LIPIDS

PREPARED BY:
FRANCIS CARLO A. LAO
COLLEGE OF PHARMACY
Lesson Objectives
At the end of the discussion, the students should able to:
o Define the common terms in lipids and its components;

o Determine the different transport and shuttle systems used in lipids;

o Classify lipids based on its functions;

o Categorize lipids based on its physicochemical properties; and

o Explain the etiology, symptoms, and treatment of different lipid related diseases.
Fat isn’t needed in our Fat raises blood
diet glucose

MYTHS ON
FATS
Fat raises cholesterol
Fat increases body
weight
WHAT ARE
LIPIDS?
• organic compound found in living
organisms
• are a heterogeneous group of
compounds, including fats, oils,
steroids, waxes, and related
compounds, which are related more by
their physical than by their chemical
properties.
 Serves as thermal
insulator

GENERAL
Precursors for
FUNCTIONS OF Energy reservoir
hormones LIPIDS

Structure Dissolves
vitamins
CLASSIFICATION OF
LIPIDS
 LIPIDS

CHEMICAL SAPONIFIABILI CARBON CHAIN

FUNCTION TY LENGTH
CHEMICAL FUNCTIONS
 Energy storage

Membrane lipids

Chemical Emulsification
Functions lipids

Messenger lipids

Protective coating
lipids
ENERGY STORAGE
ADIPOSE TISSUE
• storage site of triacylglycerols in the human
body, specifically in the special cells known
as ADIPOCYTES.

TRIACYLGLYCEROL
• Most abundant type of lipids present in the
body
• More efficient at storing energy than
glycogen, large quantities can be packed in
very small volume.
TRIGLYCERIDE
(TAG)
Is a lipid formed by
esterification of three fatty
acids to a glycerol molecules.
ESTERIFICATION REACTION:
Carboxylic acid + alcohol ↔ ester + H2O

Glycerol + stearic acid = triacylglycerol + H2O

FATTY ACIDS
- are naturally occurring monocarboxylic acid.
- Building blocks of lipids

FATTY ACIDS

LONG CHAIN MEDIUM CHAIN SHORT CHAIN

(C12-C26) (C8-C10) (C4-C6)
CLASSIFICATION OF
FATTY ACIDS
 FATTY ACIDS

DEGREE OF CONFIGURATION
SATURATION OF DOUBLE BONDS
DEGREE OF
SATURATION
saturated fatty acid
▪ is a fatty acid with a carbon chain in which all
carbon–carbon bonds are single bonds.
DEGREE OF
SATURATION
▪ monounsaturated fatty acid
▪ is a fatty acid with a carbon
chain in which one
carbon–carbon double bond is
present.
DEGREE OF
SATURATION
▪ polyunsaturated fatty acid
▪ is a fatty acid with a carbon chain
in which two or more
carbon–carbon double bonds are
present.
▪ IUPAC name:
cis,cis-9,12-octadecadienoic
acid
▪ Common name: linoleic acid
Unsaturated Fatty Acids and
Double-Bond Position
• SHORT HAND NOTATION:
• DELTA DESIGNATION
• The notation 18:3(∆9,12,15) denotes a C18 PUFA with three double bonds at
locations between carbons 9 and 10, 12 and 13, and 15 and 16.
Unsaturated Fatty Acids and
Double-Bond Position
SHORT HAND NOTATION:
OMEGA (ω) FAMILY DESIGNATION
• omega-3 fatty acid
• unsaturated fatty acid with its endmost double bond three carbon atoms away
from its methyl end.
Unsaturated Fatty Acids and
Double-Bond Position
omega-6 fatty acid
unsaturated fatty acid with its endmost double bond six carbon atoms away
from its methyl end.
 FATTY ACID FORMULA No. of OCCURENCE
Carbon
SATURATED FATTY ACIDS

Acetic acid CH3COOH 2 Vinegar

Propionic acid CH3CH2COOH 3 An end product of carbohydrate ermentation by rumen
Organisms

Butyric acid C3H7COOH 4 Glycerides in butter

Caproic acid C5H11COOH 6 Goat and Cow butter; Coconut fat

Caprylic acid C7H15COOH 8 Goat and Cow butter; Coconut fat; Human
Fat
Capric acid C9H19COOH 10 Goat and Cow butter; Coconut fat; Fat of
spice bush
Lauric C11H23COOH 12 Spermaceti, cinnamon, palm kernel oil,
coconut oils, laurels, butter
Myristic acid C13H27COOH 14 Nutmeg, palm kernel, coconut oils,
myrtles, butter
Palmitic acid C15H31COOH 16 Animal and vegetable fats; spermaceti;
beeswax
Stearic acid C17H35COOH 18 Animal and vegetable fats
 FATTY ACID No. of Carbon & No. of double OCCURENCE
bonds
UNSATURATED FATTY ACIDS
Monoenoic acids (one double bond)
Palmitoleic 16:1∆9 In nearly all fats
ω7
Oleic acid 18:1∆9 Animal and Vegetal fats and oil
ω9
Elaidic acid 18:1∆9 Hydrogenated and ruminant fats.
ω9
Dienoic acids (two double bonds)
Linoleic Acid 18:2∆9,12 Linseed oil, Corn, peanut, cottonseed, soybean, and many plant oils.
Ω6

Trienoic acids (three double bonds)

Gamma-Linolenic acid 18:3∆6,9,12 Linseed oil, Some plants, eg, oil of evening primrose, borage oil; minor fatty
Ω6 acid in animals.

α-Linolenic acid 18:3∆9,12,15 Frequently found with linoleic acid but particularly
ω3 in linseed oil.
Tetraenoic acids (four double bonds)
Arachidonic acid 20:4∆5,8,11,14 Lipids of the liver and brain; eggyolk.Found in animal fats and in peanut oil;
Ω6 important component of phospholipids in animals

Pentaenoic acids (five double bonds)

Timnodonic 20:5∆5,8,11,14,17 Important component of fish oils, eg, cod liver, mackerel, menhaden, salmon
oils.
Hexaenoic acids (six double bonds)
Cervonic 22:6∆4,7,10,13,16,19 Fish oils, phospholipids in brain.
ω3
TRIGLYCERIDE
(TAG)
Simple Triacylglycerol
• Is a triester formed from the esterification of
glycerol with three identical fatty acids
molecule.

Mixed Triacylglycerol
• A triester formed from the esterification of
glycerol with more than one kind of fatty acid
molecules.
 naturally occurring mixtures of
FATS & OILS triacylglycerol

FATS OILS

1. Liquid at room temp

1. Solid or semisolid at room temp
2. Obtained from plants
2. Obtained from animal sources
3. Mono and polyunsaturated compounds
3. Saturated compounds predominates
predominates
4. “Linearity” of fatty acids causing the
4. “Bends” chain causing the molecule
molecule to be closely packed
incapable of close packing
5. Higher melting point
5. Lower melting point
ESSENTIAL FATTY
ACIDS
Is a fatty acid needed in the human
body that must be obtained from dietary
sources.
ESSENTIAL FATTY
ACIDS
FUNCTIONS:
▪ are needed for proper membrane structure
▪ serve as starting materials for the production of several nutritionally
important longer chain omega-6 and omega-3 acids.

DEFICIENCIES:
▪ The skin reddens and becomes irritated
▪ infections and dehydration are likely to occur,
▪ liver abnormalities
MEMBRANE LIPIDS
• All cells are surrounded by membrane
that confines their contents.
• Up to 80% of the mass if a cell
membrane can be lipid material, the rest
is primarily protein.
MEMBRANE LIPIDS

FATTY ACIDS

PHOSPHOLIPID SPHINGOGLYC
CHOLESTEROL
S OLIPIDS
PHOSPHOLIPIDS
is a lipid that contains one or more fatty acids, a
phosphate group, a platform molecule to which
the fatty acid(s) and the phosphate group are
attached, and an alcohol that is attached to the
phosphate group.
PHOSPHOLIPIDS
PHOSPHOLIPIDS
1. GLYCEROPHOSPHOLIPIDS or
GLYCEROPHOSPHATIDES
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
GLYCEROPHOSPHATIDES
Phosphatidylserine (PS)

• used for Alzheimer's

disease, age-related
decline in mental function,
• attention
deficit-hyperactivity
disorder (ADHD),
depression
GLYCEROPHOSPHOLIPIDS
2. Phosphatidylcholine (PC)
(LECITHIN)
dipalmitoyl phosphatidylcholine (DPPC, or
dipalmitoyl lecithin) - is the major lipid
component of lung surfactant—the extracellular
fluid layer lining the
alveoli.
GLYCEROPHOSPHOLIPIDS
3. Plasmalogens

Formed when the fatty acid at carbon 1 of a

glycerophospholipid is replaced by an
unsaturated alkyl group attached by an ether
linkage to the core glycerol molecule.
GLYCEROPHOSPHOLIPIDS
4. Platelet-activating factor (PAF)
- unusual ether glycero - phospholipid, with a
saturated alkyl group in an ether link to carbon
1 and an acetyl residue (rather than a fatty acid)
at carbon 2 of the glycerol backbone.
GLYCEROPHOSPHOLIPIDS
4. Platelet-activating factor (PAF)
triggers potent thrombotic and acute
inflammatory events. For example, PAF
activates inflammatory cells and mediates
hypersensitivity, acute inflammatory, and
anaphylactic reactions. It causes platelets to
aggregate and degranulate, and neutrophils and
alveolar macrophages to generate superoxide
radicals
SPHINGOPHOSPHOLIPIDS
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
1. SPHINGOMYELINS
- Sphingophospholipids in which the alcohol
esterified to the phosphate group is choline.

- are found in all cell membranes and are

important structural components of the myelin
sheath, the protective and insulating coating that
surrounds nerves.
SPHINGOPHOSPHOLIPIDS
1. SPHINGOMYELINS
- Sphingophospholipids in which the alcohol
esterified to the phosphate group is choline.

- are found in all cell membranes and are

important structural components of the myelin
sheath, the protective and insulating coating that
surrounds nerves.
SPHINGOPHOSPHOLIPIDS
2. SPHINGOGLYCOLIPIDS
is a lipid that contains both a fatty acid and a
carbohydrate (mono or oligosaccharide)
component attached to a sphingosine molecule.
Differ with sphingomyelin because it does not
contain phosphate group.
SPHINGOGLYCOLIPIDS

SPHINGOGLYCOLIPIDS

NEUTRAL ACIDIC
NEUTRAL
GLYCOSPHINGOLIPIDS
1. CEREBROSIDES
• occur primarily in the brain (7% of dry
mass).
• simplest sphingoglycolipids
• a ceramide that contain a single
monosaccharide unit—either glucose or
galactose
• Ceramide-galactose or galactocerebroside –
most common cerebroside found in myelin
NEUTRAL
GLYCOSPHINGOLIPIDS
1. CEREBROSIDES
• Ceramide-glucose or glucocerebroside –
intermediate in the synthesis and degradation
of the more complex glycosphingolipids
NEUTRAL
GLYCOSPHINGOLIPIDS
2. GLOBOSIDES (CERAMIDE
OLIGOSACCHARIDE)
• is a type of glycosphingolipid with more than
one sugar as the side chain (or R group) of
ceramide. Ex. Ceramide-glucose-galactose
(aka lactosylceramide)
• The additional monosaccharides can include
substitute sugar such as
N-acetylgalactosamine
ACIDIC GLYCOSPHINGOLIPIDS

• are negatively charged at physiologic pH,

provided by N-acetylneuraminic acid
(NANA)(a sialic acid) in ganglioside or by
sulphate groups in sulfatides
ACIDIC GLYCOSPHINGOLIPIDS

1. GANGLIOSIDES
• More complex sphingoglycolipids
• Residues occur in the gray matter of the brain
as well as in the myelin sheath or in the
ganglion cells of the CNS particularly in
nerve endings
• Contain a branched chain of up to seven
monosaccharide residues since it’s a
derivative of ceramide oligosaccharide
ACIDIC GLYCOSPHINGOLIPIDS

2. SULFATIDES
• aka sulfoglycosphingolipids or sulphated
cerebrosides
• found predominantly in the brain and
kidneys.
• Has sulfate group in galactose
Sphingolipodoses
a lysosomal lipid storage disease due to the partial or
total missing of the specific lysosomal enzyme acid
hydrolase needed for the synthesis of
glycosphingolipids.

Degradation of sphingolipids showing the lysosomal

enzymes affected in related genetic diseases, the
sphingolipidoses. All of the diseases are autosomal
recessive except Fabry disease, which is X-linked, and
all can be fatal in early life.
Sphingolipodoses
1. FABRY DISEASE
o Accumulation of globosides
o Deficiency in a-galactosidase
o Reddish-purple skin rash
o Kidney and heart failure
o Burning pain in lower extremities
Sphingolipodoses
1. FABRY DISEASE
o Accumulation of globosides
o Deficiency in a-galactosidase
o Reddish-purple skin rash
o Kidney and heart failure
o Burning pain in lower extremities
Sphingolipodoses
2. TAY-SACHS DISEASE
o Accumulation of gangliosides (GM2)
o Deficiency in β-Hexosaminidase A
(α-subunit)
o Rapid, progressive, and fatal
neurodegeneration
o Blindness
o Cherry red macula
o Muscular weakness
o Seizures
Sphingolipodoses
3. KRABBE DISEASE
o Deficiency in β-Galactocerebrosidase
o Accumulation of galactocerebrosides
o Mental and motor deterioration
o Blindness and deafness
o Near total loss of myelin
o Globoid bodies in white matter of brain
Sphingolipodoses
CHOLESTEROL
o C27 steroid molecule that is a
component of cell membranes and a
precursor for other steroid-based lipids.

o most abundant steroid in the human

body (cell membrane up to 25% by
mass), in nerve tissue, in brain tissue
(about 10% by dry mass)
CHOLESTEROL
o Biosynthetic cholesterol is distributed to cells throughout the body for various uses
via the bloodstream. Because cholesterol is only sparingly soluble in water (blood), a
protein carrier system is used for its distribution. These cholesterol–protein
combinations are called lipoproteins.
CHOLESTEROL
• LDL - carry cholesterol from the liver to
various cells or tissues of the body
• HDL - carry excess cholesterol from
body tissues back to the liver for
degradation to bile acids
• VLDL – transport triacylglycerols from
the liver to adipose tissue
• CHYLOMICRONS – transport dietary
triacylglycerols from the intestines to the
liver and adipose tissue
Atherosclerosis
a form of cardiovascular disease
characterized by the buildup of plaque
along the inner walls of arteries.

PLAQUE
is a mound of lipid material mixed with
smooth muscle cells and calcium. Much of
the lipid material in plaque is cholesterol.
CELL MEMBRANE
is a lipid-based
structure that separates a cell’s aqueous-based
interior from the aqueous environment
surrounding the cell.

LIPID BILAYER
is a two-layer-thick structure of
phospholipids and glycolipids in which the
nonpolar tails of the lipids are in the middle
of the structure and the polar heads are on the
outside surfaces of the structure
CELL MEMBRANE
a. 3 distinct parts to the bilayers.

b. Held together by intermolecular interactions,

not by covalent bonds.

c. Most lipid molecules in the bilayer contain at

least one unsaturated fatty acid.

d. Cholesterol molecules

e. Proteins are also components of lipid bilayers.

f. Small carbohydrate molecules, usually

oligosaccharides, are also components of cell
membranes.
MEMBRANE PROTEINS
1. INTEGRAL MEMBRANE
PROTEIN
is a membrane protein that penetrates the
cell membrane

2. PERIPHERAL MEMBRAIN
PROTEIN
is a nonpenetrating membrane protein
located on the surface of the cell
membrane.
TRANSPORT MECHANISM
EMULSIFICATION LIPIDS
EMULSIFI
ER
is a substance that can disperse and
stabilize water-insoluble substances as
colloidal
particles in an aqueous solution.

BILE ACIDS

Cholesterol derivatives that act as

emulsifying agents that facilitate the
absorption of dietary lipids in the intestine
EMULSIFICATION LIPIDS
BILE
SALTS
Formed by conjugation of bile acids with
taurine and glycine residues to give anions.

BILE

Fluid containing emulsifying agents that is

secreted by the liver, stored in the gall
bladder, and released into the small
intestine during digestion.
Obtained by oxidation of cholesterol, bile
acids differ structurally from cholesterol in
three respects:

1. They are tri- or dihydroxy cholesterol

derivatives.
2. The carbon 17 side chain of cholesterol has
been oxidized to a carboxylic acid.
3. The oxidized acid side chain is bonded to an
amino acid (either glycine or taurine) through
an amide linkage.
BIOCHEMICAL
RELATIONSHIP BETWEEN
CHOLESTEROL and BILE
ACIDS
Increased secretion of cholesterol and a
decrease in the size of the bile pool, can upset
the balance between the cholesterol present in
bile and the bile acid derivatives needed to
maintain cholesterol’s solubility in the bile. The
result is the precipitation of crystallized
cholesterol from the bile and the resulting
formation of gallstones in the gallbladder.
MESSENGER LIPIDS
HORMONE
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, though not all,
are lipids.

STEROID HORMONE

a hormone that is a cholesterol derivative.

STEROID HORMONES
SEX HORMONES
control reproduction and secondary sex
characteristics

ADRENOCORTICOI
D
regulate numerous biochemical processes
in the body
SEX HORMONES
ESTROGENS
o Female sex hormone

o Synthesized in ovaries and adrenal

cortex

FUNCTIONS:

Responsible for the development of female secondary sex characteristics at the onset of
puberty, regulation of menstrual cycle, stimulate the development of mammary glands
during pregnancy and induce estrus (heat) in animals
SEX HORMONES
ANDROGENS
o Male sex hormone

o Synthesized in testes and adrenal cortex

FUNCTIONS:
promote the development of male secondary sex characteristics and also promote muscle
growth

FORM:
TESTOSTERONE
SEX HORMONES
PROGESTINS
o Pregnancy hormones

o Synthesized in ovaries and the placenta

FUNCTIONS:
prepare the lining of the uterus for implantation of the fertilized ovum and also suppress
ovulation

FORM: PROGESTERONE
CORTICOSTEROIDS
MINERALOCORTICOIDS

o Example: Aldosterone

FUNCTIONS:
stimulates renal reabsorption of Na+ and
excretion of K+
CORTICOSTEROIDS
GLUCOCORTICOID

o Example: Cortisol

FUNCTIONS:
- control glucose metabolism and
counteract inflammation

- Cortisol and its synthetic ketone

derivative cortisone exert powerful
anti-inflammatory effects in the body
EICOSANOID
an oxygenated C20 fatty acid derivative that functions as a messenger lipid. The term
eicosanoid is derived from the Greek word eikos, which means “twenty.” The metabolic
precursor for most eicosanoids is arachidonic acid, the 20:4 fatty acid.
Characteristics of
Eicosanoids
Have profound
Produced by physiological effects
all cells except at Hormone-like Short lifespan
extremely low
RBC concentrations
THE PHYSIOLOGICAL EFFECTS OF EICOSANOIDS
INCLUDE MEDIATION OF:

1. The inflammatory response, a normal response to tissue damage

2. The production of pain and fever
3. The regulation of blood pressure
4. The induction of blood clotting
5. The control of reproductive functions, such as induction of labor
6. The regulation of the sleep/wake cycle.
PROTECTIVE COATING
LIPIDS
BIOLOGICAL WAX

a lipid that is a monoester of a long-chain fatty acid and a long chain alcohol.
Characteristics:
o are monoesters, unlike fats and oils, which are triesters.
o the fatty acids found in biological waxes generally are saturated and contain from 14 to
36 carbon atoms.
o the alcohols found in biological waxes may be saturated or unsaturated and may contain
from 16 to 30 carbon atoms.
o Its water-insoluble, water-repellent properties of biological waxes result from the
complete dominance of the nonpolar nature of the long hydrocarbon chains present
(from the alcohol and the fatty acid)
Functions
o water-repellent
o to protect hair and skin and to keep it pliable and lubricated
o for plant leaves, to prevent excessive evaporation of water and to protect against
o parasite attack
NOTABLE BIOLOGICAL
WAXES
1. Carnauba wax
o (obtained from a species of Brazilian palm tree)
o is a hard wax whose uses involve high-gloss finishes: automobile wax, boat wax, floor
wax, and shoe wax

2. Lanolin wax
o a mixture of waxes obtained from sheep wool
o is used as a base for skin creams and ointments intended to enhance
o retention of water (which softens the skin)
WAXES
a pliable, water-repelling substance used particularly in protecting surfaces and
producing polished surfaces

MINERAL WAX
o a mixture of long-chain alkanes obtained from the processing of petroleum.
o Also known as paraffin wax
o resist moisture and chemicals and have no odor or taste.
o They serve as a waterproof coating for such paper products as milk cartons and waxed
paper.
PHYSICAL PROPERTIES OF
LIPIDS
WATER SOLUBILITY
Based on carbon chain length
• Solubility decreases as carbon chain length increases
• Short-chain fatty acids have a slight solubility in water.
• related to the polarity of the carboxyl group present.
• Long-chain fatty acids are essentially insoluble in water.
• the nonpolar nature of the hydrocarbon chain completely dominates
solubility considerations.
PHYSICAL PROPERTIES OF
LIPIDS
MELTING POINT
Based on carbon chain length
• As carbon chain length increases, melting point increases. This trend is related to
the greater surface area associated with a longer carbon chain and to the increased
opportunities that this greater surface area affords for intermolecular attractions
between fatty acid molecules.
PHYSICAL PROPERTIES OF
LIPIDS
MELTING POINT
Based on degree of unsaturation
• saturated fatty acids have higher melting points than unsaturated fatty acids with
the same number of carbon atoms.
• The greater the degree of unsaturation, the greater the reduction in melting points.
• Long-chain saturated fatty acids tend to be solids at room temperature, whereas
long-chain unsaturated fatty acids tend to be liquids at room temperature
MELTING POINT
o The decreasing melting point associated with increasing degree of unsaturation in
fatty acids is explained by decreased molecular attractions between carbon chains.
o The double bonds in unsaturated fatty acids, which generally have the cis
configuration, produce “bends” in the carbon chains of these molecules These
“bends” prevent unsaturated fatty acids from packing together as tightly as saturated
fatty acids.
o The greater the number of double bonds, the less efficient the packing. As a result,
unsaturated fatty acids always have fewer intermolecular attractions, and therefore
lower melting points, than their saturated counterparts
QUESTIONS?