LIPIDS

Chapter 4

Chem 40: Fundamentals of

Biochemistry
 Outline
 Introduction about Lipids
 Structures & Properties of Triglycerides
 Structures of Complex Lipids
 Role of Lipids in the Structure of Membranes
 Glycerophospholipids
 Sphingolipids
 Glycolipids
 Steriods
 Physiological Roles of Steroid Hormones
 Bile Salts
 Protaglandins, Thromboxanes, and Leukotrienes
LIPIDS
 common defining feature of lipids is their
insolubility in water
 but can be dissolved in nonpolar solvents
such as ether, chloroform, and acetone
 are amphipathic (polar and nonpolar)
Functions:
 Stored forms of energy (e.g. fats and oils)
 Structural components of cell membranes (e.g.
phospholipids, sphingolipids and steroids)
 Intercellular messengers (e.g. steroid hormones,
thromboxanes)
 Enzyme cofactors
 Electron carriers
 Vitamins (e.g. A,E,D,K)
 Light-absorbing pigments (e.g. carotenoids)
 Protective or waterproofing functions
 Categories of Biological Lipids
Category
Categories Code
Examples
Fatty Acids FA Oleate, stearoyl-CoA, palmitoylcarnitine

Glycerolipids GL Di- and Triacylglycerols

Phosphatidylchloline, phosphatidylserine,
Glycerophospholipids GP
phosphatidylethanolamine
Sphingolipids SP Sphingomyelin, ganglioside GM2

Sterol lipids ST Cholesterol, progesterone, bile acids

Prenol lipids PR Farnesol, geraniol, retinol, ubiquinone
Saccrarolipids SL Lipopolysaccharide
Polyketides PK Tetracycline, aflatoxin B1
4.1 FATTY ACIDS
Fatty acids
 are hydrocarbon derivatives
 are carboxylic acids with hydrocarbon chains
ranging from 4 to 36 carbons long (C4 to C36)
 The most common biological fatty acids have an
even number of carbons between 12 and 24
carbons.
 chain can be unbranched and fully saturated
(contains no double bonds)
 chain can contain one or more double bonds
(unsaturated)
 a few contain three-carbon rings, hydroxyl
groups, or methylgroup branches
Nomenclature
 a simplified nomenclature for unbranched fatty acids
specifies the chain length and number of double bonds,
separated by a colon
Nomenclature
 a simplified nomenclature for unbranched fatty acids
specifies the chain length and number of double bonds,
separated by a colon
Saturated fatty acids
 hydrocarbon chain has no double bonds
 pack close together
 less fluid (can’t move as freely)
 higher melting point
 likely to be solid at room temperature
Unsaturated fatty acids
 hydrocarbon chain has ONE or MORE
DOUBLE BONDS
 double bonds are “cis” configuration
 kink or bend in the chain
 more fluid than saturated
 lower melting point than the saturated
 likely to be liquid at room temperature
 Some naturally occurring SATURATED fatty acids

Note trends
in the
melting
points

Note even carbon

progression
Some naturally occurring UNSATURATED fatty acids
Structure of some naturally occurring fatty acids
Essential fatty acids
 a PUFA that is needed by the human body
 must be obtained from dietary sources coz
it cannot be synthesized within the body
 examples are: linoleic and linolenic acids
 Omega (ω) fatty acids
 a fa has two ends, the methyl (CH3) and the
carboxyl (COOH) end
 omega classification system for fa’s is based on
numbering chain beginning at the methyl end
* omega-3(ω3) fatty acid is a PUFA w/ its
endmost double bond three carbons away from its
methyl end
* omega-6(ω6) fatty acid is a PUFA w/ its
endmost double bond six carbon away from its
methyl end
Linolenic acid
 the primary member of the ω3 family of fa’s
Function
 structure and function of cell membranes
* retina of the eye and the CNS
Source
 fish
*cold-water fish have higher ω3
concentrations than warm-water fish
Linoleic acid
 the primary member of the ω6 family of fa’s
Function
 essential for growth, skin integrity, fertility,
and maintaining red blood cell structure
* lack of linoleic acid can cause skin
redness and irritation
Source
 vegetables and meat
*human breast milk have higher % of
linoleic acid than cow’s milk
Arachidonic acid
 an ω6 fatty acid synthesized from linoleic acid
Function
 precursor for the family of molecules called
eicosanoids w/c are oxygenated derivatives
of this acid
 Eicosanoids
 are hormone-like molecules
 present in cell except in the red blood cells
 they are not transported in the bloodstream to
their site of action but rather exert their effects
in the tissues where they are synthesized
 ex. prostaglandins, leukotrienes &
thromboxanes
Biological processes regulated by eicosanoids
 Blood clotting
- Thromboxane A2 & prostacyclin stimulates
constriction of blood vessels and platelet
aggregation
 Inflammatory response
- Prostaglandins mediate aspects of inflammatory
response
 Reproductive system
- PGE2 stimulates smooth muscle
Biological processes regulated by eicosanoids
 Gastrointestinal tract
- Prostaglandins inhibit gastric secretion of
protective mucus, inhibition of hormone-sensitive
lipases
 Kidneys
- Prostaglandin dilates renal blood vessels w/c
results in increase water and electrolytes
excretion
 Respiratory tract
- Leukotrienes promote the constriction of
bronchi
- Prostaglandins promote bronchodilation
4.2 GLYCERIDES

4.2.1 Neutral glycerides (TAG)

4.2.2 Phosphoglycerides
 Glycerides
 these are glycerol-
containing lipids
4.2.1 Neutral glycerides
 so named because they are nonionic and
nonpolar
 produced from the esterification of
glycerol with one or more fatty acids:
monoglycerides; diglycerides; triglycerides
Triglycerides (or triacylglycerol,TAG)
 are esters of
glycerol with three
fatty acid
molecules
 serve as energy
storage in adipose
cells
a) Simple triglycerides
 if all three –OH group of glycerol molecule
are esterified with the same fatty acid
 have been synthesized in the lab but rarely
occur in nature
b) Mixed triglycerides
 contain 2 or 3 different fatty acid
components
 most fats and oils are mixed TAG

(Myristic)

(Palmitic)

(Oleic)
 Fats and Oils
Fats
• contains a greater
proportion of saturated
fa’s than unsaturated fa’s
• solid or semisolid @
room temp
• e.g. beef tallow, pork lard
• animal sources hence
usually called “animal fat”
Oils
• contain a greater proportion
of unsaturated fa’s than
saturated
• liquid @ room temp
• e.g. soybean oil, canola oil,
peanut oil
• vegetable sources hence
usually called “vegetable oil”
Table 13.1 Introduction to General, organic, and Biochemistry by Betteleim, Brown, Campbell and Farrell
 Advantages to using triacylglycerols
as stored fuels
1. the carbon atoms of fatty acids are more reduced than
those of sugars, and oxidation of triacylglycerols yields
more than twice as much energy, gram for gram, as the
oxidation of carbohydrates
2. because triacylglycerols are hydrophobic and therefore
unhydrated, the organism that carries fat as fuel does not
have to carry the extra weight of water of hydration that
is associated with stored polysaccharides (2 g per gram of
polysaccharide)
 Fat substitute – Olestra (Olean)
 chemically synthesized
 mixture of sugars and fatty acids
 has between 6-8 fa’s attached to alcohol groups
 not absorbed and metabolized
- therefore not caloric
Soaps and Detergents
 are sodium or potassium salt of long-chain
fatty acid
 is composed of a large nonpolar
hydrocarbon portion (hydrophobic) and a
carboxylate salt end (hydrophilic)
The cleansing action of the soap

C17 H35COONa + MgSO4 (C17 H35COO) 2 Mg + Na2 SO4

Sodium stearate insoluble scum
(soap)

C17 H35COONa + CaCl2 (C17 H35COO) 2 Ca + 2 NaCl

insoluble scum
 Soaps vs. Detergents
Soaps Detergents
• are natural, commonly • are synthetic, usually made
prepared from fats & oils from petroleum chemicals

• are fatty acid salts w/ • contains sulfonate group

carboxylate group

• will form an insoluble • will form salts of

precipitate of salts when alkylsulfonic acids w/c are
dissolved in water rich in more soluble in water
metal ions
 Types of Detergents
1. Anionic detergents
- are sulfates of fatty acids
or sulfonate salts of
hydrocarbons.
- commonly used in home
laundry products
- ex. are
alkylbenzenesulfonates
- bile acids (deoxycholic
acid)
 Types of Detergents
2. Cationic detergents
- referred to as invert soap
because their water-soluble
end carries a positive than
negative charge
- widely used in hospitals
- good cleansing agents
- used in fabric softeners and
disinfectant soaps
 Types of Detergents
3. Nonionic detergents
- contain polar covalent
structures that provide the
required water solubility
- are low-sudsing and
effective in low temperature
- used extensively in
dishwashing liquid and on all
occasions that call for
absence of inorganic ions.
Properties of Lipids
1. Hydrolysis
2. Hydrogenation
3. Halogenation
4. Rancidity
a. hydrolytic rancidity
b. oxidative rancidity
HYDROLYSIS
 lipids can be hydrolyzed by an alkali or by enzymes
called lipases, that is, they can react with water to
form their carboxylic acids and alcohols
 the reaction term is saponification because one of
the products is a soap, generally Na- or K- salts of
fatty acids.
 HYDROGENATION
 converts oils to fats (hardening)
 hydrogen is bubbled through hot oil in the presence of
a catalyst
 control of the degree of hydrogenation gives the
various types of partially hydrogenated vegetable
products like soft
margarine, shortenings
 partial hydrogenation
generates trans fats w/c is
thought to raise blood
cholesterol.
HALOGENATION
 a test for unsaturation
 the amount of halogen absorbed by the lipid can be
used as an index of the degree of unsaturation
 iodine number – the number of grams of iodine that
will add to 100g of fat or oil
RANCIDITY
 the development of disagreeable odor
 when the double bonds of fats & oils are oxidized
by oxygen and lipases
 formation of short-chain fatty acids and aldehydes
which have the disagreeable odor.
a. hydrolytic rancidity – e.g. butyric acid causes
rancidity of butter
b. oxidative rancidity
4.2.2 PHOSPHOGLYCERIDES

4.2.2.1 Lecithins
4.2.2.2 Cephalins
4.2.2.3 Phosphatidgylinositols
PHOSPHOGLYCERIDES
 also known as glycerophospholipids
 a group of lipids containing a phosphate group
 abundant in the liver, brain & spinal tissue and are
found in the outer membranes of most cells
PHOSPHOGLYCERIDES

Cephalin is derived from the Greek word Kephalikos meaning head

 PHOSPHOGLYCERIDES

Phosphatidylinositols serve as signaling molecules in chemical communication.

4.3 NONGLYCERIDES

4.3.1 Waxes
4.3.2 Sphingolipids
4.3.3 Steroids
WAXES
• complex mixture of nonpolar lipids
• protective coating on leaves, stems, and fruit of
plants, and skin and fur of animals
• main constituent of waxes: esters composed of
long chain fatty acids and long-chain alcohols

• also contains hydrocarbons, aldehydes, and sterols

• serves as energy stores and water repellants
 Carnauba wax – produced by the leaves of
Brazilian palm
main consituent: ester melissyl cerotate
CH3(CH2)24 – COO – (CH2)29CH3
 known as “queen of waxes”
 can produce a glossy finish and
as such used in automobile
waxes, polishes, floor wax,
coatings of paper & sweets.
 used in cosmetics because of
its hypoallergenic property
 Beeswax
 a by-product when the honey is harvested
and refined
main constituent: tricontyl hexadecanoate
 consist of C40 to C46
 used as shoe polishes, candles wax paper
 Spermaceti
- wax extracted from spermaceti
oil (from the head cavities of the
sperm whales) @ 6oC
- forms brilliant white crystals
that are hard but oily to touch
are devoid of taste and smell
- widely used in the manufacture
of lotions, ointments, soaps and
polishes.
 Lanolin
- wax from the wool
- yellow waxy substance secreted by
the sebaceous glands of wool-bearing
animals
- mixture of cholesterol & esters of
several fatty acids
- used in skin ointments & lotions to
aid retention of water w/c softens the
skins
- lanolin’s role in nature is to protect
wool and skin against the ravages of
climate and the environment.
SPHINGOLIPIDS
• derived from sphingosine, an 18-carbon
unsaturated amino dialcohol
• can be regarded as derivatives of ceramide (core
of each type of sphingolipid)
• are compounds consisting of sphingosine and a
fatty acid
 Spingomyelin
• the white matter of the myelin
sheath
• function principally in brain and
nerve tissue
• essential to proper cerebral
function and nerve transmission
• found in all cell membrane
 Glycolipids (cerebrosides)
• occur primarily in the brain (7% of
the solid matter) and myelin sheath
of nerves
• composed of sphingosine, a fatty
acid and a sugar moiety
• reside in the cell membranes w/
their carbohydrates segments
extending into the fluid surrounding
the cells.
 Gangliosides
• similar to cerebrosides but contain
oligosaccharide groups with one or
more sialic acid residue
• important in cell membranes as
receptors for hormones, viruses,
and several drugs.
 Importance of Sphingolipids
Cell surface antigens  Apparently, when Johann
Thudichum discovered
sphingolipids at the turn of the
20th century, he had no idea why
they were present. That’s why the
name is derived from the Sphinx.
 We now know that many are
involved as cell surface recognition
sites.
 One well-known function of
sphingolipids is that they function
as cell surface antigens, defining the
various blood types.
 Importance of Sphingolipids
 The human blood groups are
Cell surface antigens determined in part by the type of
sugars located on the head groups. In
the ABO system, the determinating
gene is located on chromosome 9, and
encodes one of several
glycosyltransferases.
 If the gene encodes a protein that
transfers an N-acetylgalactosamine
group, this corresponds to the A
antigen.
 If the gene encodes a protein that
transfers a galactose group, this
corresponds to the B antigen.
 If the gene does not encode an active
glycosyltransferase, this corresponds to
the O antigen.
Sphingolipid storage disease
 disease caused when some of the enzymes needed to
decompose the complex lipids are defective or
missing
 as a consequence, the complex lipids accumulate and
cause an enlarged liver and spleen, mental retardation,
blindness and in certain cases, early death
 at present, no treatment is available for these disease.
 the best way to prevent them is by genetic counseling
 Sphingolipid storage disease

Disease Symptom Sphingolipid Enzyme

Tay-Sachs Blindness, Ganglioside β-hexose-
muscles weak aminidase A
Gaucher’s Liver & spleen Glucocerebroside β-glucosidase
enlarge, MR
Krabbe’s Demyelation, Galactocerebroside β-galactosidase
MR
Nieman-Pick MR Sphingomyelin Sphingomyelinase
 STEROIDS
• complex derivatives of triterpenes
• found in plant(cycloartenol) and animal tissues, and
molds (lanosterol), but not in bacteria,
• may exist free of combined with fatty acids or
carbohydrates
• have cyclopentanoperhydrophenanthrene
nucleus.
 Sterols
• steroids containing one, two, or three double bonds
and one or more hydroxyl groups
• e.g. cholesterol
 Cholesterol
• the best known and most abundant steroid in the
body
• name derived from the Greek, chole – bile, steros -
solid
• functions
- plasma membrane component in all animal cells
e.g. in red blood cells
- raw material of other steroids, vit. D and bile salts
 Cholesterol
 high occurrence in the brain and
nerve tissue, the principal constituent
of gallstones
 not necessary in the diet
- our liver synthesize about 1g of
cholesterol each day
 cholesterol in the body is in a
dynamic state
 being hydrophobic, it needs a water-
soluble carrier to circulate in the
aqueous medium of blood
Lipoproteins: Carriers of cholesterol
 Cholesterol and other lipids
in the body are transported
from one organ to another
through the bloodstream via
plasma lipoproteins.
 Consist of a core of
hydrophobic molecules
(triglycerides and cholesterol
esters) surrounded by a shell
of hydrophilic molecules
(proteins and phospholipids)
Lipoproteins: Carriers of cholesterol
Lipoproteins: Carriers of cholesterol
 Chylomicron transports dietary
TAG, cholesterol, etc. from the
intestines to other tissues
(adipose tissue and liver).
 HDL transports cholesterol from
peripheral tissues to the liver.
 LDL carry cholesterol to
peripheral (adipose) tissues and
help regulate cholesterol levels in
those tissues; regulates de novo
synthesis of cholesterol. The liver
LDL receptors enable large
amounts of cholesterol to be
removed from the blood.
 HDL transports cholesterol from
peripheral tissues to the liver
High Blood Cholesterol
 is a condition in which
you have too much
cholesterol in your
blood.
 Atherosclerosis
- coronary heart
disease in which
plaque builds up inside
the coronary heart
 Bile Acids / Bile Salts
 bile is produced by the liver, stored in
the gall bladder, and secreted into the
intestine
 Bile salts are the most important
constituents of human bile
- an emulsifying agent that makes dietary
lipids soluble in the aqueous
environment of the digestive tract
- facilitate the absorption of fats
- are cholesterol oxidation products
where cholesterol is oxidized to
carboxylic acid w/c is bonded to an
amino acid by amide linkage
 Hormones
 A hormone is a chemical
messenger secreted by specific
glands and carried by the blood to
a target tissue, where it triggers a
particular response.
 Hormones serve as a means of
communication between various
tissues.
 Hormones, together with the
central nervous system (CNS), are
regulators of body reactions like
metabolism, growth and
development, etc.
Steroid Hormones
 are steroids that act as a hormone
 help control metabolism, inflammation, immune functions, salt
and water balance, development of sexual characteristics, and
the ability to withstand illness and injury
 can be grouped according to the receptors to which they bind
a) Adrenocorticoid hormones
1. Glucocorticoids – control carbohydrate metabolism
2. Mineralocorticoids – regulate the concentration of ions
b) Sex hormones
1. Androgens – the male sex hormone e.g. testosterone
2. Estrogens – the female sex hormone e.g. estradiol
3. Progestins – the pregnancy hormones produced in the
ovaries and in the placenta
Steroid Hormones
Synthetic Steroids
 increased knowledge of the structures and functions of sex
hormones has led to the development of a number of; among
the best known are oral contraceptives and anabolic agents.
 anabolic steroid abuse can result in a wide range of harmful
side effects such as acne; liver tumors; breast development in
men; growth of facial hair, baldness, deepening of the voice and
menstrual irregularities in women.

(a synthetic progestin) (a synthetic tissue-building steroid)

 Lipids as Signals, Cofactors & Pigments
Beyond the Passive Roles of Lipids in Storage & Structure

• Active roles for lipids and their derivatives

Intracellular signaling – Phosphatidylinositol
 Paracrine hormones – Eicosanoids
Steroid hormones –polar cholesterol derivatives
Vitamins – A, D, E, and K
• Provide crucial parameters of membrane
fluidity