Chapter 2 Lipids • Triacylglycerol – are carboxylic acid are

carboxylic acids triesters glycerols. They are a

Objectives: major source of biochemical energy.
• Structure and classification of lipids • Glycerophospholipids – triesters glycerols that
• Types of Fatty Acids contain charged phosphate diesters. They help
• Physical Properties of Fatty Acids to control the flow of molecules into and out of
• Energy-Storage Lipids: Triacylglycerol cells.
• Dietary Considerations and Triacylglycerol • Sphingomyelins – amides derived from an
amino alcohol, also contain charged phosphate
Lipids are naturally occurring molecules are naturally group. They are essential to the structure of cell
occurring molecules from plants or animals that are membranes.
soluble in nonpolar organic solvents. • Glycolipids –amides derived from sphingosine,
contain polar carbohydrate groups. On the cell
CHARACTERISTICS OF LIPIDS surface, they connect with by intracellular
1. Lipids are mostly hydrophobic - they don't mix well messenger
with water.
2. They are made up of mostly C-H bonds LIPIDS THAT ARE NOT ESTERS OR AMIDES:
(Hydrocarbons) • Steroids – They performs various functions such
3. Useful for long term energy storage as hormones and contributes to the structure of
4. Make up the membranes of cells cell membranes.
5. Provide thermal insulation and protection • Eicosanoids – They are carboxylic acids that are
a special type of intracellular chemical
STRUCTURE AND CLASSIFICATION OF LIPIDS messengers.
Lipids are organic compounds that are found in
living organisms that are soluble in non-polar organic CLASSIFICATION OF LIPIDS
solvents. • Lipids are divided into:
Unlike the other types of compounds, we’ve Saponifiable lipids — contain esters, which can
seen so far, there are no characteristic functional undergo saponification (hydrolysis under basic
groups in lipids that indicate their structure. conditions) (waxes, triacylglycerols, phospholipids,
sphingoglycolipids)
A lot of structural variety is represented by lipids. Nonsaponifiable lipids — do not contain ester groups,
They are typically: and cannot be saponified (cholesterol, steroids, bile
- insoluble in H2O acids and eicosanoids)
- soluble in NP • Saponifiable lipids can also be divided into groups:
solvents Simple lipids — contain two types of components (a
fatty acid and an alcohol)
Complex lipids — contain more than two components
(fatty acids, an alcohol, and other components)

TYPES OF FATTY ACIDS

• Fatty acids is a naturally occurring
LIPIDS CATEGORIES ( based on function ) monocarboxylic acid because of the pathway by
• Energy Storage –Triacylglycerols (fats) which they are biosynthesized, fatty acids nearly
•Membrane structure –Phospholipids, always contain an even number of carbon
Sphingoglycolipids, and cholesterol atoms and have a carbon chain that is
• Emulsification–Bile acids unbranched. In terms of carbon chain length,
• Messenger molecules–Steroid hormones; eicosanoids fatty acids are characterized as long-chain fatty
• Protective coating –Biological waxes acids (C12 to C26), medium-chain fatty acids (C8
and C10), or short-chain fatty acids (C4 and C6).
LIPIDS THAT ARE ESTER OR AMIDES OF FATTY ACIDS:
• Waxes – are carboxylic acids ester where both R • Fatty acids are rarely found free in nature but
groups are long straight hydrocarbon chain. rather occur as part of the structure of more
Performs external protective functions. complex lipid molecules.
SATURATED AND UNSATURATED FATTY ACIDS
 The carbon chain of a fatty acid may or may not UNSATURATED FATTY ACIDS AND DOUBLE-BOND
contain carbon-carbon double bonds. On the basis of POSITION
this consideration, fatty acids are classified as saturated • A numerically based shorthand system exists for
fatty acids (SFAs), fatty acids (MUFAs), or specifying key structural parameters for fatty
polyunsaturated fatty acids (PUFA monounsaturated). acids.
• Saturated fatty acids is a fatty acids with
carbon chain in which all carbon-carbon bonds
are single bonds. The structural formula for the
16- carbon SFA is
• Omega-3 fatty acids is an unsaturated fatty
acid with its endmost double bond three carbon
atoms away from its methyl end. An example of
an omega-3 fatty acid is

• The structural formula for a fatty acid is usually

written in a more condensed form than the • Omega-6 fatty acid is unsaturated fatty acid
preceding structural formula < Two alternative with its endmost double bond six carbon atoms
structural notations for palmitic acid are away from its methyl end.
The following three acids all belong to the
omega-6 fatty acid family:

and

• Monounsaturated fatty acids is a fatty acid PHYSICAL PROPERTIES OF FATTY ACIDS

with a carbon chain in which one carbon-carbon Water solubility for fatty acids is a direct function of
double bond is present. In biochemically carbon chain length.
important MUFAs, the configuration about the • Solubility decreases as carbon chain length
double bond is nearly always cis > Different increases.
ways of depicting the structure of a MUFA • Short-chain fatty acids have a slight solubility in
follow. water.
Melting points for fatty acids are strongly influenced by
both carbon chain length and degree of unsaturation
(number of double bonds present).

• Polyunsaturated fatty acid is a fatty acid with a

carbon chain in which two or more carbon- Melting point increases with increasing carbon chain
carbon double bond s are present. Up to six length.
double bonds are found in biochemically • Greater surface area increases intermolecular
important PUFAs. attractions.
• Fatty acids are nearly always referred to using
their common names, IUPAC names for fatty
acids, although easily constructed, are usually
quite long. These two types of name for 18-
carbon PUHA containing cis double bonds in the
9 and 12 positions are follows:
Melting point decreases a agree of unsaturation
(number of double bonds) increases.
• The number of bends in a fatty acids chain
increases as the number of double bonds
increases,
• Less efficient packing
• Fewer intermolecular interactions 2 GENERAL WAYS TO PRESENT THE STRUCTURE OF
• Long – chain saturated fatty acids tend to be TRIACYLGLYCEROL ARE:
solids at room temperature.
• Unsaturated ones are liquids.

1. Block Diagram- shows 4 sub units (building blocks)

present in the structure.
2. General Function Formula- shows the three ester
linkages present in triacylglycerol.

• Formally defined, Triacylglycerol is a lipid

formed by esterification of three fatty acids to
glycerol molecule.
• Within the name of Triacylglycerol is the term
acyl group (is the portion of a carboxylic acid
that remains after the –OH group is removed
from carboxyl carbon atom.

• Triglyceride - older name of triacylglycerol.

ENERGY-STORAGE LIPIDS: TRIACYLGLYCEROL Simple triacylglycerol
Triacylglycerol • is triester formed from esterification of glycerol
• also known as triglycerides, are the simplest with three identical fatty acid molecules.
lipids formed by fatty acids. It is made up of Mixed triacylglycerol
three fatty acids ester linked to a single glycerol. • is triester formed from esterification of glycerol
• stored as fat droplets in large amounts in with more than one kind of fatty acid molecule
vertebrate fat cells, and in plants as oils in the Most biochemically important triacylglycerol are mixed
seeds.  triacylglycerol
• Much more efficient at storing energy than is
glycogen because large quantities of them can
be packed into very small volume.
• Most abundant type of lipid present in the
human body.
• In terms of functional groups present,
triacylglycerol are triesters.
• Triesters- 3 ester functional groups are present.
• Ester- a compound produced from the reaction
of an alcohol with a carboxylic acid.
• The alcohol involved in triacylglycerol formation
is always a glycerol, a 3 carbon alcohol with 3
hydroxyl groups.
• Fatty acids are the carboxylic acids involved in
triacylglycerol formation. In the esterification
reaction producing a triacylglycerol, a single
molecule of glycerol reacts with three fatty acid
molecules, each of the 3 hydroxyl groups
present is esterified.
Fats and oil Cold-water Fish
• are naturally occurring mixtures of • Also called fatty fish because of the extra
triacylglycerol molecules in which many amounts of fat they have for insulation against
different kinds of triacylglycerol molecules are the cold contain more omega-3 acids.
present Warm-water fish
How do they differ? • Do not appear to offer as great a positive effect
• In their physical state of room temperature. on heart health as do their “fatter”
Fats- solid or semi-solid at a room temperature of 25C. counterparts.
- obtain from animal sources. Essential Fatty Acids
Oils- liquid, at room temperature of 25 C. • Is a fatty acid needed in the human body that
- obtain from plant sources. must be obtained from dietary sources because
it cannot be synthesized within the body, in
adequate amounts from other substances.
Essential Fatty Acids
1. Linoleic acid (18:2)- primary member of omega-
3
- maintain a certain level of membrane fluidity
FAT of the transdermal water barrier of the epidermis.
- the starting material for the biosynthesis of
arachidonic
2. Linolenic acid (18:3)- primary member of omega-6
-reduced inflammation and prevention of
certain chronic diseases.
- the starting material for the biosynthesis of 2
additional omega-3 acids
• EPA (eicosapentaenoic) and DHA
(docosahexaenoic acid) are important
OIL constituents of the communication membranes
of the brain and are necessary for normal brain
development and are also active in the retina of
the eye.
Fat Substitutes (Artificial Fats)
• Substances that replicate the tastes, texture
and cooking properties of fats but are
themselves not lipids.
• When this 2 are missing from the diet, the skin
reddens and become irritated, infection and
dehydration, and liver may develop
abnormalities.
DIETARY CONSIDERATIONS AND TRIACYLGLYCEROL Triglycerides – Fats & Oils
“Good Fats” Versus “Bad Fats” 1. Predominate form of fat in foods
The term fat is used as a substitute for the term and major storage form of fat in
of triacylglycerol. Thus, fat can be either fat or and oil. the body
Saturated Fats 2. Structure – composed of 3 fatty
• are bad fats acids + glycerol
• Can increased heart disease risk
Monounsaturated Fats CHEMICAL PROPERTIES OF TRIACYLGLYCEROL
• are good fats The CHEMICAL REACTIONS of triacylglycerols are similar
• Reduce heart disease and breast cancer risk to those of alkenes and esters.
• Helps reduce the stickiness of blood platelets • In hydrolysis, ester bonds are split by water in
Polyunsaturated Fats the presence of an acid, a base, or an enzyme.
• both good and bad fats • Is the reverse of the esterification reaction
• Reduce heart disease risk but promote the risk • Requires the presence of an acid or base
of certain types of cancers. • In the human body, hydrolysis is catalyzed by
enzymes during digestion .
OMEGA-3 AND OMEGA-6 FATTY ACIDS
• Occurs stepwise
• Omega-6 is a fatty acids from plant oil
• Omega-3 is a fatty acids from fishes • Outer fatty acids are removed first, leaving a
• Several studies now confirmed that benefits can monoacylglycerol (partial hydrolysis)
be derived from eating several servings of fish
each week.
• However, not all fishes are equal in omega-3
fatty acid content.
• Cold-water fish and Warm-water fish.
 SAPONIFICATION
 a triacylglycerol reacts with a strong base
 a triacylglycerol splits into glycerol and the salts
of fatty acids
 soaps (salts of fatty acids) form

OXIDATION
• Double bonds is triacylglycerols are subject to
oxidation with oxygen in air producing short-
chain aldehydes or a carboxylic acids.
- Often have objectionable odor; fats and oils are
said to be rancid.
- antioxidants are added as preservation.
• Natural : vitamins C and E
• Synthetic : BHT and BHA

HYDROGENATION
The hydrogenation of LIPIDS
 converts double bonds to single bonds
 adds hydrogen (H2) to the carbon atoms of
double bonds
 increases the melting point
 produces solids such as margarine and
shortening
 In hydrogenation, double bonds in unsaturated
fatty acids react with H2 in the presence of a Ni
or Pt catalyst.
 Chapter 2 Lipids 2nd Reporter

Subtopics:
a. Membrane Lipids: Phospholipids
b. Membrane Lipids: Sphingoglycolipids
c. Membrane Lipids: Cholesterol
d. Cell Membranes
e. Emulsification Lipids: Bile Acids

Phospholipids o Phosphoric acid structures were considered

most abundant type of membrane lipid when esters of inorganic acids were considered.
• Contains one or more fatty acids o The alcohol attached to the phosphate group in
• Phosphate group a glycophospholipid is usually three amino
• Platform molecule to which fatty acid(s) and the acids:
phosphate group are attached. • Choline
• Alcohol that is attached to the phosphate • Ethanolimine
group. • Serine

A platform molecule on which a phospholipid is built The structures of the three amino alcohols
may be;
• The 3-carbon alcohol GLYCEROL
• More complex C18 aminodialcohol
SPHINGOSINE.
  Glycerophospholipids containing these three amino
Glycerol-based = Glycophospholipids alcohols are known as:
Sphingosine-based =Sphingophospholipids • Phosphatidylcholines
• Phosphatidylethanolamines
• Phosphatidylserines
 
The fatty acid, glycerol, and phosphate portions of
glycerophospholipid structure constitute a Phosphatidyl
group.

Phosphatidylcholines
- also known as lecithins
- waxy solids that form colloidal suspensions in water
- within the body, this is prevalent in cell membranes
Glycerophospholipids - in food industry, it acts as an emulsifier to promote the
• A lipid that contains two fatty acids. mixing of immiscible materials
• A phosphate group esterified to a glycerol
molecule. Cephalins
• Alcohol esterified to the phosphate group. - Phosphatidylethanolamines and phosphatidylserines
Glycerophospholipids have four ester linkages. - Found in heart and liver tissue and in high
• Glycerophospholipids undergo hydrolysis and concentration in the brain
saponification reactions - Important in blood clotting
Triacylglycerols have three ester linkages.
Lecithinase
- Hydrolyzes most of the phosphatidylcholine taken
orally before it passes into the body fluids

Difference between glycerophospholipids and

triacylglycerols

Phosphoric acid
Source for the minus one charged phosphate group.
The structures of the two entities:
STRUCTURAL FORMULA OF PHOSPHATIDYLCHOLINE Sphingoglycolipids
MOLECULE is a lipid that contains both a fatty acid and a
carbohydrate component attached to a sphingosine
molecule.
A fatty acid is attached to the sphingosine through an
amide linkage, and a monosaccharide or oligosaccharide
is attached to the sphingosine at the terminal; OH
carbon atom through a glycosidic linkage.
• Sphingoglycolipids have a “head and two tails”
structure. Sphingoglycolipids and
sphingophospholipids have similar “tails”, but
their polar “heads” differ in the constituents
present (mono- or oligosaccharide versus
phosphate-alcohol).
Sphingoglycolipids undergo hydrolysis and
saponification reactions; both the amide and the
glycosidic linkages can be hydrolyzed.

MOLECULAR MODEL SHOWING THE “HEAD” AND

“TWO TAILS” STRUCTURE
Two important notes on this model:
There is a “head” part, the choline and phosphate; and
There are two “tails”, the two fatty acid carbon chains Cerebrosides
Polar head – soluble in water contain a single monosaccharide unit –either glucose or
Nonpolar tail – insoluble in water but soluble in galactose. As the name suggests, cerebrosides occur
nonpolar substances primarily in the brain.
  - They are present in the myelin sheath of nerves. The
Hydrophilic specific structure for a cerebroside in which stearic acid
water loving; polar head (18:0) is the fatty acid and galactose is the
as a group, it is the polar portion of a molecule that is monosaccharide
attracted
to water and is able to mix with it
Hydrophobic
water-fearing; nonpolar tails
as a group, is the nonpolar portion of a molecule that
has little
or no attraction for water and is unable to mix with it

Gangliosides
contain a branched chain of up to seven
monosaccharide residues. These substances occur in
the gray matter of the brain as well as in the myelin
sheath.
-Gangliosides are sialic acid-containing
glycosphingolipids. They occur especially on the cellular
surfaces of neuronal cells, where they form a complex
pattern, but are also found in many other cell types.
 - LDLs (low-density lipoproteins)
Sphingoglycolipids - HDLs (high-density lipoproteins)

Terminology and Structural Relationships among

Various Types of Fatty-Acid-Containing Lipids

Cholesterol
Cholesterol
• If the body has too much LDLs or too little HDLs,
• is the third of the three major types of
the imbalance results in an increase in blood
membrane lipids
cholesterol level. High blood cholesterol levels
• Cholesterol’s structure differs markedly from
contribute to atherosclerosis - a form of
other membrane lipids, in that:
cardiovascular disease characterized by the
(1) there are no fatty acid residues present and;
buildup of plaque along the inner walls of
(2) neither glycerol nor sphingosine is present
arteries.
as the platform molecule
Plaque
• Cholesterol is a STEROID
• is a mound of lipid material mixed with smooth
muscle cells and calcium.
Steroid
• Plaque deposits in the arteries that serve the
- is a lipid whose structure is based on a fused-
heart, reduce blood flow to the heart muscle
ring system that involves three 6-membered
and can lead to a heart attack.
rings and one
5-membered ring.
o Steroid nucleus – steroid fused-ring
system

Cell membranes
Cholesterol structure
• Is a lipid based structure that separates a cell’s
• is a C27 steroid molecule that is a component of
aqueous-based interior from aqueous
cell membranes and a precursor for other
environment surrounding the cell.
steroid-based lipids.
• It also controls the movement of substance into
• It is the most abundant steroid in the human
and out the cell.
body.

Structural basis of a cell

1. The virtually insoluble nature of membrane
lipids in water
Cholesterol
2. The head and two tails structure of
• Cholesterol is obtained from dietary intake and
phospholipids and sphingoglycolipids
most of it is biosynthesized by the liver and (to a
lesser extent) the intestine.
3 major components of phospholipids
• Since cholesterol is only sparingly soluble in
1. Phosphate head
water (blood), a protein carrier is used for its
2. Glycerol backbone
distribution. These cholesterol – protein
3. Fatty acid tails
combination are called LIPOPROTEINS
• Two types of Lipoproteins:
Lipid bilayer
is a two-layer thick structure of phospholipids and
glycolipids in which the non-polar tails of lipids are in
the middle of structure and polar heads are on the
outside surface.

Bile acids

Emulsification: Bile acids

Emulsifier
is a substance that can disperse and stabilize water
Transport across cell membrane insoluble substances as colloidal particles in an aqueous
solution.
Passive transport Bile acids
substance moves across a cell membrane by is a cholesterol derivative that functions as a lipid-
diffusion from a region higher concentration to a region emulsifying agent in the aqueous environment of the
of lower concentration without the expenditure of any digestive tract.
cellular energy.
Two types of Bile acids exist
Simple bile acids
simple (free) bile acids are steroid
monocarboxylic acids, obtained by oxidation of
cholesterol, that differ from cholesterol in two aspects:
1. They are tri- or dihydroxy cholesterol
derivatives
2. The carbon 17 side chain of cholesterol has
been oxidized to a carboxylic acid.
The figure beside contrasts the structure of cholesterol
with that of three major types of simple bile acids
Facilitated transport produced from biochemical oxidation of cholesterol:
the transport process in which substance moves • Cholic acid
across a cell membrane, with aid of membrane proteins, • 7-deoxycholic acid
from a region of higher concentration to a region of • 12-deoxycholic acid
lower concentration without the expenditure of cellular
energy.

Complexed bile acids

have enhanced emulsifying ability stemming
from one end of the molecule being strong hydrophilic
Transport across cell membrane and the rest of the molecule being largely hydrophobic.

Active transport Bile

transport process in which a substance moves is a fluid containing emulsifying agents that is secreted
across a cell membrane, with the acid of membrane by the liver, stored in the gallbladder and released into
proteins, against a concentration gradient with the small intestine during digestion.
expenditure of cellular energy
a