LIPIDS

LIPIDS ARE KNOWN AS FATS,

PROVIDE A MAJOR WAY OF
STORING CHEMICAL ENERGY
AND CARBON ATOMS IN THE
BODY
 LIPIDS
▪ They are organic molecules of varying
chemical composition that are grouped
together on the basis of their solubility.

▪ 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.

▪ They dissolve in nonpolar solvents such as

benzene, carbon tetrachloride and diethyl
ether.
FIVE CATEGORIES BASED ON FUNCTION:
 MAJOR CLASSES OF LIPIDS

1. FATTY ACIDS 6. STEROIDS

2. TRIGLYCERIDES 7. PROSTAGLANDINS

3. GLYCEROL 8. FAT-SOLUBLE
PHOSPHATIDES VITAMINS

4. SPHINGOMYELINS 9. WAXES

5. GLYCOLIPIDS
 Major Classes of Lipids:
1. Fatty Acids
◼ Straight chain aliphatic monocarboxylic (RCOOH)
acids.
◼ Fundamental builing blocks of stored fats and
many structural lipids.
◼ General formula:
O
||
R-C-OH

(R should be 5, 6 or greater: to become insoluble in water)

1. FATTY ACIDS
▪ Naturally occurring monocarboxylic acid.
▪ Always contains an even number of carbon
atoms and have a carbon chain that is
unbranched.

▪ Characterized as:
long-chain fatty acids (C12-C26)
medium-chain fatty acids (C8-C10)
short-chain fatty acids (C4-C6).

▪ Rarely found in nature

 Physical Properties of
Fatty Acids
▪ Water solubility: Short chain fatty acids
have some solubility whereas long chain fatty
acids are insoluble

▪ Short chain fatty acids are sparingly soluble

because of carboxylic acid polar group
 Physical Properties of
Fatty Acids

Melting Point
depends upon:

Length of carbon chain

Degree of unsaturation
(number of double
bonds in a molecule)
 Physical Properties of
Fatty Acids
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
 TYPES OF FATTY ACIDS

It is a fatty acid with It is a fatty acid It is a fatty acid with

a carbon chain in with a carbon a carbon chain in
which all carbon to chain in which which 2 or more
carbon bonds are one carbon to carbon to carbon
single bonds carbon double double bonds are
bond is present. present.
Symbol: 6:0
Based on the symbol:
6 – tells the number of carbon atoms
including the carbon in –COOH

0 - tells the number of double bonds

in the R group

R= CnH2n+1 : no double bond

: saturated fatty acids
Naturally Occurring Fatty Acids
◼ Saturated Fatty Acids: all single bonds

Symbol R-group Common Name Systematic Name

6:0 C5H11COOH caproic acid hexanoic
8:0 C7H15COOH caprylic acid octanoic
10:0 C9H19COOH capric acid decanoic
12:0 C11H23COOH lauric acid dodecanoic
14:0 C13H27COOH myristic acid tetradecanoic
16:0 C15H31COOH palmitic acid hexadecanoic
18:0 C17H35COOH stearic acid octadecanoic
20:0 C19H39COOH arachidic acid eicosanoic
24:0 C23H47COOH lignoceric acid tetracosanoic
Naturally Occurring Fatty Acids

◼ Unsaturated Fatty Acids: with double bonds

Symbol R-group Common Name

16: 1∆9 C15H29COOH palmitoleic acid

18: 1∆9 C17H33COOH oleic acid
18: 2∆9,12 C17H31COOH linoleic
18: 3∆9,12,15 C17H29COOH linolenic acid
20: 4∆5,8,11,14 C19H31COOH arachidonic acid
Essential Fatty Acids
◼ Cannot be synthesized by humans and animals
and have to be included in the diet.

◼ Include the following:

1. Linoleic
2. Linolenic
3. Arachidonic
Eicosapentaenoic acid (EPA)
Eicosapentaenoic acid (EPA)

Structure of EPA
Docosahexaenoic acid (DHA)

Structure of DHA
Top 5 food groups based on the mean one-day per capita food
consumption: (2015 Household Food Consumption Survey, FNRI-DOST)
1. Cereal & Cereal products
2. Fish & Fish Products
3. Meat & Meat Products
4. Vegetables
5. Miscellaneous
 Some Generalizations
About Fatty Acids
1. Nearly all occurring fatty acids have an even
number of carbon atoms, most have between
12 and 20 in an unbranched chain.
2. The most abundant are palmitic, stearic and
oleic acids.
3. The essential fatty acids are linoleic, linolenic
and arachidonic.
4. In most unsaturated fatty acids, cis isomers
predominate; trans isomers are rare.
5. As the number of carbon atoms in a saturated
fatty acid increases, its melting point also
increases.

6. Unsaturated fatty acids have lower melting

points than their saturated counterparts.

7. The greater the degree of unsaturation in a

fatty acid, the lower the melting point.
(The presence of the double bond lowers the
melting point.)
 2. Triglycerides
◼ Also known as acylglycerides, acylglycerols or
triacylglycerols
◼ Fatty acid esters of glycerol;
◼ Natural fats (fats and oils)
◼ Depot or storage lipids in plants and animals
◼ General Formula:
O
||
O CH2-O-C-R1 When:
|| | R1 = R2 = R3 - simple
R2-C-O-CH R1 ≠ R2 ≠ R3 - mixed
|
CH2-O-C-R3
||
O
2. Triglycerides (Energy-Storage Lipid)
◼ With the notable exception of nerve cells,
human cells store small amounts of energy
providing materials:
◼ The most widespread energy storage

material -carbohydrate glycogen

◼ Present in small amounts

◼ Storage material is the triacylglycerols:

◼ Triacylglycerols are concentrated primarily in

special cells (adipocytes)

◼ Nearly filled with the material.
 2. Triglycerides
◼ Types of Triglycerides:
1. Simple Triacylglycerols: Three identical fatty acids
are esterified
◼ Naturally occurring simple triacylglycerols are rare

2. Mixed Triacylglycerols: A triester formed from the

esterification of glycerol with more than one kind of fatty
acid
◼ In nature mostly mixed triacylglycerols are found

and are different even from the same source

depending on the feed, e.g., corn, peanut and
wheat -fed cows have different triacylglycerols
 2. Triglycerides
Difference Between FATS and OILS
A. Physical State:
◼ Fats

◼ Predominantly Saturated
◼ Solids or semisolids at room temperature
◼ Oils:
◼ Predominantly unsaturated
◼ Liquids at room temperature
B. Source:
◼ Fats: Animal source and tasteless
◼ Oils: Plants and fish oil
◼ Pure oils and fats are colorless, odorless
 2. Triglycerides
Dietary Considerations and Triacylglycerols

◼ Nations whose citizens have high dietary intakes of

fats and oils tend to have higher incidences of heart
disease and certain types of cancers

◼ Typical American diet contains too much fat and

therefore the Americans are being asked to reduce
their total dietary fat intake

◼ Other studies show that risk factor is more than

simply the total amount of triacylglycerols consumed
Reaction: Formation of Ester

H2-C-OH HO-CO-R1 H2-C-O-CO-R1

| |
H-C-OH + HO-CO-R2 H-C-O-CO-R2
| |
H2-C-OH HO-CO-R3 H2-C-O-CO-R3

Alcohol + Carboxylic acid → Ester

(glycerol)
 Examples of Simple Triglycerides

1. H2C-O-CO-C11H23 2. H2C-O-CO-C17H33
| |
H-C-O-CO-C11H23 H-C-O-CO-C17H33
| |
H2C-O-CO-C11H23 H2C-O-CO-C17H33

Trilaurin Triolein
 Examples of Mixed Triglycerides
1. H2C-O-CO-C15H31 2. H2C-O-CO-C17H29
| |
H-C-O-CO-C17H31 H-C-O-CO-C17H33
| |
H2C-O-CO-C13H27 H2C-O-CO-C17H33

1-palmito-2-linoleomyristin 1-linolenodiolein

Name the following:

3. H2C-O-CO-C17H31 4. H2C-O-CO-C17H33
| |
H-C-O-CO-C17H31 H-C-O-CO-C17H31
| |
H2C-O-CO-C13H27 H2C-O-CO-C15H31
Chemical Aspect
Hydrolysis

CH2-O-CO-C17H29 CH2-OH
| hydrolysis |
CH-O-CO-C17H33 CH-OH + C17H29COOH +
| a. enzyme |
CH2-O-CO-C17H33 lipase CH2-OH 2 C17H33COOH
b. acid/heat

glycerol fatty acids

Saponification

CH2-O-CO-C17H29 CH2-OH
| saponification |
CH-O-CO-C17H33 CH-OH + C17H29COONa +
| basic alkali, heat |
CH2-O-CO-C17H33 NaOH CH2-OH 2 C17H33COONa

glycerol soap
Soap
◼ A good emulsifying agent which contains both significantly polar
and nonpolar ends (amphiphatic molecule).
◼ Polar end reacts with water, nonpolar end reacts with oil
Catalytic Hydrogenation

1. C17H31COOH 2H2 C17H35COOH

catalysis

2. CH2-O-CO-C15H31 CH2-O-CO-C15H31
| |
CH-O-CO-C15H29 3H2 CH-O-CO-C15H31
| |
CH2-O-CO-C17H31 CH2-O-CO-C17H35

Catalyze only the R-group which does not satisfy

the formula: CnH2n+1
 Section 19.6
Chemical Reactions of Triacylglycerols
Hydrogenation
– Addition of hydrogen across double (=) bond - increases degree of
saturation
O
O
H2C O C H2C O C
O O
HC O C + 2H2
HC O C
O O
H2C O C
H2C O C

Oil Solid
– Many food products are produced by partial hydrogenation
of oils and fats
– Peanut oil + H2 → Peanut Butter
– Vegetable oil + H2 → Margarine Return to TOC

Copyright © Cengage Learning. All rights reserved 38

 Section 19.6
Chemical Reactions of Triacylglycerols
Oxidation
• Double bonds in triacylglycerols are subject to
oxidation with oxygen in air (an oxidizing agent )-
Leads to C=C breakage
• Remember that oxidation of alkenes may result into
two short chain molecules – an aldehydes or a
carboxylic acid:
– The aldehydes and/or carboxylic acids so produced often
have objectionable odors - fats and oils are said to be
rancid
– To avoid this unwanted oxidation process antioxidants are
added as preservatives, e.g., Vitamin C and vitamin E are
good antioxidant preservatives. Return to TOC

Copyright © Cengage Learning. All rights reserved 39

3. Glycerol Phosphatides
◼ Phospholipids, membrane components
◼ Hydrolyzed to yield glycerol, fatty acids, phosphate
and an amino alcohol.
◼ (structure)
◼ The amino alcohol may be:
Choline: HO-CH2-CH2-N(CH3)3 → lecithins

Ethanolamine: HO-CH2-CH2-NH3+ → cephalins

Serine: HO-CH2-CH-NH3+ → phosphatidyl serine

|
COO-
 Section 19.7
Membrane Lipids: Phospholipids
• 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 and these lipid materials are
dominated by phospholipids.

• A phospholipid contains one or more fatty acids, a

phosphate group, a platform molecule (glycerol or
sphingosine) to which the fatty acid(s) and the
phosphate group are attached, and an alcohol that is
attached to the phosphate group. Return to TOC

Copyright © Cengage Learning. All rights reserved 41

4. Sphingomyelins
◼ Phospholipids, sphingolipids, membrane components
◼ Hydrolyzed to yield sphingosine, fatty acid, phosphate
and an amino alcohol
◼ Structure: amide linkage
fatty acid R-C=O
|
NH O
| ||
CH3-(CH2)12-CH=CH-CH-CH-CH2-O-P-O-N(CH3)3
| |
OH O- amino alcohol

sphingosine phosphate
 Section 19.7
Membrane Lipids: Phospholipids
Sphingophospholipids
• 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

• 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
Return to TOC

Copyright © Cengage Learning. All rights reserved 43

5. Glycolipids
◼ Cerebrosides, sphingolipids,
◼ Membrane components
◼ Hydrolyzed to yield sphingosine, fatty acid and
sugar
◼ Structure:
R-C=O
|
NH
|
CH3-(CH2)12-CH=CH-CH-CH-CH2-O-sugar
6. Steroids
◼ Derivatives of saturated tetracyclic hydrocarbons;
◼ Do not contain fatty acids;
◼ Not amphiphatic

A. Sterols – “parent steroid” →cholesterol

◼ An essential component of biological membrane

◼ Precursor for the biosynthesis of bile acids, steroid
hormones and vitamin D.
◼ C27H45OH
 Section 19.9
Membrane Lipids: Cholesterol

Cholesterol-Third major type of membrane lipid

• Lipids: Fused Rings
• Cholesterol: C27 steroid molecule
• A steroid is a lipid whose structure is based on a fused
ring system of three 6 carbon rings and one 5 carbon
ring.
• Important in human cell membranes, nerve tissue and
brain tissue
– Important in chemical synthesis: Hormones,
vitamins essential for life

Return to TOC

Copyright © Cengage Learning. All rights reserved 46

 Section 19.9
Membrane Lipids: Cholesterol

Cholesterol in Food
• 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: Lot of cholesterol
• Plant Food: No cholesterol

Return to TOC

Copyright © Cengage Learning. All rights reserved 47

 Section 19.10
Cell Membranes

Cholesterol
• Cholesterol molecules are also components of plasma membranes:
– Cholesterol helps regulate membrane fluidity – The fused ring
system does nor allow rotation of fatty acid tails in the vicinity
– Fits between fatty acid chains of the lipid bilayer: Make it rigid
– Cholesterol thus acts a membrane plasticizer

Return to TOC

Copyright © Cengage Learning. All rights reserved 48

B. Bile Acids

◼ Synthesized in the liver from cholesterol;

◼ Principal pathway for the elimination of cholesterol from the

body

◼ Emulsify fats in the intestines, aid digestion and absorption

of dietary fats;

◼ Example: cholic acid

C. Hormones
◼ Specific substances produced by endocrine glands of
higher animals which are secreted into the blood and
carried to all parts of the body where they regulate many
metabolic functions of the organisms.

1. Androgens – testosterone (male)

2. Estrogens – estradiol (female)
3. Progestogens – progesterone (female)
4. Mineralocorticoids – aldosterone, affects water and
electrolyte balance
5. Glucocorticoids – cortisol, affects carbohyrate and protein
metabolism
7. Prostaglandins
◼ Twenty (20)-carbon fatty acids synthesized in cell
membrane from unsaturated fatty acid like
arachidonic acid

◼ Biological effects:
Raise or lower blood pressure

Regulate gastric secretion

Cause inflammation of tissues

8. Fat-soluble Vitamins
A. Vitamin A (retinol)
◼ Site of the primary photochemical reaction in
vision
◼ β- carotene is a precursor

◼ Derived from isoprene:

CH2=C CH=CH2
|
CH3
B. Vitamin D (calciferol)

◼ Regulates calcium and phosphorus metabolism;

◼ Vitamin D3 is formed from cholesterol by the

action of UV radiation from the sun;

◼ Precursor: cholesterol
C. Vitamin E (tocopherol)

◼ An antioxidant;
◼ In rats, required for reproduction and prevention
of muscular dystrophy;
◼ Derived from isoprene

D. Vitamin K (koagulation)
◼ Has a regulatory function in blood clotting;

◼ Derived from isoprene

 9. Waxes
◼ Esters of long chain fatty alcohols and long chain
fatty acids (n = 17-33);

◼ Malleable solids which melt at only moderately

elevated temperatures found in insects and whales
and on the surfaces of most plants protective, water-
resistant coatings;

◼ Important cosmetically and medicinally;

◼ Example: beeswax, C15H31COOC30H61