THE CHEMICAL NATURE OF

LIPIDS
 LIPIDS
At the end of this session you should be able to
• Define lipids
• Classify lipids on the basis of structure
• Enlist functions of lipids and dietary fats
• State the energy content of 1 gm of fat
• Differentiate between
Saturated and unsaturated fatty acids
Cis and trans fatty acids
Omega 3 and omega 6 fatty acids
Essential and non-essential fatty acids
 DEFINITION
Heterogeneous group of organic
compounds which are generally
insoluble in water, but soluble in
organic solvents such as ether,
benzene, and chloroform-methanol.
 FATTY ACIDS

• Monocarboxylic
• Usually straight-chain having even number (2-26)
of carbon atoms
• Most common are C12-C22
• Short-Chain (2-4 C atoms)
• Medium- Chain (6-10 C atoms)
• Long-Chain (12-20 C atoms)
• Very long-Chain (C22 and above)
 STRUCTURAL CLASSIFICATION
1. Simple Lipids
a. Fats & Oils (Triglycerides) - Fatty acid esters with
glycerol
 STRUCTURAL CLASSIFICATION

Simple Lipids

b. Waxes - Fatty acid esters of long chain

monohydroxy alcohols
Glycerophospholipids
 STRUCTURAL CLASSIFICATION contd.
2. Complex Lipids
a. Phospholipids (contain phosphorous)
Glycerophospholipids
Glycerol + FA + phosphate + Polar head group
Sphingophospholipids
Sphingosine + FA + phosphate + choline
b. Glycolipids
Sphingosine + FA + Carbohydrate
c. Other Complex Lipids
Sulfolipids, Aminolipids, Lipoproteins
STRUCTURAL CLASSIFICATION contd.
3. PRECURSOR & DERIVED LIPIDS
formed by the metabolic transformation of
fatty acids.
Fat Soluble Vitamins, Steroids (Cholesterol,
Steroid hormones, Bile Salts), ketone
bodies, fatty aldehydes
CHOLINE
 BILE SALTS
C D
A B
 FUNCTIONS
• FATTY ACIDS
Metabolic fuel; component of several other classes
of lipids
• TRIGLYCERIDES
Main storage form of fatty acids and chemical
energy, insulation
• PHOSPHOLIPIDS
Components of membranes; sources of arachidonic
acid, inositol trisphosphate (IP3), and diglyceride
(DAG) for signal transduction, lung surfactant etc
• SPHINGOLIPIDS
Components of membranes; Imp. in signal
transduction
 FUNCTIONS (contd.)
• CHOLESTEROL
Component of membranes; precursor of bile salts,
Vit. D and steroid hormones
• BILE SALTS
Lipid digestion and absorption; main product of
cholesterol metabolism
• STEROID HORMONES
Intracellular signals that regulate gene expression
in target cells
 FUNCTIONS (Contd.)
• EICOSANOIDS (Prostaglandins, Thromboxanes,
Leukotrienes)
Regulators of physiological functions. Local
hormones
• VITAMINS (A, D, E, K)
Vision; calcium metabolism; antioxidants; blood
coagulation
• KETONE BODIES
Metabolic fuel
 FUNCTIONS OF DIETARY FATS
1. Concentrated sources of energy
9 Kcal/g vs.4 Kcal/g for carbohydrates and
proteins
2. Carriers of fat-soluble vitamins A,D,E,K
3. Sources of Essential Fatty Acids
Linoleic acid 18:2 n-6 (w6)
α- Linolenic acid 18:3 n-3(w 3)
4. Satiety value
5. Impart taste and flavor to foods
 Saturated Fatty Acids
Most commonly occurring are
• Myristic Acid (14:0)
• Palmitic Acid (16:0)
• Stearic Acid (18:0)

Since the carboxylic group is ionized at

physiological pH, they exist as carboxylate ion
e.g. palmitate
CH3 (CH2)14-COOH CH3(CH2)14-COO- + H+
pKa 4.8
 UNSATURATED FATTY ACIDS
Contain carbon to carbon double bonds.
MUFA
• Mono-unsaturated (1 double bond)
OLEIC ACID 18:1
PUFA
• Polyunsaturated (> 1 double bond )
LINOLEIC ACID, 18:2
LINOLENIC ACID, 18:3
ARACHIDONIC ACID 20:4
 MELTING POINT OF FATTY ACIDS

Depends on the structure of the fatty acid

• Increases with no. of carbons
• Decreases with degree of unsaturation

A TAG with
• three saturated fatty acids is solid at room
temperature,
• two unsaturated fatty acids is liquid
POSITIONAL AND GEOMETRIC ISOMERISM IN
UNSATURATED FATTY ACIDS
Position and geometric configuration of double
bond (cis or trans) may vary
• cis - mostly present in naturally occurring
fatty acids
• Trans – minute quantities from meat and
dairy products. They are produced during
hydrogenation of fish and vegetable oil
POSITIONAL AND GEOMETRIC ISOMERISM
IN FATTY ACIDS
POSITIONAL AND GEOMETRIC ISOMERISM IN
UNSATURATED FATTY ACIDS (CONTD)
 POSITIONAL AND GEOMETRIC ISOMERISM IN
UNSATURATED FATTY ACIDS (CONTD)

• Melting points of fatty acids with cis

double bonds are lower than the
corresponding trans fatty acids

MELTING POINT
Stearic acid 18:0 69oC
Elaidic acid 18:1 trans ∆9 44oC
Oleic acid 18:1cis ∆9 13oC
and trans
Current concerns about trans fatty
acid intake and attempt to ↓ their
dietary intake
 Saturated (?) and trans fats are
associated with an increased risk of
coronary heart disease

Trans Fatty acids, unlike Cis isomers,

increase plasma cholesterol and LDL levels
 NOMENCLATURE
Fatty acids
Common (trivial) names
Systematic names (derives from parent hydrocarbons)
• Saturated fatty acids end with anoate
Palmitate is hexadecanoate

• Unsaturated fatty acids end with enoate

The position of the double bond (counting from
the –COOH toward CH3 group) and its geometric
configuration (cis or trans)
The palmitoeate will be called cis- ∆9 –hexadecenoate.
 NOMENCLATURE (CONTD)
There are 2 systems to number the position
of carbon to carbon double bonds
1. The ∆ system, according to which one
starts counting from carboxyl carbon as
C1 and goes toward the methyl carbon
e.g. Palmitoleate will be called 16:1 ∆9

C O C O
CH3
O
ω carbon or O
nth carbon 10 9
10 9
 NOMENCLATURE (CONTD)
2. The ω- (or n- ) system which starts counting
from the CH3 carbon as C1. The position of the
first double bond is indicated
e.g. palmitoleate will be 16: 1 ω-7 (n-7)

1
C O
CH3
ω carbon O
or nth
carbon 7 8
 ESSENTIAL FATTY ACIDS
These fatty acids cannot be synthesized by
the human body and therefore have to be
provided in the diet.
• Linoleate (linoleic acid)
18:2 ∆9,12 or 18 :2 ω -6 (n-6)
• Linolenate (linolenic acid)
18 :3 ∆9,12 ,15 or 18:3 ω-3 (n-3)
Insufficient amounts in the diet result in
EFA Deficiency
 Other Important PUFA’S
• Arachidonic Acid 20:4 ω -6
Precursor of eicosanoids
• Eicosapentaenoic Acid 20:5 ω -3
Present in fish oils
• Docosahexaenoic acid22:6 ω -3
Present in fish oils
Linolenic acid
 Vignette 1
Introduction: A 2 year old boy.
Presenting complaint: Chronic productive cough not responding to
antibiotics.
Medical history: Abdominal distention, failure to pass stool, and
vomiting (emesis) as an infant. He continues to have bulky, foul-
smelling stools.
Family history: Several relatives with chronic lung and “stomach”
problems, and some died at a young age.
Examination: Ill appearing, slender male in moderate distress. No
fever. No diarrhea. Desquamating skin lesions present on his legs. The
lung exam reveals poor air movement in the base of lungs bilateral and
a coarse rattling sound (crepitating) throughout both lung fields.
Investigations: Positive chloride sweat test.
Diagnosis: Cystic fibrosis (CF).
Genetic analysis: DNA analysis reveals the presence of the deltaF508
mutation in the CFTR gene (deletion of phenylalanine at position 508 of
the CFTR protein).
The End!