LIPIDS

General Properties

Ø are organic compounds of biologic origin

Ø are insoluble in water – hydrophobic in
nature
Ø soluble in nonpolar organic solvents such as
ether, acetone and CCl4 , benzene
Ø contains C, H, O, with N & P
General Properties

Ø yields fatty acids in hydrolysis + combine

fatty acids to form esters
Ø take part in plant and animal metabolism
Ø they are not polymer
Ø they are the chief storage form of energy
 General Properties
Ø they provide 6-fold as much energy as an
equivalent mass of glucose
Ø fat and oils are the principal store forms of
energy in many organism
Ø they participate in oxidative phosphorylation
Ø many lipids are amphipathic
In aqueous environment, lipid molecules associate
by non-covalent interaction to form
supramolecular structure like:
a)monolayers - 1 layer of 1 molecule thick

b)micelles - are aggregates of molecule in a

colloidal solution like that is
formed by detergents
c) bilayers- a film two molecules thus,
in which each molecule is
arranged with its hydrophobic
end

d) vesicle - tiny sac

 Functions: (Use of fats in the body)
Ø serve as a storage form of metabolic fuel
(fatty acid & triacylglycerol)

• as fuel, it produces more energy per gram,

metabolism of fat produce 9 kcal/g
• reserve supply of food + energy
Ø serve as a transport form of metabolic fuel (free
fatty acids, triglyceride + cholesterol ester)
Ø provide the structure components of membrane
(phospholipids, glycolipid, galactolipids,
sphingolipids)
• membrane
a)protector for vital organs
b)as insulator
Ø they serve as a part of the outer coating between
the body of the organism and the environment

Ø it serve as pigment (carotene), hormones (Vit.

A&D), signaling molecules (like eicosanoids,
phosphatidylinositol, steroid hormones),
cofactor (Vit. E& lipid quinones), detergent
(bile salt)
CLASSIFICATION OF LIPID
A. Simple Lipids or Homolipids

- Esters of fatty acid with various alcohols

- Upon hydrolysis

Simple lipid + H2O hydrolysis fatty acids + alcohol

 Fat /or Oil
Simple lipid + H2O hydrolysis 3 fatty acids +glycerol

- Fats are esters formed by combusting fatty

acids + 1 alcohol
Stearic acid + glycerol alcohol hydrolysis glycerol monostearate
 Wax
- Are produced on the reaction of a fatty acid +
monohydric alcohol

- Are insoluble in water, non-reactive + flexible

- makes a protective coating

Example:

§ Carnauba Wax – is largely an ester of myricyl

alcohol

§ Beeswax – is largely esters of long-chain fatty

acid with long chain of alcohol
The alcohol maybe sterile like:

lanosterol à was produced with

lanolin à which is widely used in cosmetics + ointment

Simple lipid + H2O hydrolysis fatty acids +

monohydric alcohol
B. Compound Lipid or Heterolipid /
Complex Lipid
- They are esters of fatty acids with alcohol and
possess additional groups
Example:
1. Phospholipid

- Are formed in all tissues in the human body

• Brain, bile, spine tissue and cell membrane

• Cell membrane – are composed on the average
of 40 to 50 % lipid
Phospholipids are divided into:

a) Phosphoglyceride

b) Phosphosphingoside
a) Phosphoglyceride

- in which the alcohol is glycerol

- One category of phospholipid
2 Types ----- are dependent on the nitrogen
compound is present
1. Lecithin/ Phosphatidylcholine
- Are particularly important in the metabolism of fats
by the liver
- The nitrogen compound – is choline and alcohol
- They are insoluble in water but good emulsifying
agents
- Good source of phosphoric acid à which is
needed for the synthesis of new tissues
Source:
- Egg yolk, soy beans
- It is used commercially as emulsifying agents in
dairy products and in the manufacture of
mayonnaise
Fats are partly converted to lecithins in the
body à and are transported as lecithin from one
part of the body to another

Lecithins – are widely distributed in all cells +

have both metabolic + structure function in the
membrane
Dipalmitoyl Lecithin – 2 Fatty acids are palmitic
acid
- Which is a very good surface active agent
- It prevents adherence of the inner surface of the
lungs
- The absence of dipalmitoyl lecithin from the
lungs of a premature infant causes Respiratory
Distress Syndrome
- The removal of 1 molecule of fatty acid from the lecithin
produces lysolecithin
- The removal of this molecule of fatty acids – is catalyzed
by the enzyme:
- Lecithanase A – which is found in the venom of
poisonous snake

Venom is poisonous because it produces lysolecithin which

in turn cause:
Hemolysisà destruction of RBC
2. Cephalins

- Phosphatidylethanolamine
- Are similar to lecithin except that another nitrogen
compound (ethanolamine) is present
- Important in the blood clotting
- Source of phosphoric acid à for the formation of
new tissue
 3. Phosphatidylserine
4. Phosphatidylinositol
5. Plasmalogens

- Structurally resemble like the lecithin + cephalic but

have an unsaturated ether at C, instead of an ester
- Constitute up to 100% of the phospholipid found in
the membrane of brain + muscle cells
B. Phosphosphingoside – in which the alcohol is
sphingosine
- Also called sphingolipid
- It has sphingosine

Example:

Sphingomyelin – present in large amount of the

brain + nerve tissue
Niemann-Pick Disease

- A disease in infancy or early childhood

- Sphingomyelin accumulate in the brain, liver and
spleen
- Its accumulation results to mental retardation +
early death
- Caused by the lack of enzyme – sphingomyelinase
Multiple Sclerosis

- A demyelinating disease process – there is a loss

of phospholipid + sphingolipid
- increase phosphate level in the CSF
(Cerebrospinal fluid)
2. Glycolipid

- also called cerebrosides because they are found in

the cerebrum of the brain
- are similar to sphingomyelin except that it contain a
carbohydrate – often galactose in form of choline &
phosphoric acid
- they produce no phosphoric acid on hydrolysis
Examples of Glycolipid:

a) kerasin
b) cerebro
c) neuro
d) oxyneuro
e) ganglio
Diseases Related to Glycolipid
1. Gaucher’s disease

- Glycolipid accumulates in the brain

- Causes severe mental retardation + death on age 3
- Enlarge spleen, kidneys, hemorrhaging, mild
anemia + fragile bones
Lack of specific enzyme à B-glucosidase
2. Tay-Sachs

- Absence of enzyme hexosamidase A

- A glycolipid will accumulate in the tissue of the
brain and eyes
- Fatal before they reach age 2
3. Sulfolipid – sulfur containing functional group

Ex. Sulfoquinovosyldiacylglycerine

– which is composed of glycoside of

sulfoquinovose + SQDG – are important member
of sulfur cycle
4. Aminolipid
Ex. Phosphatidylserine – major lipid in eukaryotic
membrane

5. Lipoprotein
- any group of soluble proteins that combine with
and transport fat or other lipid in the blood plasma
A. Derived Lipids – are the substance derived
from simple + complex or compound lipid by
hydrolysis

1. Eicosanoids – are biologically active group of

compounds derived from arachidonic acids
- are extremely potent compounds with a variety
of action
 Examples:

a) Prostaglandins

- Unsaturated fat
- Derived from arachidonic acid à which is formed
from the nutritionally essential fatty acids à linoleic
acid
PGE1 – 1 double bond
PGE2 – 2 double bonds

- they are isolated from male, female reproductive

system, liver, kidneys, pancreas, heart, lungs,
brain and intestine

Richest Source: Human Seminal Fluid

b) Thromboxanes

c) Prostacyclin

d) Leukotrienes

e) Sterols
Physical Properties of Fats
- pure fats + oils are generally white or yellow solids +
liquids
- odorless and tasteless
- lighter than water
- greasy
- form a temporary emulsion when shake with water
- fats + oils must be emulsified by bile in the body
before they can be digested
A. Fatty Acids

- Are straight chains of organic cells

- Found in natural fats

Types:
1. Saturated Fat
2. Unsaturated Fat
3. Trans Fat
1. Saturated

- Contains only single bonds between c atoms

- High melting points
- Saturated fats + oil will not readily combine
with iodine
2. Unsaturated

- Has few double bonds, between c atoms

- Low melting points
 Types:

a) Monosaturated – 1 double bond

b) PUFA – Polyunsaturated fatty acids – many

double bonds
c) Eicosanoids – are oxidized derivatives of 20C
of PUFA formed by: COX and LOX

COX – Cyclo oxygenase

LOX – Lipo oxygenase

Cytochromal Arachidonic Acid – is the usual

substrate of eicosanoids synthesis
 Ex.

a)Prostaglandis
b)Prostacyclins
c)Thromboxane
d)Leukotrienes
Functions of Prostaglandins

- regulating many body functions including:

1.Gastric acid secretion

2.Contraction and relaxation of smooth muscles
3.Inflammation and vascular permeability
4.Body temperature and blood platelet aggregation
5.Stimulate steroid production of adrenal glands
6. Stimulate the release of insulin from pancreas
7. Stimulate the movement of Ca+ from bone
8. Have also been clinically used to induce
abortion or induce labor in a term pregnancy
9. To treat hypertension
10. Relieve bronchial asthma
11. Heal peptic ulcer
12.Increase cAMP in blood platelets, thyroid, corpus
luteum, adenohypophysis + lungs but decrease in
cAMP in fat / adipose tissue

Increased production of Prostaglandin = hypocalcemia &

osteolysis by malignant tissues
PGE1 – is used to strengthen babies born with Cyanotic
Congenital Heart Disease (blue babies) to prepare them for
corrective surgery
Prostacyclin

- Potent inhibitor of platelet aggregation + is a

powerful vasodilators
- Stimulation of cAMP production
Thromboxanes

- With prostacyclin - it maintains a healthy

vascular system
- They have influence by regulating the
production of cAMP
- Inhibitor of cAMP production
Leukotrienes
- 3 alternate sets of double bond

ØLeukotriene C – involved in the body’s allergic reaction

ØIt constricts air passages to bronchi during asthma attack
2. Steroids

- High molecular mass tetracyclic compound

a) Cholesterol

- The most common sterol

- Found in animal fats – found in all animal tissue
- It aids in the absorption of fatty acids from the
small intestine
- Most of the body’s cholesterol is derived or synthesized
from other substance such as carbohydrate + protein &
fats
- The rest comes from the diet

Atherosclerosis – a form of arteriosclerosis à deposition

of excess lipid from the triglyceride + cholesterol from
bloodstream
3. Trans Fat

- Are fats made when liquid oils are turned

into solid fats, like shortening or
margarine.
- It is done through hydrogenation
Range of Cholesterol Level
200-220 mg/dL

Cholesterol-lowering drugs
• Pravastatin
• Lovastatin
b) Ergosterol
- Is a sterol similar to cholesterol
• Calciferol – Vit. D

c) Bile Salts – make it easier for your body to absorb

and digest the fats and fat soluble vitamins that you
have eaten
d) Sex hormones – female: estrogen, progesterone
e) Adrenal cortex – secretes cortisol and aldosterone
Anabolic Steroids

- Are hormones that control the synthesis of larger

molecules from smaller ones

Example:
Male hormone – testosterone
- Increase muscle mass
ØUndesirable effects: testicular athrophy, impotence,
hypercholesterolemia, breast growth, liver growth
Female

Ø Increased masculinity, formation of a

greater amount of body hair, deepening of
the voice, menstrual irregularities
A. Glycerides

- Are esters formed from glycerol reacting with

fatty acids
- their primary function is to serve as fat storage
molecule
- They may be classified based on the number of
fatty acids reacting with glycerol
B. Glycerol

- Also called as glycerin or glycerine

- A pure substance found directly in triglyceride
of fats + oils
- Is a naturally occurring alcohol (C3 H8 O3)
- Odorless liquid used as solvent, sweetening agent and
as medicine
- When glycerol is in the intestines, it attracts water
into the gut, softening stools + relieving constipation
- Viscous at low temperature + non-toxic in low
concentration
- It is a structural backbone of triacylglycer molecules
+ can be converted to a glycolytic substrate for
subsequent metabolism
Chemical Reactions
a) Hydrolysis

- When fats are treated by enzymes,

acids or bases à they are hydrolyzed to form fatty
acids + glycerol
- When fats are hydrolyzed to fatty acids + glycerol, the
glycerol separates from the fatty acids and can drawn
off + purified
- Glycerol is used both medicinally + industrially
b) Saponification

- Is the heating of a fat with a strong

base – NaOH à to produce glycerol + salt of
fatty acids
 c) Hydrogenation
- it lowers the iodine number to a value within the range
of fats
- is when vegetable oils can be converted to fats by the
addition of hydrogen in the presence of a catalyst
- is used to produce the so-called vegetable shortenings
used in homes
Ex. Oleomargarine – is prepared by hydrogenating certain fat
+ oils then adding flavoring + coloring agents + vitamin A+D
d) Acrolein Test

- A test used for the presence of glycerol

- Used as a test for fats and oils
 e) Rancidity
- Is when fats develop an unpleasant odor + taste when
allowed to stand at room temperature for a short
period of time
- Is due to hydrolysis + oxidation
- To avoid rancidity --- rapidly à add Vit. C+E (2
naturally occurring antioxidants)
Metabolism of Fats
1. Lipolysis

- Also known as triglyceride breakdown

- To obtain energy from fat, triglyceride must first be
broken down by hydrolysis into their principal
components,
Ø Fatty acids + glycerol
- It takes place in the cytoplasm
2. Fatty Acid Oxidation (Beta oxidation)
ØFatty acid shuttling
ØFatty acid activation

3. Lipogenesis (Fatty Acid Synthesis)

4. Ketone Body Synthesis
5. Cholesterol Synthesis
6. Fatty acids (FFA’s)
Metabolism
1. Lipolysis

- Is the metabolic pathway through w/c lipid triglyceride

are hydrolyzed into a glucose + free fatty acids (FFA’s)

- It is used to metabolize stored energy during fasting

or exercise and usually occurs in fat adipocytes
A. Oxidation of triglyceride in adipose tissue
B. Oxidation of Glycerol
C. Oxidation of fatty acid

C.1. B-oxidative Theory

- oxidation of the second C atom from the acid and of

fatty acid molecule (the b-carbon atom)
- in their process B-oxidative remove 2 C atom at a time
form of a chain
- that is, an 18 C atom fatty acid is oxidize to a
16 C fatty acid to 14-to 12 until the oxidation
process is complete
- enters to Krebs Cycle as does acetyl CoA
- require the presence of Vit. B12 and biotin
2. Lipogenesis

- encompasses the process of fatty acid synthesis and

subsequent triglyceride synthesis
- takes place in both liver and adipose tissue
- to produce triglyceride from acetyl-CoA subunit à
these triglyceride are then used as an energy reserve
stored in adipose tissue
Øthe conversion of glucose to fat - taken place in the
liver + adipose tissue
- insulin – is necessary for lipogenesis in
both liver + adipose tissue

- nutritive state of the organism - is the main

factor controlling the rate of lipogenesis
Steps in the synthesis of fatty acid for acetyl-Co
Another way:
Synthesis of Phospholipid
 Cholesterol à sources:

- Is normally eliminated in the bile, however it

sometimes settles out in the gallbladder as
gallstones, atherosclerosis à cholesterol
deposits in the walls of artery
 Cholesterol Synthesis
ØIt is synthesized in the liver, adrenal cortex, shin, testes,
aorta and intestine
ØIt takes place in that minisomal & autosomal fraction of
the cell
Lowering the Serum Cholesterol
Ø use of hypolipidemic drugs

Ø statins
• lovastatin inhibit
• Pravastin cholesterolsysynthesis in
• simvastin step 1of the chain
• fluvastin
• sitosterol (Cytellin) – blocks the absorption of cholesterol from
the GIT

• cholestyramine (Questran) – prevents the reabsorption of bile salt

• Gemfibrozol (Lopid) – increase the oxidation of fatty acids and

decreases the secretion of triacylglyceme

• Propanolol – increases the LDL catabolism

• Nicotinic Acid – inhibits ULDL production in the liver

Ketone (Acetone) Bodies
- In a diabetic patient or in any other situation in which
carbohydrate metabolism is restricted;
- the body uses oxaloacetate à to produce glucose – for
brain + muscle
- this reduces the amount of oxaloacetic available of
Krebs and Acetyl CoA cannot be properly metabolized
- When this occurs, the acetyl CoA is changed to
acetoacetyl CoA
Diseases

1.Ketonemia – excess accumulation of ketone bodies

2.Ketonuria – excess accumulation of ketone bodies in

urine

3.Ketosis – ketone bodies + urine