Biochemistry for medlabsci FATTY ACIDS

Handout- Week 4 – BSMT-2A1-4

Lipids
§ Lipids known as fats provide a major 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.
§ Phospholipids, glycolipids, and cholesterol (a lipid)
are the basic components of cell membranes.
§ Several cholesterol derivatives function as chemical
messengers (hormones) within the body.
§ FATTY ACID Classification Based on Configuration of
Double Bond
CLASSIFICATION OF LIPIDS § Naturally occurring fatty acids
generally contain cis double bonds.
Based on Biochemical Function § Hydrogenation converts some cis
Based on Hydrolysis Reaction (Saponification) double bonds to trans double bonds. Trans
fatty acids have effects on blood chemistry
similar to those of saturated fatty acids.
Based on Biochemical Function
1. Energy-storage Lipids FATTY ACIDS
2. Membrane Lipids
3. Emulsification Lipids
4. Messenger Lipids
5. Protective-coating Lipids

Based on Hydrolysis Reaction (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 Unsaturated Fatty Acids
occur as part of the structure of more complex lipid A numerically based shorthand system exists for
molecules. specifying key structural parameters for fatty acids.
§ 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)
Unsaturated Fatty Acids
§ (Δ) “DELTA NOTATION” always assumes a numbering
system in which the carboxyl carbon atom is C-1
denoting double-bond locations .
§ Several different “families” of unsaturated fatty acids
exist. These family relationships become apparent when
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).

Saturated Fatty Acids

 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.

Triacylglycerols (Fats and Oils)

§ Are naturally occurring mixtures of triacylglycerol

molecules in which many different kinds of triacylglycerol
molecules are present.
Physical Properties of Fatty Acids § 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.

The MELTING
POINT of a fatty acid
depends on the length of
the carbon chain and on
Essential Fatty Acids
the number of double
§ TWO ESSENTIAL FATTY ACIDS:
bonds present in the
(1) Linoleic Acid (18:2) (OMEGA-6)
carbon chain.
(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
Energy-Storage Lipids: Triacylglycerols
• Dehydration
§ Function within the body as energy-storage materials.
§ Concentrated primarily in special cells (ADIPOCYTES). • Liver abnormalities
§ 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.
Chemical Reactions of Triacylglycerols Hydrogenation
§ Hydrolysis § It involves hydrogen addition across carbon–carbon
§ Saponification multiple bonds, which increases the degree of saturation
§ Hydrogenation as some double bonds are converted to single bonds.
§ Oxidation

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.

Hydrolysis

§ REVERSE OF THE ESTERIFICATION REACTION

§ Triacylglyercol hydrolysis requires the presence of an
acid or a base.
§ Such hydrolysis requires the help of ENZYMES Membrane Lipids
(Pancreas). § All cells are surrounded by a membrane that confines
§ COMPLETE HYDROLYSIS their contents.
§ PARTIAL HYDROLYSIS § 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

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.

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.

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:

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.
 Membrane Lipids:
Sphingoglycolipids

§ The second of the

§ Phosphatidylcholines (Lecithins), three major types of
Phosphatidylethanolamines, and Phosphatidylserines membrane lipids is
(Cephalins). sphingoglycolipids.
§ Fatty Acid, Glycerol, P04 portions of a § A sphingoglycolipid is
glycerophospholipid structure constitute a a lipid that contains both a
PHOSPHATIDYL GROUP. fatty acid and a
carbohydrate component
§ Similar to triacylglycerols. attached to a sphingosine
§ Components of cell membranes. molecule.
§ Membrane lipids have polarity (Structures).
§ A phosphatidylcholine containing stearic and oleic acids § CEREBROSIDES (Simplest
will be used to illustrate this additional feature. Sphingoglycolipids), contain
§ Lecithins present in cell membranes. a single monosaccharide
§ Cephalins are important in blood clotting. unit—either glucose or
galactose.
Glycerophospholipids: Phosphatidylcholines § GANGLIOSIDES (Complex
Sphingoglycolipids), contain
a branched chain of up to
seven monosaccharide
residues.

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 Membrane Lipids:
components of the myelin Cholesterol
sheath. § 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.

Membrane Lipids: Cholesterol

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.
Sphingophospholipids in which the alcohol esterified to the
phosphate group is choline are called SPHINGOMYELINS.
§ Cholesterol’s structure differs markedly from that of other
membrane lipids in that:
(1) There are NO FATTY ACID residues present.
(2) Neither glycerol nor sphingosine is present
as the platform molecule.
§ 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.
§ Many also have a double bond from carbon 5 to either
carbon 4 or carbon 6.
§ Cholesterol is a C27 steroid molecule that is a
component of cell membranes and a precursor for
other steroid- based lipids.
§ 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.
 § Cholesterol has methyl group attachments at carbons 10
and 13, a carbon–carbon double bond between carbons
5 and 6, and an eight-carbon branched side chain at
carbon 17.
§ The “head and two tails” arrangement found in other
membrane lipids is not present.
§ The lack of a large polar head group causes
cholesterol to have limited water solubility.
§ 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”
Transport Across Cell Membranes
§ HDL “Good Cholesterol”

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.

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.

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.
Emulsification Lipids: Bile Acids CORTEX STEROIDOGENESIS
§ 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.

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.

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

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
Messenger Lipids: EICOSANOIDS
counteract infl ammation.
§ 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.

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.
Types of Lipids in Terms of How They Function