BIOCHEMISTRY

LIPIDS AND ITS PHYSIOLOGIC SIGNIFICANCE

DR. DEANNE ASDALA
• having too much will lead to obesity, diabetes, and
atherosclerosis
OUTLINE
I. Lipids II. CLASSIFICATION OF LIPIDS
II. Classification of Lipids SIMPLE LIPIDS – neutral fats
III. Classification of Fatty Acids (Saturated vs
Unsaturated) 1. Triglycerides (Fats and Oils):
IV. Classification based on essentiality • chief form of fat found in the diet
V. Properties • major storage form of fat
VI. Functions • structurally composed of 1 glycerol and 3 fatty
acids
LEARNING OBJECTIVES
• synthesized through a series of three (3)
condensation of glycerol and 3 fatty acids
1. To be able to differentiate saturated vs unsaturated fatty
acids  In each condensation reaction, the -OH group of
glycerol is removed and a covalent linkage known
2. Determine lipids based on its length as an ester linkage joints a fatty acid to the
3. Identify lipids based on essentiality glycerol
4. Know the properties of lipids  Oils are fats in liquid state

5. Know the functions of each lipid 2. Waxes

REFERENCES  Esters of fatty acids with higher molecular weight

• Baynes, J.W., Dominiczak, M.H. Medical Biochemistry monohydric alcohols
Second Edition. Elsevier Limited. 2005  Simplest fatty acid esters in nature
• Dr. Asdala’s Powerpoint Presentation on Lipids  A mixture of fatty acid-long-chain alcohol esters.
• Ferrier, D. (2011). Lippincott’s Illustrated Reviews:
Biochemistry (6th ed.) LWW
• Marieb, E. & Hoehn, K. (2011). Essentials of Human
Anatomy and Physiology (9th ed.). Pearson Education
Inc.
• Campbell, M.K. & Farell, S.O. (2012). Biochemistry (7th Figure 1: Structure of waxes
ed.). Brooks/Cole Cengage Learning.
• Various internet sources for photos
I. LIPIDS
COMPLEX LIPIDS – neutral fats + other components
• Heterogeneous group of compounds including fats,
1. Phospholipids:
oils, steroids, waxes, and related compounds
• similar to triglyceride except that 2 fatty acids are
 Related more by their physical than by their replaced by choline and phosphate
chemical properties
o Relatively insoluble in water
o Soluble in nonpolar solvents such as ether and
chloroform
BIOMEDICAL IMPORTANCE OF LIPIDS
• include fats, oils, sterols and waxes
• good source of energy
• needed for better absorption of fat soluble vitamins
A, D, E, K (essential fatty acids)
• good sources for essential fatty acids
• act as thermal insulator
o in subcutaneous tissues and around
certain organs (Adipose Tissues) Figure 2: Phospholipid structure.
• act as electrical insulator for rapid impulse in
myelinated nerve fibers
• lipoproteins serve to transport nutrients in blood
(lipoproteins)
Lecture Title:
Module:
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2. Glycolipids (glycosphingolipids) • long chain of carbon atoms with hydrogen attached
that has a carboxyl group (COOH) at one end and
 Lipids containing a fatty acid, sphingosine, and
a methyl group (CH3) at the other end
carbohydrate
• usually straight-chain and even-numbered
 Sugar as a functional group
Precursor or Derived Lipids
 chain may be saturated (containing no double
bonds) or unsaturated (containing one or more
1. Lipoproteins: transport vehicles for lipids in the lymph double bonds)
or blood (Figure 3). Nomenclature of fatty acids
• Chylomicron- transports triglycerides from the  Saturated FAs end in -anoic; unsaturated acids
intestine to the liver with double bonds end in -enoic.
• Very low density lipoprotein (VLDL) - made up  Carbon atoms are numbered from the carboxyl
of triglycerides, formed in the liver carbon (carbon no. 1). The carbon atoms adjacent
to the carboxyl carbons (nos. 2, 3, and 4) are also
 Intermediate-density lipoprotein (IDL) – VLDL
known as the α, β, and γ (alpha, beta and gamma)
remnant; the result of the removal of triacylglycerol
carbons, respectively, and the terminal methyl
from VLDL
carbon is known as ω- or n-carbon (Figure 4).
• Low density lipoprotein (LDL) - made up of
• Octanoic acid (8 carbons); Decanoic acid (10
cholesterol, formed in the liver; high levels mean
carbons)
you may have cholesterolemia (excessively high
• Double bond position designated by the number of
levels of cholesterol)
the carbon in the double bond closest to the
• High density lipoprotein (HDL) - made up of
carboxyl group
protein, formed in the liver; "healthy"
• Example: Oleic acid contains 18 carbons and a
Table 1: Class of lipoproteins double bond between position 9 and 10. It is
designated 18:1.
Lipoprotein Functions
Chylomicrons Transport dietary triacylglycerols and
cholesterol from intestine to tissues.
VLDL Transports triacylglycerols from liver to
tissues.
IDL (VLDL Picks up cholesterol from HDL to become
remnants) LDL. Picked up by the liver. Figure 4: Nomenclature for number and position of double bonds in
LDL Delivers cholesterol into cells. unsaturated fatty acids. Illustrated using oleicacid as an example. n
HDL Picks up cholesterol accumulating in blood —9 is equivalent to ω9.
vessels. Delivers cholesterol to liver and
steriodogenic tissues. Transfer III. Sterols
apolipoproteins to other lipoproteins.
• steroid alcohol
• occur naturally in plants and animals; most
important sterol in animals is cholesterol

Steroids
• compound containing a 4-ring carbon structure with
any of a variety of side chains attached

 precursor of a large number of equally important

steroids that include the bile acids, adrenocortical
hormones, sex hormones, vitamin D and cardiac
glycosides

Figure 3: Lipid transport in lipoproteins

PRECURSOR LIPIDS
• from the breakdown of both simple and complex
lipids; include fatty acids and sterols Figure 5: The steroid nucleus
1. Fatty acids (FA)

Lecture Title: Lipids 2

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
Cholesterol
o Widely distributed in all cells of the body but
particularly in nervous tissue
o Major component of plasma membranes and
plasma lipoproteins

Figure 8: Triacylglycerol structure

Figure 6: Cholesterol • rarely contain the same fatty acid at all 3 positions
and are therefore called mixed triacylglycerols
Ergosterol • unsaturated fatty acids are often esterified to
carbon 2
o Occur in plants and yeast and is important as • in the 3D configuration of glycerol, carbons 1 and
a dietary source of vitamin D 3 are not identical, and enzymes are specific for
one or the other carbon

Phosphoacylglycerol
• contains fatty acids esterified to position 1 and 2
of glycerol and a phosphate (alone or with
substituent) attached to carbon 3
• if only a phosphate group is attached to carbon 3,
the compound is phosphatidic acid

Figure 7: Structure of ergosterol

IV. Acylglycerol
• glycerol with one or more fatty acids (the acyl
group) attached through ester linkages
• May be a Mono-, Di-, or Triacylglycerol

Figure 9: Phosphoacylglycerol

V. Phospholipids
 Derivatives of phosphatidic acid
 Important intermediate in the synthesis of TAGs as
well as phosphoglycerols but is not found in any
great quantities in tissues
 General structure is shown below
Triacylglycerol
 Synonymous to triacylcglycerol, triacylglycerides or
simply TAGs

Lecture Title: Lipids 3

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 Clinical Correlate – Respiratory Distress Syndrome
(Sobrang extra lang ito…)
Usually problema ito sa mga born prematurely because
surfactant appears in the fetal lungs around the 32 nd week of
gestation. Meaning that babies born prior to the 32 nd week are
at risk of their lungs collapsing. This is known as neonate
respiratory distress syndrome.

• Amine is (+) charged at neutral pH and phosphate

(-) charged; Amphipathic compound

Figure 11: Lecithin

Lysolecithin

• Removal of a fatty acyl group from a

phosphoacylglycerol leads to a lysolipid
(lysolecithin)

 Important in metabolism and interconversion of

fatty acids
 Found in oxidized lipoproteins and has been
implicated in some of their effects in promoting
atherosclerosis

Figure 10: Phospholipids. The O- shown shaded in phosphatidic acid is

substituted by substituents shown to form the phospholipids.

Phosphatidylcholine (also called Lecithin)

 Dipalmitoyl lecithin - lung surfactant Figure 12: Lysolecithin

▪ Very effective surface-active agent and a
Ceramide
major constituent of the surfactant
preventing adherence, due to surface • Ceramides (Figure 12) are amides formed from
tension sphingosine by attaching a fatty acid to the amino
▪ SURface ACTing AgeNT group
▪ Prevents the collapsing of lungs by ▪ Sphingosine (in blue) is derived from
reducing the surface tension of the lungs serine and palmitate (16-carbon fatty
especially in smaller alveoli acid)

Ceramide = Sphingosine + Fatty Acid

Sphingosine = Serine + Palmitate

Lecture Title: Lipids 4

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 VI. Glycolipids
 Glycolipids are lipids with an attached
carbohydrate or carbohydrate chain
 Widely distributed in every tissue of the body,
particularly in nervous tissue such as brain
 They contribute to cell surface carbohydrates
which form the glycocalyx
 Galactosylceramide is a major glycosphingolipid
of the brain and other nervous tissue (Figure 16)
 Gangliosides (Figure 17) are complex
glycosphingolipids derived from glucosylceramide
that contain in addition one or more molecules of
sialic acid.
Figure 13: General structure of a ceramide o Gangliosides function in cell-cell recognition
and communication and as receptors for
 Ceramides are a components of sphingolipids and hormones and bacterial toxins such as the
glycolipids. Both of which are types of cholera toxin.
phospholipids.

Sphingolipids
 Sphingosine provides one of the hydrophobic
hydrocarbon tails (Figure 15, blue)
 The second hydrocarbon tail is from a fatty acyl
group connected by an amide link to the -NH2
group in sphingosine (Figure 15, red)
 An important sphingolipid is sphingomyelin
(Figure 15), which make up the myelin sheath of
nerve fibers and are present in large quantities in
brain tissue.

Figure 16: Structure of galactosylceramide.

Figure 15: Sphingomyelin (a sphingolipid)

Figure 14: Classification of Lipids

Lecture Title: Lipids 5

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 • Polyunsaturated fatty acid - lacks 4 or more
hydrogen atoms and has 2 or more double bonds
between carbon; examples include sunflower,
Figure 17: General structure of a ganglioside safflower, corn and soybean oils; Linoleic acid
CLASSIFICATION BASED ON LENGTH
VII. Classification of Fatty Acids
Classification based on Saturation Short chain

Saturated Fatty Acids - composed of less than 6 carbon atoms

• carry the maximum possible number of hydrogen

Acetic Acid (acetate)
atom
• most common saturated fatty acids include:

 all carbon bonds are single bonds

Table 2: Saturated fatty acids
Propionic Acid (propionate)

Butyric Acid (butyrate)

Medium chain
- composed of 6 – 12 carbons; does not need special
transport system in order to enter the mitochondria
(for β-oxidation)

Palmitic acid (C16)

Stearic acid (C18)

Long chain
- composed of 12 – 24 carbons and needs
transporters to enter mitochondria

UNSATURATED FATTY ACID

• Monounsaturated fatty acid - lacks 2 hydrogen
atoms and has 1 double bond between carbons;
examples include olive oil and canola oil
Lecture Title: Lipids 6
Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 Alpha-linolenic acid (ω-3 fatty acid)

 has double bonds 3 carbons from the methyl end

(hence, ω-3)

• derivative of eicosanoids like eicosapentanoic acid

(EPA) and docohexanoic acid (DHA)
• promotes growth and development and modulates
 Very long -composed of 22 or more (Lippincott) clotting and blood pressure
Examples: Lignoceric acid, Nervonic acid
 These 2 EFA (and their precursors) are required in
the production of eicosanoids
CLASSIFICATION BASED ON ESSENTIALITY
ESSENTIAL FATTY ACIDS (UNSATURATED) VIII. Other Fatty Classifications
 Essential fatty acids are unsaturated fatty acids Eicosanoids
supplied in the body through diet (vegetable oil) • 20-carbon fatty acids
 In humans, the desaturase system cannot • Note: 20 in Greek is icosa
introduce double bonds between the carbon 9 and
terminal methyl (ω) carbon atom  Precursor of prostaglandin, thromboxanes and
leukotrienes
Eicosapentaenoic acid (EPA) (C-20:5)
• ω-3 fatty acid
• contains 20 carbons with 5 double bonds
• Product of desaturation of linolenic acid
Docosahexaenoic acid (DHA) (C22:6)
• ω-3 fatty acid
The desaturase system in humans cannot introduce
double bonds within the red box. Therefore, EFA and its • contains 20 carbons with 6 double bonds
precursors must be taken in through diet. • product of desaturation and elongation if linolenic
acid
 Fatty acid desaturase – enzyme that creates
double bond in the a fatty acid chain by removing
two hydrogen

ESSENTIAL FATTY ACIDS

Linoleic acid (ω-6 fatty acid)

Clinical Correlation:
Essential fatty acid deficiency (rare) can result in a dry,
 has double bonds 6 carbons from the methyl end scaly dermatitis as a result of an inability to synthesize
(hence, ω-6) molecules that provide the water barrier in skin

• Arachidonic fatty acid derivative

• Promotes arterial dilatation and contractility of the
heart

Lecture Title: Lipids 7

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 IX. Properties of Lipids fatty acids to form a precipitate – the characteristic
1. Effects of heat scum left on the insides of sinks and bathtubs.
2. Rancidity  The other product of saponification, glycerol, is
3. Saponification used in creams and lotions as well as in the
4. Hydrogenation
manufacturing of nitroglycerine.
a. Structure of cis and trans fatty acids
• Cis Fatty Acid
• Trans Fatty Acid
b. Types of Hydrogenation
• Partial Hydrogenation
• Complete Hydrogenation
5. Emulsification

 The shorter the carbon chain of the fatty acid

the softer it is at room temperature.
Figure 18: Saponification
Effects of Heat
• Formation of a pungent odor Hydrogenation
• Acrolein formation upon exposure to excessive • Refers to the process of adding hydrogen to double
heat bonds to increase the degree of saturation.

 Pungent smell is commonly encountered in

cooking oil.
 Acrolein is an irritant to the skin, eyes and
nasal passages.
 Acrolein can be found in cooked french fries.
Rancidity  This is done for fats and cooking oils so that
shelf life can be prolonged.
• Refers to the unpleasant change in colors, tastes,
and odors due to the oxidation of fats and formation  However, the problem is by increasing the
of acrolein hydrogen in the double you make it more
saturated when it is healthier to consume
• Butyric acid, a by-product of this oxidative process
unsaturated products.
is responsible for this rancid taste
Structure of Cis and Trans Fatty Acid
 When fat is exposed to oxygen, it will spoil.
Ex. Spoiling of oil • Cis means that the H+ are on the same side of the
double bond and the acyl chains on the other side
Saponification
• In Trans fatty acid, the H+ are on opposite sides of
• Alkaline hydrolysis of tryglycerides to produce the double bond
glycerol and salt of long-chain carboxylic acid
• The formation of insoluble soaps in the intestinal
tract

 When an organism uses fatty acids, the ester

linkages of triacylglycerol are hydrolyzed by
enzymes called lipases. The same hydrolysis
reaction can take place outside an organism with
acids or bases as catalysts.
 When a base such as sodium hydroxide and Types of Hydrogenation
potassium hydroxide is used, the products the
products of the reaction, which is called • Partial Hydrogenation
saponification, are glycerol and the sodium or • Complete Hydrogenation
potassium salts of the fatty acids. These salts are
soaps.
EMULSIFICATION
 When soaps are used with hard water, the calcium
and magnesium ions in the water react with the • Process of dispersing fat globules onto another
liquid to become miscible

Lecture Title: Lipids 8

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
 X. Functions of Lipids
1. Storage form of energy
2. Transporter of fat

 Fat soluble vitamins (A,D,E,K)

 Vitamin A (retinol) – metabolized to retinal, which
is important for sight
 Vitamin D (1,25 – dihydroxycholecalciferol) –
important for calcium regulation
 Vitamin E (α-tocopherol) – protects against
cancer because it is a biological antioxidant
 Vitamin K (4-amino-2-methyl-1-naphthol) –
 Miscible – capable of being mixed to form a necessary for the post translational induction of
homogeneous mixture when added together. calcium binding sites
 Ex. Egg yolks being used as an emulsifier for  For better absorption and transport
water and oil. Mayonnaise is formed.
 Emulsification can be seen in digestion. Big
fat globules can be broken down into smaller 3. Sources of essential fatty acid
fat droplets or emulsion droplets. The bile  Such as linoleic, linolenic, eicosanoids, EPA
salts and phospholipids present in your bile and DHA
will help in the digestion of these fats.
4. Thermal insulation
 Aggregation of bile salts into micelles and
liposomes and the formation of mixed micelles with  Lipids gives off heat, and maintains the core
the products of fat digestion are important in body temperature of 37-37.5 °C
facilitating absorption of lipids from the intestine
 Emulsions are particles formed usually by nonpolar 5. Vital organ protection
lipids in an aqueous medium. These are stabilized
by emulsifying agents such as amphipathic lipids • Most of our internal organs are wrap by fats. During
(eg. phosphatidylecholine), which form a surface surgery, underneath the skin and subcutaneous
layer separating the main bulk of the nonpolar  layer is a yellow thick material which is the
material from the aqueous phase. adipose tissue.
 Emulsification increases the surface area of the
hydrophobic lipid droplets so that the digestive
6. Important constituent of tissue structure
enzymes, which work at the interface of the droplet
and the surrounding aqueous solution, can act  Skin – layers of fats
effectively.
 Emulsification is accomplished by two
7. Participates in the transport of nutrients and
complementary mechanisms, namely, use of the
metabolites across cell membranes
detergent properties of the conjugated bile salts
and mechanical mixing due to peristalsis. 8. Essential precursor substance
 Bile salts, made in the liver and stored in the
gallbladder, are amphipathic derivatives of
 Precursor compounds of molecules and fatty
cholesterol. Conjugated bile salts consist of a
acids
hydroxylated sterol ring structure with a side chain
to which a molecule of glycine or taurine is
covalently attached by an amide linkage. These
emulsifying agents interact with the dietary lipid
particles and the aqueous duodenal contents,
thereby stabilizing the particles as they become
smaller from peristalsis and preventing them from
coalescing.

Lecture Title: Lipids 9

Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal
Lecture Title: Lipids 10
Module: 2
Transcribed by: Lee, Mangahas, Olbes, Orosa, Yunzal