LIPIDS

By:
Roselita O. Natividad
Natural Science, CSIT – Ateneo de Zamboanga University

At the end of this module, you should be able to:

1. Classify lipids according to the complexity of their structures and functions.
2. Show how the structure of triglycerides are drawn from the combination of fatty acids and glycerol.
3. Explain how the structural properties of saturated and unsaturated fatty acids affect their biological properties.
4. Write the chemical equations of some of the common reactions of fatty acids and triglycerides.
5. Explain the role of biologically important steroids.
6. Explain the significance of steroids in sport medicine.

➢ Are diverse group of biomolecules that differ both in structure and function
➢ Define as those substances from living organisms that dissolve in nonpolar solvents such as ether, CHCl3 but not
appreciably in water
➢ Serve as food for the body and as secondary source of energy (9 kcal/gram)
➢ A primary structural component of biological membranes, as well as act as hormones, antioxidants, or vital growth
factors and vitamins
➢ Contains the elements carbon, hydrogen, and oxygen, although some also contain nitrogen and phosphorus
➢ Take part in plant and animal metabolism
➢ When allowed to hydrolyze, yield fatty acids

Question:
1. What are the elements found in all lipid molecules?

Functions
➢ As membrane structural component as well as intracellular storage depot of metabolic fuel
➢ As protective form of the cell walls of many bacteria, of the leaves of higher plants, of the exoskeleton of insects and
the skin of vertebrates
➢ As regulatory substances and as enzyme cofactor
➢ As transport form of some neurotransmitters and as receptors in nerve ending membranes

Questions:
1. Aside from the functions mentioned above, name other functions of lipids.
2. What is the significant role of lipids in membrane?

Classifications
1) Simple lipids
➢ are ester of fatty acids
➢ on hydrolysis, yield fatty acids and alcohol
o fats and oils – on hydrolysis yield fatty acids and glycerol
o waxes – on hydrolysis yield long chain fatty acids and long chain alcohol
2) Compound/complex lipids
➢ on hydrolysis yield fatty acids, alcohol and some other type of compound
o phospholipids – on hydrolysis yield fatty acids, alcohol, phosphoric acid and a nitrogen compound
o glycolipids – on hydrolysis yield fatty acids, alcohol, carbohydrate and a nitrogen compound
3) Steroids
1) Simple Lipids
➢ also called triacylglycerols or triglycerides
➢ examples are the fats and oils and with structural formula of

➢ that when hydrolyzed, gives glycerol and fatty acids

glycerol fatty acids

Fatty Acids
➢ the fatty acids in the fats and oils are monocarboxylic acids that contain hydrocarbon chains of variable length
➢ they are important components of several types of lipid molecules
➢ they occur primarily in triacylglycerols and several types of membrane – bound lipid molecules
➢ can be saturated and unsaturated and with even number of carbon atoms that form an unbranched chain
➢ the unsaturated fatty acid can be in the cis or trans isomer, although the cis isomers predominate
➢ the cis configuration causes an inflexible “kink’ in the fatty acid chains, that the fatty acids do not pack as close
together, thus, interrupt the regular packing of the chains resulting to low melting point and therefore are liquid at
room temperature
➢ the trans double bonds have three-dimensional structure that it resembles the saturated fatty acids. Saturated fatty
acids are solid at room temperature because of the regular nature of their chains allows the molecules to be packed
in a close parallel alignment
➢ the unsaturated fatty acids can be mono-unsaturated or poly-unsaturated
➢ fatty acids tend to undergo dimerization through H-bonding of the carboxyl group which then explains the
insolubility of longer fatty acids in water since the carboxyl groups, the only hydrophobic portion of the molecule,
has its H-bonding capacity completely satisfied

O ------- -- H–O

–C C–

O–H ---------- O

➢ the fatty acids that cannot be synthesized by mammals but are needed by the body are called essential fatty acids
and therefore must be obtained from the diet (examples are the linoleic and linolenic acids)

Questions:
1. Define monocarboxylic acids.
2. Differentiate between saturated and unsaturated fatty acids.
3. Give example of a fatty acid in the cis and in the trans configuration.
4. What effect does the trans configuration of fatty acids have on the physical properties of the simple lipid?
5. What effect does dimerization have on the solubility of fats in water?
Chemical Reaction of Fatty Acids
➢ typical that of short chain fatty acids
➢ can react with alcohol to form an ester

O O
R – C – OH + R” – OH ――→ R – C – O – R’ + H2 O

➢ unsaturated fatty acids can also undergo hydrogenation reaction to form saturated fatty acids
➢ unsaturated fatty acids are also susceptible to oxidative attack
.
Question:
1. Explain hydrogenation reaction. Give example.

Fats and Oils

➢ also known as triacylglycerols or triglycerides but can also be monoacylglycerol and diacylglycerol
➢ on hydrolysis yield fatty acids and glycerol

O
C–O–C–R C – OH
O
C–O–C–R C – OH + 3RCOOH
O
C–O–C–R C – OH

➢ have no charge thus referred to as neutral fats

➢ at room temperature, fats are solid because they contain large portion of saturated fatty acids while oils are liquid
because of their relatively high unsaturated fatty acid content
➢ practically unbranched carboxylic acids

Question:
1. What makes fats solid at room temperature?
2. What makes oil liquid at room temperature?
3. What unique characteristic in structure does fatty acids have?

Functions
➢ major storage and transport form of fatty acid
o hydrophobic in nature and so they coalesce into compact, anhydrous droplets within cells
o store in the adipose tissues (while the glycogen binds a substantial amount of water)
o less oxidize than carbohydrates, when degraded release 9kcal/gram (thus a secondary source of energy)
➢ efficient energy storage
➢ serve as protectors for vital organs
➢ provide insulation in low temperature
o fat is a poor conductor of heat
o prevents heat loss
➢ present in fur and feather as water repellant

Sources
➢ seeds – peanut, corn, palm, safflower, soybean
➢ fruits – avocado, olive
➢ others
 Properties
➢ fats from animals are solid and those from plants and fishes are liquid
➢ colorless, odorless and tasteless
➢ can undergo hydrogenation reaction (addition of hydrogen)
➢ can also undergo saponification (reaction with sodium or potassium hydroxide)

Physical Properties
➢ generally white if solid and yellow if liquid
➢ odorless and tasteless, insoluble in water

Chemical PropertiesSpecific test for glycerol

➢ can undergo hydrolysis
➢ Acrolein test

C – OH O=C–
C – OH heat, KHSO4 C– + 2H2O
C – OH –C–

Glycerol acrolein

Waxes
➢ complex mixtures of nonpolar lipids
➢ protective coatings on leaves, stems, fruits of plants and skin and fur of animals
➢ compose of long chain fatty acids and long chain alcohols
➢ examples are carnauba wax (in Brazilian wax palm and beeswax)
➢ also contain hydrocarbons, alcohols, fatty acids, aldehydes and sterols (steroid alcohols)

O
CH3 – (CH2)24 – C – O – (CH2)29 – CH3
Mellissyl cerotate (predominant constituent of carnauba wax)

2) Complex Lipids
➢ constitute the main components of membranes
➢ classified into two groups: phospholipids and glycolipids

Phospholipids
➢ structural components of membranes
➢ contain an alcohol, two fatty acids and a phosphate group
➢ several are emulsifying agents and surface active agents
➢ an amphipathic molecule, that is, consist of the hydrophobic end (composed largely of HC chains of fatty acids) and
the hydrophilic end (the polar head group contains PO4- and other charged or polar groups)
➢ of two types: phosphoglycerides and sphingomyelins

Question:
1. What is meant by amphipathic molecule?
 Phosphoglycerides
o The structure is similar to that of simple fat
o Contains glycerol, fatty acid, phosphate and alcohol (choline)
o The two OH is esterified by fatty acids while the third OH is esterified by a phosphate group which is
esterified to another alcohol
o Most numerous in cell membrane
o The simplest is the phosphatidic acid, a precursor for all other phosphoglycerides
o Are classified according to which alcohol is attached to the phosphate group:
▪ Choline – phosphatidylcholine (lecithin)
– insoluble in water but good emulsifying agent
▪ Ethanolamine – phosphatidylethanolamine
▪ Serine – phosphatidylserine
▪ Glycerol – diphophatidylglycerol
o Most common fatty acids have carbon atoms between 16 – 20
o Saturated fatty acid usually at C – 1 of glycerol, the C – 2 contains the unsaturated fatty acid

Question:
1. Describe the similarity in structure of simple fat and phosphoglyceride.

Sphingolipids (phosphosphingolipids)
o important components of animal and plant membranes
o coating nerve axons (myelin) of the different kinds of complex lipids
o contain long chain amino alcohol
o in animal, the alcohol is primarily sphingosine
o the core is called ceramide
o sphingomyelin is found in greatest abundance in the myelin sheath of nerve cells (facilitate the rapid
transmission of nerve impulses)

An example of a sphingolipid structure

Glycolipids
➢ are complex lipids that contain carbohydrate (galactose
➢ do not contain phosphate group
➢ found in large amount in the brain of tissues
➢ most important glycolipid classes are the cerebrosides, sulfatides and the gangliosides
➢ galactocerebrosides, the most common of this class, are almost entirely found in the cell membrane of the brain

An example of a glycolipid structure

Peculiar Properties of Phospholipids

➢ the fatty acid is hydrophobic while the nitrogen compound and the phosphoric side are hydrophilic and is called
amphipathic
➢ may form bilayer between two aqueous layers, thus responsible for passage of various substances into and out of
the cells

3) Steroids
➢ third major class of lipids
➢ each type of steroid is composed of four fused ring
➢ most common is cholesterol

Cholesterol
➢ most abundant in the human body and most important
➢ serve as membrane component mostly in the plasma membrane of red blood cells and in the myelinated nerve cells
➢ also serve as raw materials for other steroids that serve as precursor in the biosynthesis of all steroid hormones such
as sex and adrenocorticoid hormones, and bile salts
➢ exists both in the free and esterified with fatty acid
➢ gallstones contain free cholesterol

Structure of cholesterol
Lipoproteins
➢ any protein that is covalently bonded to lipid groups
➢ plasma lipoproteins transport lipid molecules through the bloodstream from one organ to another
➢ classified according to their density:
o chylomicrons – large lipoproteins of extremely low density
o very low LP – (0.95 – 1.006 g/cc)
– synthesized in the liver, transport lipids to tissues
– as are being transported, they become depleted of fats, as well as some
proteins and phospholipids
o LDL – (1.006 – 1.06 g/cc)
− carry cholesterol to tissues
o HDL – (1.063 – 1.210 g/cc)
− produce in the liver
− appears to be the scavenging of excessive cholesterol from cell membranes
− liver is the only organ that can dispose of excess cholesterol

“ Plasma lipoproteins transport lipids through the bloodstream.

On the basis of density, lipoproteins are classified into four major classes.”

The Fate of Cholesterol

➢ cholesterol along with fat, is being transported from the liver to the pheripheral tissues by lipoproteins (the LDL and
HDL)
➢ HDL (50% protein, 18% cholesterol) transport cholesterol to the liver and also transfer cholesterol to LDL
➢ LDL (25% protein, 45% cholesterol) plays an important role in cholesterol metabolism
o The core contains fats and esters of cholesterol in which linoleic acid is an important constituent
o On the surface are phospholipids, free cholesterol and proteins (the molecules contain many polar groups
so that water molecules in the blood plasma can solvate them by forming H-bonding, making LDL soluble in
the blood plasma)
o The LDL carries cholesterol to the cells, where specific LDL – receptor molecules line the cell surface in
certain concentrated areas called coated pits (in particular, one of the proteins on the surface of the LDL
binds specifically to the LDL – receptor molecules in the coated pits)
o After binding, the LDL is taken inside the cell through the process called endocytosis, where enzymes break
it down liberating the free cholesterol from the cholesterol esters which can now be used as a component
of the membrane
o This is the normal fate of LDL and the normal course of cholesterol transport

LP and Atherosclerosis

➢ most of the cholesterol found in plaque is obtain by the ingestion of LDL by foam cells
➢ high LDL is directly correlated with high risk for coronary artery disease
➢ high plasma HDL is associated with low risk for coronary artery disease
➢ liver cells are the only cells that possess HDL receptors
➢ the binding of LDL to LDL – receptors initiate endocytosis
➢ because LDL – receptor function is usually highly regulated, the intake of a relatively large number of LDL is followed
by decreased synthesis of LDL – receptors
➢ atherosclerotic plaque possesses high levels of LDL – receptors with affinity for oxidized LDL
➢ clinical and animal studies reveal that diets supplemented with ascorbic acid and
α-tocopherol, two powerful antioxidants, can retard or arrest plaque formation
Membrane Lipid
➢ most of the properties attributed to living organisms depend either directly or indirectly on membranes
➢ when amphipathic molecules are suspended in water, they spontaneously rearrange into ordered structures so that
the hydrophobic part is buried into the interior while the hydrophilic part are oriented so that they are exposed to
water (the basis of membrane structure)
➢ largely responsible for several other important features of biological membrane

1) membrane fluidity
▪ largely determines by the percentage of unsaturated fatty acids in its phospholipids molecules

2) selective permeability
▪ because of the hydrophobic in nature, the HC chains provide impenetrable barriers to ionic and
polar substances
▪ ionic and polar substances must shed some or all of its hydration sphere by binding to a carrier
protein for membrane translocation or to pass through an aqueous protein channel
▪ the nonpolar substances simply diffuse through the lipid bilayer down their concentration
gradients

3) self sealing capacity

▪ when lipid bilayers are disrupted, they immediately and spontaneously reseal because a break in a
lipid bilayer exposes the hydrophobic HC chains to water
▪ resealing property is critical because breaching in cell membranes can be lethal

4) asymmetry
▪ lipid composition of each half of a bilayer is different
▪ membrane asymmetry is not unexpected since each side of a membrane is exposed to a different
environment

“ All membranes are composed of lipids and proteins. Membrane lipids are mostly amphipathic molecules,
which are principally responsible for such properties as membrane fluidity, selective permeability,
self-sealing capacity, and asymmetry. Membrane proteins are structural components,
enzymes, hormone receptors or transport proteins.”

• Activity 1
o Film viewing – Lorenzo’s Oil
o At the end of the film, please answer the following:
▪ What struck you the most and why?
▪ What learning did you have after watching the movie?
▪ What were some of the most interesting discoveries you have after watching the movie?
▪ What did you feel after watching the movie?
▪ What conclusion can you make about the movie?

• Activity 2
o Read about the disqualification of an internationally recognized athlete due to use of steroids; find out why
the particular steroid is banned from the athlete’s sport. Write a crtique paper about the incident.
That is . . . . .

➢ Lipids are a diverse group of biomolecules that dissolve in nonpolar solvents

➢ Can be separated into the following classes: fatty acids and their derivatives, triacylglycerols, wax esters,
phospholipids, sphingolipids and the isoprenoids
➢ Fatty acids are monocarboxylic acids that occur primarily in triacylglycerols, phospholipids, and sphingolipids
➢ The triacylglycerols are esters of glycerol with 3 fatty acid molecules that can be solid (fats) or liquid (oils) at room
temperature
➢ Triacylglycerols, the major storage and transport form of fatty acids, are important energy storage form in animals,
in plants they store energy in fruits and seeds
➢ Phospholipids are structural components of membranes and of two types: phosphoglycerides and sphingomyelins
➢ Sphingomyelins are also important components of animals and plants membranes. They contain long chain amino
alcohol. In animals, the alcohol is sphingosine
➢ Glycolipids are sphingolipids that possess carbohydrate groups and no phosphate
➢ Isoprenoids are molecules that contain repeating five-carbon structural units known as isoprene units. Isoprenoids
consist of the terpenes and the steroids
➢ Plasma lipoproteins transport lipid molecules through the bloodstream from one organ to another. They are
classified according to their density
➢ Chylomicrons are large lipoproteins of extremely low density that transport dietary triacylglycerols and cholesteryl
ester from the intestine to the tissues
➢ VLDL, which are synthesized in the liver, transport lipids to tissue. As VLDL travel through the bloodstream, they are
converted to LDL
➢ LDL are engulfed by cells after binding to LDL receptors on plasma membranes. LDL plays an important role in the
development of atherosclerosis
➢ HDL, also produced in the liver, scavenge cholesterol from cell membranes
➢ The basic nature of membranes is a lipid bilayer in which proteins float. Membrane lipids are primarily responsible
for the fluidity, selective permeability, and self-sealing properties of membranes
➢ Membrane proteins usually define the biological functions of specific membranes

Questions:

1) Use your own words to define each of the following terms:

a. Simple and compound lipid d. wax
b. Essential fatty acid e. saturated and unsaturated
c. Triacylglycerol fatty acid

2) Write the structural formula for a triacylglycerol formed between glycerol, palmitic acid, stearic acid and oleic acid.
Is the structure a simple or mixed triacylglycerol?
3) Would you expect the triacyl glycerol formed in #2 to have a high or low iodine number? Is the compound likely to
be a liquid or solid at room temperature?
4) What are the elements found in all lipid molecules?
5) How are lipids classified?
6) What are the hydrolysis products of simple lipids?
7) What is the important constituent in blood clotting?
8) What group of lipid molecules has a characteristic fused ring?
9) Where can you find the first double bond in unsaturated fatty acids?
10) What substance is being used to convert fatty acid to soap?
11) What is the process called when fatty acid is being converted to soap?
12) What do you call a molecule with polar and nonpolar end?
13) Differentiate oil from fat.
14) What are the functions of lipids?
15) Why is it that fatty acids found in nature contain even number of carbon atoms?
16) What is the importance of the polar and nonpolar end of fatty acids?
17) What is the structure of cholesterol?
18) What role does plasma play in the human body? Why do plasma lipoproteins require a protein component to
accomplish their role?
19) What are isoprenoids? Eicosanoids?