Lipids

 Lipids known as fats provide a major

Biochemistry
way of storing chemical energy and
carbon atoms in the body.
 Fats insulate vital body organs,
providing protection from mechanical
shock and preventing excessive loss of
heat energy.
 Lipids
 Phospholipids, glycolipids, and

Biochemistry
cholesterol (a lipid) are the basic
components of cell membranes.
 Several cholesterol derivatives
function as chemical messengers
(hormones) within the body.
 FATTY ACID
CLASSIFICATION OF LIPIDS

Biochemistry
Based on Biochemical Function

Based on Hydrolysis Reaction

(Saponification)
CLASSIFICATION OF LIPIDS
Based on Biochemical Function

Biochemistry
1. Energy-storage Lipids
2. Membrane Lipids
3. Emulsification Lipids
4. Messenger Lipids
5. Protective-coating Lipids
CLASSIFICATION OF LIPIDS

Based on Hydrolysis Reaction

Biochemistry
(Saponification)

1. Saponifiable Lipids
2. Non-saponifiable Lipids
FATTY ACIDS
 A fatty acid is a naturally occurring monocarboxylic acid.
 Fatty acids are rarely found free in nature but rather occur as

Biochemistry
part of the structure of more complex lipid molecules.
 In terms of Saturation:
Saturated Fatty Acids
Unsaturated Fatty Acids
 In terms of carbon chain length:
Long-chain fatty acids (C12 to C26)
Medium-chain fatty acids (C8 and C10)
Short-chain fatty acids (C4 and C6)
FATTY ACIDS
Saturated Fatty Acid
Is a fatty acid with a carbon
chain in which all carbon–
carbon bonds are single bonds.
The structural formula for a
fatty acid is usually written in a
more condensed form than the
preceding structural formula.
Biochemistry

Saturated Fatty Acids

N
O
T
E
FATTY ACIDS

Monounsaturated F.A.
Is a fatty acid with a carbon
chain in which ONE CARBON–
CARBON DOUBLE BOND IS
PRESENT.
The first of these structures
correctly emphasizes that the
presence of a cis double bond in
the carbon chain puts a rigid 30
bend in the chain.
Classification Based on Configuration of Double Bond

 Naturally occurring fatty

acids generally contain cis
double bonds.
 Hydrogenation converts
some cis double bonds to
trans double bonds. Trans
fatty acids have effects on
blood chemistry similar to
those of saturated fatty
acids.
FATTY ACIDS
Polyunsaturated F.A.
Is a fatty acid with a carbon chain in
which TWO OR MORE CARBON–
CARBON DOUBLE BONDS ARE
PRESENT.
Up to six double bonds are found in
biochemically important PUFAs.
Classification Based on Location of
Double Bond (Omega 3 or Omega 6).
Unsaturated Fatty Acids
A numerically based shorthand system exists for
specifying key structural parameters for fatty acids.
Biochemistry

Unsaturated Fatty Acids

 (Δ) “DELTA NOTATION” always assumes a numbering
N system in which the carboxyl carbon atom is C-1 denoting
O double-bond locations .
 Several different “families” of unsaturated fatty acids
T exist. These family relationships become apparent when
E double-bond position is specified relative to the methyl
(non-carboxyl) end of the fatty acid carbon chain.
 Double-bond positioning determined in this manner is
denoted by using the Greek lowercase letter omega (ꙍ).
Biochemistry

Unsaturated Fatty Acids

N
O
T
E
Biochemistry

Unsaturated Fatty Acids

N
O
T
E
Biochemistry
Physical Properties of Fatty Acids
 Direct function of carbon chain length.
 SHORT-CHAIN FATTY ACIDS have a slight
Water
solubility in water.
Solubility  LONG-CHAIN FATTY ACIDS are essentially
insoluble in water.
 Are strongly influenced by both carbon chain
length and degree of unsaturation.
Melting
 ↑ Carbon chain length, ↑ Melting Point.
Points  Saturated fatty acids have higher melting
points than UNSATURATED FATTY ACIDS.
Biochemistry
Physical Properties of Fatty Acids
The MELTING
POINT of a fatty
acid depends on
the length of the
carbon chain and
on the number of
double bonds
present in the
carbon chain.
Biochemistry
Energy-Storage Lipids: Triacylglycerols
 Function within the body as energy-storage materials.
 Concentrated primarily in special cells (ADIPOCYTES).
 Adipose tissue containing these cells is found in various
parts of the body: under the skin, in the abdominal cavity,
in the mammary glands, and around various organs.
 More efficient at storing energy than is glycogen.
 These energy storage lipids are the most abundant type of
lipid present in the human body.
 Triacylglycerols are triesters; three ester functional groups
are present.
Biochemistry
Energy-Storage Lipids: Triacylglycerols
Biochemistry
Triacylglycerols
 Triacylglycerol is a lipid formed by esterification
of three fatty acids to a glycerol molecule
(RESIDUES).
 An older name that is still frequently used for a
triacylglycerol is TRIGLYCERIDE.
 A SIMPLE TRIACYLGLYCEROL is a triester formed
from the esterification of glycerol with three
identical fatty acid molecules.
 A MIXED TRIACYLGLYCEROL is a triester formed
from the esterification of glycerol with more than
one kind of fatty acid molecule.
Biochemistry
Triacylglycerols
Biochemistry

Triacylglycerols (Fats and Oils)

 Are naturally occurring mixtures of triacylglycerol
molecules in which many different kinds of
triacylglycerol molecules are present.
 A FAT is a triacylglycerol mixture that is a solid or a semi-
solid at room temperature (25 C).
 An OIL is a triacylglycerol mixture that is a liquid at room
temperature (25 C).
 Composition depends on both dietary and climatic
factors.
Biochemistry

Triacylglycerols (Fats and Oils)

FATS OILS
MONO- &POLYUNSATURATED
SATURATED FATTY ACIDS
FATTY ACIDS
Oils typically come from
Animal Fat
plants
Pure Fats and Pure Oils are colorless, odorless, and
tasteless.
Biochemistry
Essential Fatty Acids
 TWO ESSENTIAL FATTY ACIDS:
(1) Linoleic Acid (18:2) (OMEGA-6)
(2) Linolenic Acid (18:3) (OMEGA-3)
 Proper membrane structure and serve as starting materials
for the production of several nutritionally important.
 DEFICIENCY: Skin reddens and irritated
Infections
Dehydration
Liver abnormalities
Biochemistry
Essential Fatty Acids

ARACHIDONIC ACID (substances that help regulate blood pressure,

clotting, and several other important functions).

EPA and DHA are important constituents of the communication

membranes of the brain and are necessary for normal brain
development and also active in the retina of the eye.
Biochemistry
Chemical Reactions of Triacylglycerols

 Hydrolysis
 Saponification
 Hydrogenation
 Oxidation
Biochemistry
Chemical Reactions of Triacylglycerols
Hydrolysis
 REVERSE OF THE ESTERIFICATION REACTION
 Triacylglyercol hydrolysis requires the presence of an acid
or a base.
 Such hydrolysis requires the help of ENZYMES (Pancreas).
 COMPLETE HYDROLYSIS
 PARTIAL HYDROLYSIS
Biochemistry
Chemical Reactions of Triacylglycerols
Hydrolysis
Biochemistry
Chemical Reactions of Triacylglycerols
Hydrolysis
Biochemistry
Chemical Reactions of Triacylglycerols
Saponification
 A reaction carried out in an alkaline (basic) solution.

 For fats and oils, the products of saponification are

glycerol and fatty acid salts.

 The overall reaction of triacylglycerol saponification

can be thought of as occurring in two steps.
Biochemistry
Chemical Reactions of Triacylglycerols
Saponification
The FIRST STEP is the hydrolysis of the ester linkages:

The SECOND STEP involves a reaction between the fatty acid and
the base (usually NaOH) in the alkaline solution:
Biochemistry
Chemical Reactions of Triacylglycerols
Hydrogenation
 It involves hydrogen addition across carbon–carbon
multiple bonds, which increases the degree of saturation
as some double bonds are converted to single bonds.
Biochemistry
Chemical Reactions of Triacylglycerols
Oxidation
 The carbon–carbon double bonds present in the fatty acid
residues of a triacylglycerol are subject to oxidation with
molecular oxygen (from air) as the oxidizing agent.
Biochemistry
Membrane Lipids

 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; the rest is primarily protein.
 Three common types of lipids: Phospholipids
Sphingoglycolipids
Cholesterol
Biochemistry
Membrane Lipids: Phospholipids

 The most abundant type of

membrane lipid.
 A phospholipid 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.
Biochemistry
Membrane Lipids: Two Types of Phospholipids
Biochemistry
Membrane Lipids: Phospholipids
Biochemistry
Membrane Lipids: Phospholipids
Glycerophospholipids
 A lipid that contains two fatty acids and a phosphate group
esterified to a glycerol molecule and an alcohol esterified
to the phosphate group.
 The alcohol attached to the phosphate group in a
glycophospholipid is usually one of three amino alcohols:
CHOLINE, ETHANOLAMINE, or SERINE.
Biochemistry
Membrane Lipids: Phospholipids
Glycerophospholipids

 Phosphatidylcholines (Lecithins), Phosphatidylethanolamines, and

Phosphatidylserines (Cephalins).
 Fatty Acid, Glycerol, P04 portions of a glycerophospholipid
structure constitute a PHOSPHATIDYL GROUP.
Biochemistry
Membrane Lipids: Phospholipids
Glycerophospholipids
 Similar to triacylglycerols.
 Components of cell membranes.
 Membrane lipids have polarity (Structures).
 A phosphatidylcholine containing stearic and oleic acids will
be used to illustrate this additional feature.
 Lecithins present in cell membranes.
 Cephalins are important in blood clotting.
Biochemistry
Membrane Lipids: Phospholipids
Glycerophospholipids: Phosphatidylcholines
Biochemistry
Membrane Lipids: Phospholipids
Sphingophospholipids
 A lipid that contains one fatty acid
and one phosphate group
attached to a sphingosine
molecule and an alcohol attached
to the PO4 group.
 Found in all cell membranes and
are important structural
components of the myelin
sheath.
Biochemistry
Membrane Lipids: Phospholipids
Sphingophospholipids

All phospholipids derived from sphingosine have:

1. Fatty acid attached to the sphingosine -NH2 group via an amide
linkage.
2. Phosphate group attached to the sphingosine terminal -OH group via an
ester linkage.
3. An additional alcohol esterified to the phosphate group.
Biochemistry

Sphingophospholipids in which the alcohol esterified to the

phosphate group is choline are called SPHINGOMYELINS.
Biochemistry
Membrane Lipids: Sphingoglycolipids

 The second of the three

major types of membrane
lipids is sphingoglycolipids.
 A sphingoglycolipid is a lipid
that contains both a fatty
acid and a carbohydrate
component attached to a
sphingosine molecule.
Biochemistry
Membrane Lipids: Sphingoglycolipids
 CEREBROSIDES (Simplest
Sphingoglycolipids), contain
a single monosaccharide
unit—either glucose or
galactose.
 GANGLIOSIDES (Complex
Sphingoglycolipids), contain
a branched chain of up to
seven monosaccharide
residues.
Biochemistry
Biochemistry
Membrane Lipids: Cholesterol
 Cholesterol is a
steroid.
 A steroid is a lipid
whose structure is
based on a fused
ring system that
involves three 6-
membered rings
and one 5-
membered ring.
Biochemistry
Membrane Lipids: Cholesterol
 Cholesterol’s structure differs markedly from that of
other membrane lipids in that:
N
(1) There are NO FATTY ACID residues present.
O (2) Neither glycerol nor sphingosine is present as
T the platform molecule.
E  Location of double bonds within the fused-ring system and the
nature and location of substituents distinguish one steroid from
another.
 Most steroids have an oxygen functional group (=O or -OH) at
carbon 3 and some kind of side chain at carbon 17.
Biochemistry
Membrane Lipids: Cholesterol
 Many also have a double bond from carbon 5 to either
N carbon 4 or carbon 6.
O  Cholesterol is a C27 steroid molecule that is a component
of cell membranes and a precursor for other steroid-
T based lipids.
E  It is the most abundant steroid in the human body.
 The -ol ending in the name cholesterol conveys the
information that an alcohol functional group is present in
this molecule; it is located on carbon 3 of the steroid
nucleus.
Biochemistry
Membrane Lipids: Cholesterol
 Cholesterol has methyl group attachments at carbons 10
N and 13, a carbon–carbon double bond between carbons
O 5 and 6, and an eight-carbon branched side chain at
carbon 17.
T  The “head and two tails” arrangement found in other
E membrane lipids is not present.
 The lack of a large polar head group causes cholesterol
to have limited water solubility.
Biochemistry
Membrane Lipids: Cholesterol

 Cholesterol is found in human cell membranes (up to

25% by mass), in nerve tissue, in brain tissue (about
10% by dry mass), and in virtually all fluids.
 Typically, 800–1000 mg are biosynthesized each day
by the Liver.
 Insoluble to H20.
 Plasma Lipoproteins: LDL “Bad Cholesterol”
HDL “Good Cholesterol”
Biochemistry

Cell Membranes
 A cell membrane is a lipid-based structure that separates
a cell’s aqueous-based interior from the aqueous
environment surrounding the cell.
 Key structural basis for a cell membrane:
(1) Insoluble nature of membrane lipids in H20
(2) The “head and two tails” structure
 Cell membranes are also commonly called PLASMA
MEMBRANES.
Biochemistry

Cell Membranes
Biochemistry

Cell Membranes
A 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.
Biochemistry

Cell Membranes
 A lipid bilayer is held together by intermolecular
interactions, not by covalent bonds.
 LIPIDS: Cholesterol,
Glycerophospholipids,
Sphingoglycolipids
 PROTEINS: Integral Membrane Protein
Peripheral Membrane Protein
 CARBOHYDRATES: Glycoproteins
Glycolipids
Biochemistry

Cell Membranes
COMPONENTS OF CELL MEMBRANE
Cholesterol Regulate membrane rigidity.
Integral Membrane A membrane protein that penetrates the
Protein cell membrane.
A non-penetrating membrane protein
Peripheral
located on the surface of the cell
Membrane Protein
membrane.
Carbohydrates Surface marker.
Biochemistry
Biochemistry
Transport Across Cell Membranes
FACILITATED
PASSIVE TRANSPORT ACTIVE TRANSPORT
TRANSPORT
A transport process in
A transport process in
which a substance A transport process in
which a substance
moves across a cell which a substance
moves across a cell
membrane, with the moves across a cell
membrane by diffusion
aid of membrane membrane, with the
from a region of higher
proteins, from a region aid of membrane
concentration to a
of higher concentration proteins, against a
region of lower
to a region of lower concentration gradient
concentration without
concentration without with the expenditure of
the expenditure of any
the expenditure of cellular energy.
cellular energy.
cellular energy.
Biochemistry

Cell Membranes

Transport Across Cell Membranes

PASSIVE FACILITATED ACTIVE
TRANSPORT TRANSPORT TRANSPORT
O2, N2, H2O, urea, Glucose, chloride Sodium, potassium,
and ethanol ion, and and hydronium
bicarbonate ions
Biochemistry

Cell Membranes
Transport Across Cell Membranes
Biochemistry

Emulsification Lipids: Bile Acids

 An emulsifier is a substance that can disperse and stabilize
water-insoluble substances as colloidal particles in an
aqueous solution.
 BILE ACID is a cholesterol derivative that functions as a lipid-
emulsifying agent in the aqueous environment of the
digestive tract.
 From one-third to one-half of the daily production of
cholesterol by the LIVER.
 Bile is a fluid containing emulsifying agents that is secreted by
the liver, stored in the GALLBLADDER, and released into the
SMALL INTESTINE during digestion.
Biochemistry

Emulsification Lipids: Bile Acids

Biochemistry

Emulsification Lipids: Bile Acids

 Bile is 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.
Biochemistry

Emulsification Lipids: Bile Acids

Biochemistry

Messenger Lipids
 STEROID HORMONES and
EICOSANOIDS are two large
families of lipids that have
messenger functions.
 Steroid hormones, which
are cholesterol derivatives.
 Eicosanoids, which are fatty
acid derivatives.
Biochemistry

Messenger Lipids: STEROID HORMONES

 A hormone is a biochemical substance, produced
by a ductless gland, that has a messenger
function.
 Hormones serve as a means of communication
between various tissues.
 There are two major classes of steroid hormones:
(1) Sex Hormones
(2) Adrenocorticoid Hormones
Biochemistry

Messenger Lipids: STEROID HORMONES

The SEX HORMONES can be classified into three major groups:
1.Estrogens—the female sex hormones
2.Androgens—the male sex hormones
3.Progestin—the pregnancy hormones

There are two types of ADRENOCORTICOID HORMONES.

1.Mineralocorticoids control the balance of Na+ and K+ ions in
cells and body fluids.
2.Glucocorticoids control glucose metabolism and counteract
infl ammation.
Biochemistry

Messenger Lipids: STEROID HORMONES

 Are synthesized in the ovaries and adrenal
cortex
 Responsible for the development of female
secondary sex characteristics at the onset of
Estrogens
puberty and for regulation of the menstrual
cycle.
 They also stimulate the development of the
mammary glands during pregnancy.
Biochemistry

Messenger Lipids: STEROID HORMONES

 Are synthesized in the testes and adrenal
cortex and promote the development of male
Androgens
secondary sex characteristics.
 They also promote muscle growth.
 Are synthesized in the ovaries and the placenta
and prepare the lining of the uterus for
Progestin
implantation of the fertilized ovum.
 They also suppress ovulation.
Major Mineralocorticoid is Aldosterone.
Major Glucocorticoid is Cortisol (Hydrocortisone).
 CORTEX STEROIDOGENESIS
Biochemistry
Biochemistry
Biochemistry

Messenger Lipids: EICOSANOIDS

 Is an oxygenated C20 fatty acid derivative that functions as a
messenger lipid.
 The metabolic precursor for most eicosanoids is arachidonic
acid, the 20:4 fatty acid.
 Almost all cells, except red blood cells, produce eicosanoids.
 Hormone-like molecules.
 They exert their effects in the tissues where they are
synthesized.
 Short life-span (seconds).
 Residues are eliminated in the urine.
Biochemistry

Messenger Lipids: EICOSANOIDS

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.
Biochemistry

Messenger Lipids: EICOSANOIDS

 A messenger lipid that is a C20-fatty-acid
derivative that contains a CYCLOPENTANE RING
and oxygen-containing functional groups.
 Raising body temperature.
 Inhibiting the secretion of gastric juices,
Prostaglandins increasing the secretion of a protective mucus
layer into the stomach.
 Relaxing and contracting smooth muscle.
 Directing water and electrolyte balance,
 Intensifying pain.
 Enhancing inflammation responses.
Biochemistry

Messenger Lipids: EICOSANOIDS

 A messenger lipid that is a C20-fatty-acid
derivative that contains a CYCLIC ETHER RING
and oxygen-containing functional groups.
Thromboxanes  Promote the formation of blood clots.
 Thromboxanes are produced by blood platelets
and promote platelet aggregation.
 A messenger lipid that is a C20-fatty-acid
derivative that contains three conjugated double
Leukotrienes bonds and hydroxy groups.
 Found in leukocytes.
 Various inflammatory and hypersensitivity.
Types of Lipids in Terms of How They Function
Types of Lipids in Terms of How They Function
Types of Lipids in Terms of How They Function
Biochemistry