LIPIDS

● Lipids- These are organic compounds found in living organisms that are insoluble (or
only sparingly soluble) in water but soluble in polar organic solvents.

Basic Functions of Lipids

1. Provides a major way of storing chemical energy and carbon atoms in the body.
2. Surround and insulate vital organs, protecting regularly from mechanical shock and
excessive heat loss.
3. The basic components of cell membranes.
4. Acts as chemical messengers in the body (hormones).

5 Major Categories of Lipids

● Fatty acids- Are structural components of almost all lipids except CHOLESTEROL,
BILE ACIDS, and STEROID HORMONES. These are naturally occurring
monocarboxylic acids.
 ● Because of the pathway by which they are biosynthesized, fatty acids nearly always
EVEN NUMBER of carbons atoms and have UNBRANCHED carbon chains.
● Rarely found free but rather occur as part of more complex lipid molecules.

Fatty Acids type based on Carbon Chain Length

1. Long-chain fatty acids (C12 to C26)
2. Medium-chain fatty acids (C8 to C10)
3. Short-chain fatty acids (C4 to C6)

Characteristics of Natural Fatty Acids

● Contains an unbranched carbon chain.
● Has an even number of carbon atoms in a chain.
● When double bonds are present, it is nearly always in “cis” form.
● More than 500 different fatty acids have been isolated from the lipids of microorganisms,
plants, animals, and humans.

Classification of Fatty Acids

● Saturated fatty acids (SFA’s)- These are fatty acids that have a carbon chain in which all
carbon-carbon bonds are all single bonds.
● Monounsaturated fatty acids (MUFA’s)- These are fatty acids with a carbon chain in
which one carbon-carbon double bond is present.
● Polyunsaturated fatty acids (PUFA’s)- These are fatty acids with a carbon chain in which
two or more carbon-carbon double bonds are present.

Notation for Unsaturated Fatty Acids and Double Bond Positions

1. Specifying the number of carbon atoms and number of double bonds present. (indicated
by two numbers separated by a colon)
Example: 18:0 denotes a C18 fatty acid with no double bonds
18:2 signifies a C18 fatty acid with 2 double bonds
2. Specifying the position of the double bond. (indicated by Greek capital letter delta Δ
followed by one or more subscript numbers)
Example: 18:3(Δ9,12,15) denotes a C18 PUFA with 3 double bonds located between
carbons 9 and 10, 12 and 13, 15 and 16.
3. Specifying the double bond position relative to the methyl (non-carboxyl) end of the fatty
acid chain. (indicated by Greek lower-case letter omega ω)
- An omega-3 fatty acid is an unsaturated fatty acid with its endmost double bond
three carbon atoms away from its methyl end.
- An omega-6 fatty acid is an unsaturated fatty acid with its endmost double bond
six carbon atoms away from its methyl end.

Physical Properties of Fatty Acids

1. SOLUBILITY IN WATER – solubility of fatty acids in water decreases as the carbon
length increases.
- Short-chain fatty acids – slightly soluble in water (due to polarity of –COOH
group)
- Long-chain fatty acids – insoluble in water (due to the non-polar nature of
hydrocarbon chain)
2. MELTING POINTS
a. Carbon Chain length – as the carbon chain length increases, also its melting point
is due to the increased surface area which enhances intermolecular forces of
attraction between fatty acid molecules.
b. Degree of unsaturation – the more the double bonds present, the lower the melting
point will be. It is due to decreased molecular attractions between carbon chains.
 c. Long-chain saturated fatty acids are solids at r.t. while long-chain unsaturated
fatty acids are liquids at r.t.

ENERGY-STORING LIPIDS
● Triacylglycerols- It is a lipid formed by the esterification of three fatty acids to a glycerol
molecule.
● TRIGLYCERIDE was the older name for triacylglycerols.
● It serves as energy storage for the materials in the body and is the most abundant type of
lipid present in the body.
● Normally concentrated on special cells called ADIPOCYTES.

Triacylglycerol types based on the Fatty Acids attached

1. Simple triacylglycerol – is a triester formed from the esterification of glycerol with 3
identical (the same) fatty acid molecules.
2. Mixed triacylglycerol – is a triester formed from the esterification glycerol with more
than 1 kind of fatty acid molecule.
Naturally occurring simple triacylglycerols are rare and the most biochemically important
triacylglycerols are mixed triacylglycerols.

Fats and Oils

● FAT- is a naturally occurring triacylglycerol mixture that is solid or semi-solid at room
temperature.
● OIL- is a naturally occurring triacylglycerol mixture that is liquid at room temperature.

Comparison between fats and oils

Fats Oils

Generally obtained from animals hence Obtained from plant sources although “fish
animal fat oils” of animal origin

Cannot be represented by a single formula, Same as fat, no such single formula

consist of a regular mixture of fatty acids representation
which are dependent on dietary and climatic
factors

Saturated fatty acids predominate in fats thus MUFA and PUFA are present in large
its high melting point amounts thus its liquid form

Pure form is colorless, odorless, and tasteless Same as fat, no color, no odor, and tasteless in
very pure form.

The taste, odors, and colors associated with fats and oils are caused by small traces of other
naturally occurring substances present in the plant or animal that have been carried over during
processing. The presence of those compounds is considered to be “desirable”.

Dietary Considerations and Triacylglycerols

● In dietary discussions, the term “FAT” is used as a substitute for the term triacylglycerol.
Thus dietary fat could mean either a “fat” or “oil”.
● Limit fat intake up to 30% of the total calorie intake ( 15% MUFA, 10% PUFA, and only
5% SFA).
● In simple terms, research studies indicate:
○ Saturated FATS – BAD FATS
○ Monounsaturated FATS – GOOD FATS
○ Polyunsaturated FATS – Can be both GOOD or BAD FATS ( e.g. the omega-3
and omega-6 fatty acids)
 ● Studies indicate that a high-fat diet with a high amount of omega-6 fatty acids often has a
high incidence of heart disease. However, it was also found out that a high-fat diet with a
high amount of omega-3 fatty acids does not correlate to heart disease like the Inuit
people.
● For Monounsaturated Fatty Acids (MUFA);
○ Helps reduce the stickiness of blood platelets which helps prevent blood clots.
○ May also dissolve (blood clots) once they form.
○ Olive, canola, and avocado oils are good sources.
○ Most tree nuts and PEANUTS are also good sources.
○ Many people usually believe in a myth that nuts are UNHEALTIFUL FAT foods.
Although, numerous studies indicate that nuts have STRONG POSITIVE
EFFECT against coronary heart disease.

Essential Fatty Acids- These are fatty acids needed in the human body that must be obtained
from dietary sources because they cannot be synthesized within the body, in adequate amounts,
from other substances.

Two types of Essential Fatty Acids

1. Linoleic Acid- Utilized as starting material for the biosynthesis of arachidonic acid.
(Arachidonic acid (AA) is the major starting material for eicosanoids – blood pressure
and clotting regulation.)
2. Linolenic Acid- Utilized as starting material for the biosynthesis of other two important
omega-3 fatty acids.
(EPA and DHA are important for normal brain development – communication
membranes of the brain.)
(EPA and DHA are also necessary for vision development – active in the retina of the
eye.)

Fat Substitutes (Artificial Fats)- are substances that create the sensation of “RICHNESS” of taste
and “CREAMINESS” of the texture of food without negative effects – obesity and heart disease.
● Simplesse
○ Best known calorie-reduced fat substitute with FDA approval in 1990.
○ From protein egg white via microparticulation.
○ Unsuitable for frying and baking – will turn to gel if heated.
● Olestra
○ Best known calorie-free fat substitute with FDA approval in 1996.
○ Produced by heating soybean/cottonseed oil with sucrose in the presence of
methanol.
○ Heat-stable artificial fat.
○ Can cause gastrointestinal irritation & diarrhea.
○ Interferes cholesterol absorption.
○ Reduces the absorption of fat-soluble vitamins (vitamins A, D, E, and K).

Chemical Reactions of Triacylglycerols

Four common reactions;
● HYDROLYSIS- is the reverse of esterification reaction by it was formed. In the lab, the
reaction needs acid or base. In the human body, hydrolysis occurs in digestion with the
aid of pancreatic enzymes.
○ Complete Hydrolysis- is hydrolysis that occurs in a situation in which all three
fatty acids are removed.
○ Incomplete Hydrolysis- is hydrolysis that occurs in a situation where one or more
fatty acid residues remain attached to glycerol.
 ● SAPONIFICATION- is a reaction for triacylglycerols that is carried out in an alkaline
(basic) solution. For fats and oils, the products of saponification are glycerol and fatty
acid salts. Soaps are made via this reaction.
● HYDROGENATION- It involves hydrogen addition across carbon-carbon multiple
bonds, which decreases the degree of unsaturation. With this change, its melting point
also increases.
● OXIDATION- The carbon-carbon double bonds present in the fatty acid residues can be
subject to oxidation with molecular oxygen (from the air) as the oxidizing agent. Such
oxidation breaks the carbon-carbon bonds, producing both aldehyde and carboxylic acid.
○ The products of oxidation have objectionable odors, and fat and oils containing
them are said to have become “rancid”.

MEMBRANE LIPIDS
80% of the cell membranes are lipids, the rest are proteins. DUAL POLARITY- Structural
characteristics of most membrane lipids.

Three types of Membrane Lipids

1. Phospholipids- is a lipid that contains one or more fatty acids, a phosphate group, and a
platform molecule to which the fatty acids and phosphate group are attached, and alcohol
that is attached to the phosphate group. Platform Molecule in Phospholipids:
a. Glycerol – GLYCEROPHOSPHOLIPIDS- a lipid that contains two fatty acids
and a phosphate group esterified to a glycerol molecule and alcohol esterified to
the phosphate group.
i. All bonds are in a form of ESTER LINKAGES similar to triacylglycerols.
ii. With that ester linkages, glycerophospholipids will undergo hydrolysis and
saponification.
iii. Phosphoric acid is the parent source for the minus one charged phosphate
group used in the formation of glycerophospholipids.
iv. The alcohol attached to the phosphate group in a glycerophospholipid is
usually one of three amino alcohols;
1. Choline (Phosphatidylcholine)- Also known as LECITHIN, are
waxy solids that form a suspension in water. Egg yolks and
soybeans are good dietary sources. Considered as a non-essential
nutrient – can be synthesized in the liver. The food industry uses
lecithins as emulsifiers to promote mixing in mayonnaise, ice
cream, and custards.
2. Serine (Phosphatidylserine) and Ethanolamine
(Phosphatidylethanolamine)- Also known as CEPHALIN, has a
high concentration in the brain, also found in the heart and liver
tissue. It is important in blood clotting.
b. Sphingosine – SPHINGOPHOSPHOLIPIDS- a lipid that contains one fatty acid
and one phosphate group attached to a sphingosine molecule and an alcohol
attached to the phosphate group.
i. It also contains HEAD and TWO TAILS structure that exhibits DUAL
POLARITY, similar to glycerophospholipids.
ii. It also participates in saponification reactions.
iii. Sphingomyelins- sphingophospholipids in which the alcohol esterified to
the phosphate group is choline.
iv. It is found in all cell membranes.
v. Important structural components of MYELIN SHEATH, the protective
and insulating coating that surrounds the nerves.
2. Sphingoglycolipids- is a lipid that contains both fatty acid and a carbohydrate component
attached to a sphingosine molecule. It can undergo saponification reactions, both AMIDE
and GLYCOSIDIC linkages can be hydrolyzed.
 a. Cerebrosides- are the simplest type of sphingoglycolipids. It contains a SINGLE
MONOSACCHARIDE unit – either glucose or galactose and occurs primarily in
the brain (7% dry mass).
b. Gangliosides- is a more complex sphingoglycolipid. It contains up to SEVEN
MONOSACCHARIDE residue – oligosaccharide and occurs in the brain’s GRAY
MATTER.
3. Cholesterol- Is a C27 steroid molecule that is a component of cell membranes and also a
precursor for other steroid-based lipids.
(STEROID – is a lipid whose structure is based on a fused-ring system that involves three
six-membered and one five-membered ring.)
a. UNIQUE Structural Characteristics of Cholesterol from Other Membrane Lipids
i. No fatty acid residue present
ii. Absence of any platform molecule - no glycerol - no sphingosine

iii. Cholesterol is the most abundant steroid in the human body. (Cell
membranes (up to 25% by mass), nerve and brain tissue (10% dry mass),
and virtually all body fluids)
iv. For every 100 mL of normal human BLOOD; 50 mg free cholesterol and
170 mg cholesterol esterified with various fatty acids.
v. Relative high cholesterol levels in the blood can contribute to
ATHEROSCLEROSIS and HEART DISEASE.
vi. Cholesterol is only sparingly soluble in blood. A Protein-carrier system is
used for the distribution of LIPOPROTEINS.
vii. Two types of cholesterol-protein carrier system:
1. HDL (“Good Cholesterol”)- it scrapes away necessary LDL from
the artery walls, preventing the formation of plaques.
2. LDL (“Bad Cholesterol”)- deposits excess cholesterol on the artery
walls, thus promoting plaque formation.
viii. Smoking can also significantly reduce HDL levels. Exercising regularly
tends to increase HDL levels.

Cell Membranes
● Cell membrane- is a lipid-based structure that separates the cell from the aqueous outside
environment. It also acts for control of the movement of substances “in” and “out” of the
cell.
● 80% lipid / 20% protein by mass – myelin sheath of nerve cells
● 20% lipid / 80% protein by mass – inner mitochondrial membrane
● 50% lipid / 50% protein by mass – red blood cell membrane
● Lipid-Bilayer- it is the structural basis of a cell membrane.
○ About 6 to 9 nanometers thick
○ Cholesterol regulates the fluidity of the membrane
○ PROTEIN COMPONENT – responsible for moving substances across such as
nutrients and electrolytes. Also as receptors for hormones and neurotransmitters.
 ○ CARBOHYDRATE COMPONENT – in the form of glycolipid and glycoprotein,
usually found outside of the bilayer. Serves as markers for cell–to–cell recognition
process.
● Transport
○ Passive Transport- Only a few types of molecules like O2, N2, H2O, urea, and
ethanol can cross membranes in this manner.
○ Facilitated Transport- Proteins act as gates. Glucose, chloride ion, and bicarbonate
ion cross membranes in this manner.
○ Active Transport- Proteins serve as pumps. Sodium-ion, potassium ion, and
hydronium ion cross membranes through active transport.

EMULSIFICATION LIPIDS
● Emulsifier- is a substance that can disperse and stabilize water-insoluble substances as
colloidal particles in an aqueous solution. Their mode of action is much like soap during
washing.
● Bile Acids- these are cholesterol derivatives that function as LIPID-EMULSIFYING
AGENT in the aqueous environment of the digestive tract to FACILITATE the
ABSORPTION of dietary lipids in the intestine. Approximately 1/3 of daily cholesterol
production in the liver is converted to bile acids.
○ Three major types of bile acids: Cholic Acid, 12-deoxycholic acid, 7-deoxycholic
acid
○ Bile acids always carry an amino acid (either glycine or taurine) attached to the
side-chain carboxyl group via an amide linkage.
○ The presence of amino acid increases the POLARITY of the carboxylic acid and
its SOLUBILITY in water.
○ Average Bile Acid Composition of Human Bile: 38% cholic acid, 34%
7-deoxycholic acid, and 28% 12-deoxycholic acid derivatives.
● Bile- is a fluid that contains the emulsifying agents that are secreted by the liver, stored in
the gallbladder, and released into the small intestine during digestion.
○ Components of Bile; Bile acids, Bile pigments, Cholesterol, and Electrolytes like
HCO3
○ Gallstones form in the gallbladder when cholesterol levels are high. They are
almost pure crystallized cholesterol that precipitated out from bile. Gallstone
formation is due to the upset of the balance between cholesterol and bile acid
derivatives in bile.

MESSENGER LIPIDS
● Hormone- It is a biochemical substance, produced by a ductless gland, that has a
messenger function. It serves as a means of communication between various tissues.
Some hormones, though not all, are lipids.
Two General Types of Messenger Lipids:
1. Steroid Hormones- is a hormone that is a cholesterol derivative. Two Major Classes:
a. Sex hormones- Hormones that control the reproduction and secondary sex
characteristics. Major Groups of Sex Hormones:
i. ESTROGENS (female sex hormones)- Synthesized in the ovaries and
adrenal cortex.
1. Responsible for female secondary sex characteristics.
2. The primary estrogen is ESTRADIOL.
3. Important in the regulation of the menstrual cycle.
4. Can stimulate mammary gland development during pregnancy.
ii. ANDROGENS (male sex hormones)- Synthesized in the testes and
adrenal cortex.
1. Promotes secondary male sex characteristics.
2. Primary androgen is TESTOSTERONE.
 3. Also promotes muscle development and growth.
iii. PROGESTINS(pregnancy hormones)- Synthesized in the ovaries and the
placenta.
1. Primary estrogen is PROGESTERONE.
2. Produced when uterus lining is preparing for fertilized ovum
implantation.
Those mentioned hormones earlier are examples of NATURAL STEROID HORMONES. Also,
there are synthetic compounds that have a similar mode of action to natural hormones.
➢ NORETHYNODREL- Known commercially as ENOVID. Was one of the first synthetic
progestin used as an oral contraceptive in the 1960s.
➢ RU-486- Also known as MIFEPRISTONE. Controversial “morning-after pill” developed
in FRANCE. It is a synthetic ABORTION DRUG. Terminates pregnancy within the first
9 weeks of gestation. More safe and effective than surgical methods.
➢ METHANDROSTENOLONE- A synthetic tissue building steroid.
Anabolic Agents- These include illegal steroid drugs used by some athletes to build up muscle
strength and enhance endurance but are known to have serious side effects.
b. Adrenocortoid Hormones- Produced by ADRENAL GLANDS and second major
group of steroid hormones. Two Types of Adrenocortoid Hormones:
i. Mineralocorticoids- Controls the balance of Na+ and K+ ions in the cells
and body fluids. ALDOSTERONE is the major mineralocorticoid.
ii. Glucocorticoids- control glucose metabolism and counteract
inflammation. Major glucocorticoids are CORTISOL (hydrocortisone).
Cortisol is the largest (in amount), a hormone synthesized in adrenal
glands.
2. Eicosanoids- are oxygenated C20 fatty acid derivative that functions as a messenger lipid.
a. Derived from the Greek word “eikos”, which means TWENTY.
b. The metabolic precursor of most eicosanoids is arachidonic acid.
c. Almost all cells produce eicosanoids except for RED BLOOD CELLS.
d. The concentration needed is very low (less than 1pbb) to exert a physiological
effect.
i. Inflammatory response; normal response to tissue damage.
ii. Production of pain and fever.
iii. Regulation of blood pressure.
iv. Induction of blood clotting.
v. Control of reproductive function, such as induction of labor.
vi. Regulation of sleep/wake cycle.
e. Prostaglandins- Messenger lipid that is a C20 fatty acid derivative with
cyclopentane ring and oxygen-containing functional groups. Named after prostate
gland – which was thought the only source. More than 20 prostaglandin types
have been isolated in various tissues, from both sexes. The mode of action of
aspirin and analgesics is the deactivation prostaglandin synthesis enzyme which
results in inflammation and fever reduction. Regulatory Functions of
Prostaglandins
i. Raising body temperature
ii. Gastric juice secretion inhibition
iii. Increasing protective mucus secretion in the stomach
iv. Smooth muscle contraction and relaxation
v. Directing water and electrolyte balance
vi. Pain intensification
vii. Enhancement of inflammation response
f. Thromboxanes- Messenger lipid that is a C20 fatty acid derivative with cyclic
ether ring and oxygen-containing functional groups. One important function is to
promote blood clot formation. Produced by blood platelets and promotes platelet
aggregation.
 g. Leukotrienes- Messenger lipid that is a C20 fatty acid derivative that contains
three conjugated double bonds and hydroxyl groups. Normally found in
LEUKOCYTES (white blood cells). In elevated levels, if there is hypersensitivity,
allergy, and inflammatory response.

PROTECTING-COATING LIPIDS
● Biological Waxes- A lipid that is a monoester of a long-chain fatty acid and long-chain
alcohol. The water-insoluble, water-repellent properties of biological waxes were due to
the complete dominance of the nonpolar nature of the long hydrocarbon chains present
over the weak polar ester group that links the two chains together.

Functions of Biological Wax

1. Water-repellent as PROTECTION (Humans and animals have skin glands for this
function, the hydrophobic property of FUR, in birds (aquatic birds) waxes secreted by
preen glands keeping their feathers DRY.).
2. As INSULATOR to prevent body heat LOSS (Birds in COLD WEATHER).
3. Prevents excessive WATER LOSS and PARASITE ATTACK in plants (arid plants).

Examples of Biological Wax

1. Beeswax- from bee honeycomb.
2. Carnauba Wax- obtained from a species of Brazilian palm trees used for high gloss
finishes like automobile, boat, floor, and shoe wax.
3. Jojoba Wax- obtained from jojoba bush that can be used in soaps, cosmetics, and candles.
4. Lanolin- a mixture of waxes from sheep’s wool. Used as a base for skin creams and
ointments intended to enhance water retention.

● Wax- is a pliable, water-repelling substance utilized for protecting and polishing surfaces.
● Mineral Wax- also called PARAFFIN WAX. It is a mixture of long-chained ALKANES
from petroleum processing.
● Earwax’s medical name is cerumen.

PROTEINS
● Protein- is a polymer in which the monomer units are amino acids.
● Comes from the Greek word “PROTEIOS” which means “of first importance”.
● Next to water, proteins are the most abundant substance in most animal cells (10% - 20%
of cell mass).
● Proteins contain the following elements: Carbon, Hydrogen, Oxygen, and Nitrogen.
Though it can also contain sulfur.
● Specialized proteins contain other elements that make up their structure aside from C, H,
O, and N. They also contain phosphorus, iodine, and iron.
● A typical human cell contains about 9000 different proteins.
● The Human body has about 100,000 different proteins.

Classification of Proteins
1. Catalytic Proteins (ENZYMES)- primary role as catalysts.
2. Defense Proteins (ANTIBODIES and IMMUNOGLOBINS)- central to the functioning
of the body’s immune system.
3. Transport Proteins (HEMOGLOBIN, HDL & LDL, TRANSFERRIN)- the movement of
materials.
4. Messenger Proteins (INSULIN, GLUCAGON, and HUMAN GROWTH HORMONE)-
transmit signals to coordinate processes between different cells, tissues, and organs.
5. Contractile Proteins (ACTIN and MYOSIN)- necessary for all forms of movement.
6. Structural Proteins (COLLAGEN & KERATIN)- confer stiffness and rigidity to
otherwise fluid-like biochemical systems.
7. Transmembrane Proteins- span a cell membrane help control the movement of small
molecules and ions through the cell membrane.
8. Storage Proteins (FERRITIN & MYOGLOBIN)- bind and store small molecules for
future use.
9. Regulatory Proteins- act as sites at which the messenger molecules can bind and thereby
initiate the effect that the messenger carries (found in the exterior surface of the cell
membrane).
10. Nutrient Proteins (CASEIN & OVALBUMIN)- proteins important particularly in the
earlier stages of life, from embryo to infant.