monounsaturated fat
 10% - Polyunsaturated
 <10% - Saturated fats
Studies also indicate that:
• 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”
GLYCEROPHOSPHOLIPID
• Omega 3 and 6 are important “good fats”
Chemical reactions of triglycerides
HYDROLYSIS
SPHINGOPHOSPHOLIPID
• Hydrolysis of a triacylglycerol is the reverse of the
esterification reaction by which it was formed
• Under acidic conditions, the hydrolysis products are
glycerol and fatty acids. Under basic conditions, the
hydrolysis products are glycerols and fatty acid salts.
• Within the human body, triacylglycerol hydrolysis
occurs during the process of digestion.
• In situations where all three fatty acids are removed,
the hydrolysis process is referred to as complete
hydrolysis
• If one or more of the fatty acid residues remains
attached to the glycerol, the hydrolysis process is
called partial hydrolysis
SAPONIFICATION
• is a reaction carried out in an alkaline (basic)
solution. For fats and oils, the products of
saponification are glycerol and fatty acid salts.
A saponifiable lipid is a lipid that undergoes hydrolysis in
basic solution to yield two or more smaller product
molecules.
A nonsaponifiable lipid does not undergo hydrolysis in basic
solution.
HYDROGENATION
• Addition of hydrogen across double (=) bond - increases
degree of saturation
• It involves hydrogen addition across carbon–carbon
multiple bonds, which increases the degree of saturation
as some double bonds are converted to single bonds.
• Hydrogenation involving just one carbon–carbon bond
within a fatty acid residue of a triacylglycerol can be
diagrammed as follows:
OXIDATION
The carbon–carbon double bonds present in the fatty acid
residues of a triacylglycerol are subject to oxidation with
molecular oxygen (from air) as the oxidizing agent. Such
oxidation breaks these bonds, producing both aldehyde and
carboxylic acid products.
The short-chain aldehydes and carboxylic acids so
Emulsification lipids: bile acids
produced often have objection- able odors, and fats and
oils containing them are said to have become rancid.
• To avoid this unwanted oxidation process,
commercially prepared foods containing
fats and oils nearly always contain
antioxidants—substances that are more
easily oxidized than the food.
PHOSPHOLIPID
• Phospholipids are the most abundant type of
membrane lipid. A phospholipid is a lipid that
contains one or more fatty acids, a phosphate group, a
4
platform molecule to which the fatty acid(s) and the
phosphate group are attached, and an alcohol that is
attached to the phosphate group.
• A glycerophospholipid is a lipid that contains two
fatty acids and a phosphate group esterified to a
glycerol molecule and an alcohol esterified to the
phosphate group.
• Structures based on the 18-carbon monounsaturated
aminodialcohol sphingosine
• Contains one fatty acid and one phosphate group
attached to a sphingosine molecule and an alcohol
attached to the phosphate group
• Saponifiable lipids
• A sphingophospholipid is a lipid that contains one
fatty acid and one phosphate group attached to a
sphingosine molecule and an alcohol attached to the
phosphate group.
• Sphingophospholipids in which the alcohol esterified
to the phosphate group is choline are called
sphingomyelins.
• Sphingomyelins are found in all cell membranes and
are important structural components of the myelin
sheath of neurons
• Sphingoglycolipids: is a lipid that contains both a
fatty acid and a carbohydrate component attached to a
sphingosine molecule.
• The simplest sphingoglycolipids, which are called
cerebrosides, contain a single monosaccharide unit
—either glucose or galactose. As the name suggests,
cerebrosides occur primarily in the brain (7% of dry
mass). They are also present in the myelin sheath of
nerves
• More complex sphingoglycolipids, called
gangliosides, contain a branched chain of up to
seven monosaccharide residues. These substances
occur in the gray matter of the brain as well as in the
myelin sheath.
• Phosphatidylcholines are also known as lecithins.
• Periodically, claims arise that phosphatidylcholine
should be taken as a nutritive supplement; some even
maintain it will improve memory.
• There is no evidence that these supplements are
useful
• The phosphatidylcholine present in cell membranes is
made by the liver; thus phosphatidylcholines are not
essential nutrients.
• Phosphatidylethanolamines and phosphatidylserines
are also known as cephalins.
• These compounds are found in heart and liver tissue
and in high concentrations in the brain. They are
important in blood clotting.
• An emulsifier is a substance that can disperse and
stabilize water-insoluble substances as colloidal
particles in an aqueous solution.
• Cholesterol derivatives called bile acids function as
emulsifying agents that facilitate the absorption of
dietary lipids in the intestine. Their mode of action
is much like that of soap during washing
• A bile acid is a cholesterol derivative that functions
as a lipid-emulsifying agent in the aqueous
environment of the digestive tract. From one-third to
 5

one-half of the daily production of cholesterol by
the liver is used to replenish bile acid stores.
• The medium through which bile acids are supplied to
the small intestine is bile.
• Bile is a fluid containing emulsifying agents that is
secreted by the liver, stored in the gallbladder, and
released into the small intestine during digestion.
Messenger lipids: 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.
• Some hormones are lipids.
•
The lipids that play the role of “chemical messengers” include:
• Inhibiting the secretion of gastric juices,
• Increasing the secretion of a protective
mucus layer into the stomach,
• Relaxing and contracting smooth muscle,
directing water and electrolyte balance,
intensifying pain, and enhancing
inflammation responses.
2. Thromboxanes: C20-fatty-acid derivative containing a
cyclic ether ring and oxygen-containing functional
groups
Promote platelet aggregation.
3. Leukotrienes: C20-fatty-acid derivative containing
three conjugated double bonds and hydroxy groups
Promote inflammatory and hypersensitivity
(allergy) responses
PROTECTIVE COATING LIPIDS: BIOLOGICAL WAXES
Properties of Biological waxes: Water-insoluble and water-
repellent because of long nonpolar hydrocarbon chains.
Humans and animals secrete biological waxes from skin
glands

• Steroid hormones: derivatives of cholesterol Function of biological waxes:

• Eicosanoids: derivatives of arachidonic acid • Protect hair and skin; and keep it pliable and lubricated.
• Impart water repellency to animal fur.
There are two major classes of steroid hormones: • Birds keep their feathers water repellent and help
minimize loss of body heat
• Sex hormones: control reproduction and secondary • Plants coat their leaves with a thin layer of biological
sex characteristics waxes to prevent excessive evaporation of water and to
• Adrenocorticoid hormones: control numerous protect against parasite attack.
biochemical processes in the body
Classified into three major groups:
• Estrogens - the female sex hormones
• Androgens - the male sex hormones
• Progestins - the pregnancy hormones

ADRENOCORTICOID HORMONES
• Produced by the adrenal glands - small organs located
on top of each kidney
• 28 Different hormones have been isolated from the
adrenal cortex
Two types of adrenocorticoid hormones:
• Mineralocorticoids - control the balance of Na and K
ions in cells
• Glucocorticoids - control glucose metabolism and
counteract inflammation
messenger lipids: EICOSANOIDS
• An eicosanoid is an oxygenated C20 fatty acid Lipid bilayer
derivative that functions as a messenger lipid. The
A lipid bilayer is the fundamental structure associated
term eicosanoid is derived from the Greek word
with a cell membrane.
eikos, which means “twenty.” The metabolic
precursor for most eicosanoids is arachidonic acid, It is a two-layer structure of lipid molecules (mostly
the 20:4 fatty acid. phospholipids and glycolipids) in which the nonpolar
tails of the lipids are in the interior and the polar heads
Physiological effects: EICOSANOIDS
are on the outside surfaces
1. The inflammatory response, a normal response to
Membrane transport mechanisms
tissue damage
2. The production of pain and fever The transport mechanisms by which molecules enter
3. The regulation of blood pressure and leave cells include passive transport, facilitated
4. The induction of blood clotting transport, and active transport.
5. The control of reproductive functions, such as
induction of labor Passive and facilitated transport follow a concentration
6. The regulation of the sleep/wake cycle gradient and do not involve cellular energy expenditure.
Active transport involves movement against a
THREE TYPES OF EICOSANOIDS
concentration gradient and requires the expenditure of
1. Prostoglandins: C20-fatty-acid derivative containing
cellular energy
cyclopentane ring and oxygen-containing functional
groups
• Involved in raising body temperature,
6