LIPIDS 4.

Lipophilic bile acids aid in lipid

solubilization.
- Collective term for fixed oil, fats and waxes.
- Lipids are biomolecules that are soluble in Biomedical Importance
organic solvents and insoluble in water.
• Fat
- They are not defined by a particular
stored in adipose tissue serves as
functional group, thus they have a variety of
thermal insulator in the subcutaneous
structures and functions.
tissues and around certain organs;
- They contain many nonpolar C—C and C—H
• Nonpolar lipids
bonds and few polar bonds resulting in their
act as electrical insulator, allowing
water insolubility.
rapid propagation of depolarization
- Are heterogeneous group of compounds
waves along myelinated nerves;
(fats, oils, steroids, waxes and related
• Lipoproteins
compounds), that are related more by their
occur in both cell membrane and
physical than by their chemical properties.
mitochondria, and also serve to
Common properties: transport lipid in the blood

– (1)Relatively insoluble in water

Lipids
– (2) Soluble in non-polar solvents
• Important dietary constituents
– High energy value
Properties of Lipids – Contains fat-soluble vitamins and
essential fatty acids
• Greasy to touch, leaves a permanent oily – Essential Fatty Acids (EFA’s)
stain on paper; • Are necessary fats that
• Lighter than water; humans cannot synthesize,
• Soluble in organic solvent, insoluble in and must be obtained
water; • When pure, colorless with bland through diet.
odor and taste; • Are long-chain
• Yellow color in fat is due to carotene polyunsaturated fatty acids
(provitamin A); derived from linolenic,
• When heated strongly, undergoes linoleic, and oleic acids.
decomposition forming acrid flammable
vapors and when ignited, they burn with a II. CLASSIFICATIONS OF LIPIDS
sooty flame.
Classification of Based on the “alcohol component”

• Simple lipid: Ester of fatty acid and _____

• Fats/fixed oil - ester of fatty acid and ____
– Triglycerides - esters of three molecules
of fatty acids plus one molecule of
glycerol.
– Found in adipose tissue, butterfat, lard,
suet, fish oils, olive oil, corn oil

• Waxes - ester of fatty acid and _____

– beeswax, head oil of sperm whale,

Major Roles of Biological Lipids cerumen, carnauba oil, and lanolin.
1. They serve as structural components of
biological membranes.
2. They provide energy reserves,
predominantly in the form of triacylglycerols.
3. Both lipids and lipid derivatives serve as
chemical messengers.
 Lipids can be categorized as:

1. Hydrolyzable lipids can be converted into smaller

molecules by hydrolysis.
•Oleic acid (mp 16 oC) is an unsaturated fatty acid.

2. Nonhydrolyzable lipids cannot be cleaved into

smaller molecules by aqueous hydrolysis.

HYDROLYZABLE LIPIDS

Fatty Acids

– Hydrolyzable lipids are derived from fatty

acids.
– Fatty acids are carboxylic acids (RCOOH)
with long C chains of 4-36 C atoms.
– An example is CH3 (CH2 )14COOH
(palmitic acid):

– Naturally occurring fatty acids have an

even number of C atoms. Fatty Acids: Nomenclature
– Saturated fatty acids have no double
 Simplified: Chain length : Double bonds (e.g.,
bonds in their long hydrocarbon chains.
16:0, 18:1)
– Formula, Suffix
 Carboxyl carbon: C1 20
– Unsaturated fatty acids have 1 or more
 Positions of any double bond:
double bonds (generally cis) in their long
𝚫 (specified relative to C1 by a superscript
hydrocarbon chains. Formula, Suffix
number indicating the lower-numbered C in
– As the number of double bonds in the
the double bond)
fatty acid increases, the melting point
– Example: 𝚫9
decreases.
– Stearic acid (mp 71 oC) is a saturated
fatty acid.
 UNSATURATED FATTY ACIDS

• MONOUNSATURATED

o (Monoethenoid,
monoenoic) acids
containing double bond

• POLYUNSATURATED
Omega-n Nomenclature:
o (polyethenoid, polyenoic)
 alternative nomenclature applied in human
acids containing two or
nutrition
more double bonds
 n = the carbon at which the first double
bond occurs in the carbon chain • EICOSANOIDS
(beginning at the end of the chain
o Derived from eicosa- (20
containing methyl group) 22
carbon) polyenoic fatty
 Linolenic acid is called an omega-3 acid, because
acids
of the position of the first C=C in the nonpolar
o Arachidonic acid is the
chain.
major precursors
-Prostanoids
-Leukotrienes (LTs )
-Lipoxins (LXs)

PROSTANOIDS

 Humans require omega-3 linolenic acid o Are part of a family of biologically active
 Essential FA lipids derived from the twenty-carbon
 Precursor in the synthesis of eicosapentaenoic essential fatty acids or eicosanoids;
acid (EPA) and docosahexaenoic acid (DHA) o Relates to the products of the
cyclooxygenase pathway
PHYSICAL and PHYSIOLOGIC PROPERTIES OF FATTY o Prostanoic acid as the central structural
ACIDS element
• MELTING POINT o Three main groups ▫
 Prostaglandins (PGs)
–of even numbered carbon fatty  Prostacyclins (PGIs)
acids:  Thromboxanes (TXs)
o increases with chain
length
o decreases according to
unsaturation
• TRIACYLGLYCEROL
– containing three saturated fatty
acids of 12 C or more is solid at
body temperature
o 18:2 fatty residues are
liquid at body
temperature to below 0°C

• MEMBRANE LIPIDS

– must be fluid at all environmental

conditions: More unsaturated than
storage lipids
 •General formation of waxes:
PROSTAglandins
• Acts as local hormones
• Synthesized from eicosanoic polyunsaturated
fatty acids (arachidonic acid) to form
cyclopentane ring
• PG1, PG2, and PG3– numbers are based on
the double bonds in the side chain •For example, shown below is the formation of
• The letter component identifies the functional spermaceti wax, isolated from the heads of sperm
groups of the cyclopentane ring whales.
o PGE – keto group in 9 position
o PGF – hydroxyl group in 9 position

THROMBOXANES
• Cyclopentane ring interrupted with an oxygen
atom;
• The two major thromboxanes are
thromboxane A2 and thromboxane B2
• Its role is in clot formation (thrombosis)

•Because of their long nonpolar C chains, waxes are

very hydrophobic.

•They form protective coatings on bird’s feathers

and sheep’s wool and make up beeswax.

Beeswax (myricyl palmitate):

LEUKOTRIENES and LIPOXINS
• Formed via the lipooxygenase pathway
• Has three (leukotrienes) to four (lipoxins)
conjugated double bonds
• Leukotrienes - a proinflammatory agents and
causes bronchoconstriction, thus play a part
in asthma –

Common leukotriene inhibitors: •Like other esters, waxes are hydrolyzed with water
• Zyflo – Zileuton in the presence of acid or base to re-form the
• Accolate – Zarfirlukast carboxylic acid and alcohol they came from.
• Singulair – Montelukast

Waxes

 are esters formed from a fatty acid and a high

molecular weight alcohol.

•General structure of waxes:

 Triacylglycerols—Fats and Oils • Saturated triacylglycerols contain only
saturated fatty acids; they make up most
•Triacylglycerols (triglycerides) are three esters
animal fat and are solids at room
formed from glycerol and three molecules of fatty
temperature.
acids.. Main storage forms of fatty acids.

•Below is a generalized block diagram of a

triacylglycerol:

• Unsaturated triacylglycerols contain at

least one unsaturated fatty acid; they
make up most vegetable oils and are
liquids at room temperature.
• Monounsaturated triacylglycerols have 1
•The general reaction for the formation of a C=C bond.
triacylglycerol is: • Polyunsaturated triacylglycerols have
many C=C bonds
• Increasing the number of double bonds in
the fatty acid chain decreases the melting
point of the triacylglycerol.

An unsaturated triacylglycerol:

General Features

• Simple triacylglycerols have three

identical fatty acid side chains.

•Fats have higher melting points; they are solids at

room temperature.
•Mixed triacylglycerols have two or three
•Oils have lower melting points; they are liquids at
different fatty acids. room temperature.

•Fats are derived from fatty acids with few double

bonds.

•Oils are derived from fatty acids having a larger

number of double bonds.
Focus on Health & Medicine: Fats and Oils in the Diet Focus on the Human Body
Metabolism of Triacylglycerols
• Fats are used to build cell membranes, insulate
the body, and store energy for later use. •Humans store energy as triacylglycerols in adipose
• It is recommended that no more than 20-35% of a cells below the surface of the skin, in the breast area,
person’s caloric intake should come from lipids. and surrounding internal organs.
• A high intake of saturated triacylglycerols is
•The number of adipose cells is constant; weight
linked to heart disease.
gained or lost causes them to swell or shrink, but not
• Saturated fats stimulate cholesterol synthesis,
decrease or increase in number.
which can lead to cholesterol plaques building up
inside arteries. •To metabolize triacylglycerols for energy, the esters
• The result is high blood pressure, heart attack, are hydrolyzed by enzymes called lipases.
and even stroke.
• Unsaturated triacylglycerols lower the risk of •Complete metabolism of a triacylglycerol yields CO2
heart disease by decreasing the level of , H2O, and a great deal of energy.
cholesterol in the blood. Compound Lipids
• Triglycerols formed from omega-3 fatty acids are
very helpful in lowering the risk of heart attack. ▫ Esters of fatty acid, alcohol and another compound.
• However, if the double bond of the unsaturated A. PHOSPHOLIPIDS
triacylglycerol is trans, the beneficial effect is lost.
• Trans fats, which are primarily synthesized • Fatty acid and alcohol plus a
instead of naturally occurring, act like saturated _______ residue;
fats and increase the cholesterol levels in the • Frequently have nitrogen-
blood. containing bases and other
substituents
(glycerophospholipids, the alcohol
is ______; sphingophospholipids,
the alcohol is __________)

B. GLYCOLIPIDS

• Glycosphingolipids –fatty acid and

sphingosine plus carbohydrate.

C. OTHER COMPLEX LIPIDS

• sulfolipids and aminolipids

• Lipoproteins
Hydrolysis of Triacylglycerols
Phospholipids
•Triacylglycerols are hydrolyzed with water in the
presence of acid, base, or enzymes (in the body). •Phospholipids are lipids that contain a P atom.

•Two common types of phospholipids are

phosphoacylglycerols and sphingomyelins.
• Main lipid constituents of membrane

• Derivatives of phosphatidic acid

• Phosphate is esterified with the –OH of a suitable

alcohol

• Phosphatidic acid – intermediate in the synthesis of

triacylglycerols

•One of the main types of phosphoacylglycerols is

cephalin:

Phosphoacylglycerols

•Phosphoacylglycerols are the main component of

most cell membranes.

•Structurally, they resemble a triacylglycerol, except

the third fatty acid has been replaced with a •The second of the main types of phosphoacyl-
phosphodiester bonded to an alcohol. glycerols is lecithin:

•The two fatty acid side chains form two nonpolar

“tails” that lie parallel to each other.

•The phosphodiester end of the molecule is a

charged or polar “head”.
 PHOSPHATIDYLCHOLINES (Lecithins) complexes important to the
electron transport chain
• Phosphoacylglycerol containing choline

– Most abundant phospholipids of

the cell membrane and represent
a large proportion of the body’s
store of choline

• CHOLINE LYSOPHOSPHOLIPIDS
– important in nervous transmission,
as acetylcholine, and as a store of – Are intermediates in the
labile methyl group metabolism of phosphoglycerols
– Important in the metabolism and
• DIPALMITOYL LECITHIN interconversions of phospholipids
(lysophosphatidylcholine)
– Effective surface-active agent
– Found in oxidized lipoproteins
– Major constituent of the
and can promote atheroschlerosis
surfactant preventing adherence,
due to surface tension, of the Sphingomyelins
inner surfaces of the lungs.
– Absence: Respiratory distress – Sphingomyelins do not contain a
syndrome glycerol backbone, they have a
sphingosine backbone instead.
PHOSPHATIDYLETHANOLAMINE (Cephalin) and – Sphingomyelins do not contain an
PHOSPHOTIDYLSERINE (tissues) ester; their single fatty acid is bonded
to the backbone by an amide bond.
– Ethanolamine or serine replaces
choline

PHOSPHATIDYLETHANOLAMINE (Cephalin) and

PHOSPHOTIDYLSERINE

– PHOSPHOTIDYLSERINE (tissues) –
Serine replaces choline

PHOSPHATIDYLINOSITOL
PLASMALOGENS
• Precursor of second messenger • 10% of the phospholipids of the
• Inositol is present as brain and muscle
stereoisomer, myoinositol • Resemble
• Phosphatidylinositol 4,5- phosphatidylethanolamine (ether
biphosphate important linked)
constituent of the cell membrane • Alkyl radical is an unsaturated
phospholipids and cleaved into alcohol
diacylglycerol and inositol • Choline, serine or inositol ---- may
triphosphate (internal signals or be substituted for ethanolamine
second messenger)

CARDIOLIPIN

• bisphosphatidyl glycerol
• Is an important component of the
inner mitochondrial membrane,
where it constitutes about 20% of
the total lipid
• It serves as an insulator and
stabilizes the activity of protein
 SPHINGOMYELINS GLYCOLIPIDS (GLYCOSPHINGOLIPIDS)

• Found in large quantities in brain

and nerve tissues • Distributed in every tissue of the body
• Yields fatty acid, phosphoric acid, o – Nervous tissues (brain)
choline, and a complex amino o – Plasma membrane – cell
alcohol, sphingosine surface carbohydrates
• Glycosphingolipids
o – Major glycolipids in animal
tissues
o – Ceramide + sugar
• GALACTOSYLCERAMIDE
o – Major sphingolipid of brain
& other nervous tissue, C24
fatty acids
• GANGLIOSIDES
• Are complex glycosphingolipids
derived from glucosylceramide
that contain in addition one or
more molecules of a sialic acid

• NEURAMINIC ACID

– principal sialic acid found in

human tissues.
•An example of sphingomyelin:
• GM3

– contains ceramide, one

molecule of glucose, one
molecule of galactose and
one molecule of NeuAc –
The simplest gangliosides
in tissues

Derived Lipid
•The myelin sheath, the coating that
surrounds nerve cells, is rich in – product of simple and
sphingomyelins. compound lipid upon
hydrolysis.

• Fatty acids
CERAMIDE
– occur in plant and animal
• Sphingosine plus amino acid
foods
• Structure found in
– also exhibit in complex
glycosphingolipids
forms with other
substances – obtained
from hydrolysis of fats
– usually contains an even
number of carbon atoms
and are straight chain
derivative
 • Glycerol •Two important classes of steroid hormones include
• Steroids sex hormones and adrenal cortical steroids.
• Other alcohols
•The female sex hormones are estrogens and
• Fatty aldehydes
progestins.
• Ketone bodies
• Hydrocarbons, Lipid-soluble •The male sex hormones are called androgens.
vitamins
• Hormones * Acylglycerols, Steroid Hormones Female Sex Hormones: Estrogens
cholesterol, and cholesteryl ester •The estrogens estradiol and estrone control
are uncharged, so are termed development of secondary sex characteristics,
NEUTRAL LIPIDS regulate the menstrual cycle, and are made in the
NON-HYDROLYZABLE LIPIDS ovaries.

Focus on Health & Medicine Cholesterol

Steroids

• are a group of lipids whose carbon

skeletons contain several fused rings:

Female Sex Hormones: Progestin

•The progestin progesterone is called the “pregnancy

hormone”; it is responsible for the preparation of the
uterus for implantation of a fertilized egg.

• This nucleus, partially or completely

hydrogenated, is generally substituted by
methyl groups at C10 and C13.

• A chemical group (ketone, hydroxyl...) or

an alkyl side-chain may also be present at C17

•Cholesterol, the most prominent steroid, is

synthesized in the liver and found in almost all Male Sex Hormones: Androgens
body tissues.
•Testosterone and androsterone are androgens
made in the testes.

•They control the development of secondary sex

characteristics in males.

•It is obtained in the diet from many sources,

including meat, cheese, butter, and eggs.

Steroid Hormones

•A hormone is a molecule that is synthesized in one

part of an organism, which then elicits a response at a
different site.
 •Prolonged use of these steroids can have undesired
side effects, including bone loss and high blood
Anabolic Steroids
pressure.
• Synthetic androgen analogues, called
•Prednisone, a synthetic alternative, has similar anti-
anabolic steroids, promote muscle
inflammatory properties.
growth.
• They have the same effect as Fat-Soluble Vitamins
testosterone, but are more stable, so
•Vitamins are organic compounds required in small
they are not metabolized as quickly.
quantities for normal metabolism and must be
• They have come to be used by athletes
obtained from the diet.
and body builders, but are not permitted
in competitive sports. •Vitamins are either water soluble or fat soluble.
• Prolonged use of anabolic steroids can
cause physical and psychological •The four fat-soluble vitamins (A, D, E, and K) are
problems. found in fruits, vegetables, fish, liver, and dairy
products.
•Some examples of anabolic steroids:
•They are stored in adipose cells to be used when
needed.

Vitamin A

• is found in liver, fish, and dairy products, and is

made from β-carotene.
• It is needed for vision and for healthy mucous
membranes.
• Vitamin A deficiency causes night blindness and
dry eyes and skin.

Adrenal Cortical Steroids

•Three examples of adrenal cortical steroids are:

Vitamin D

• can be synthesized from cholesterol.

• It can be obtained in the diet from many foods,
especially milk, and helps regulate Ca and K
metabolism.
• A deficiency of vitamin D causes rickets (bone
malformation).

Aldosterone

• regulates blood pressure and volume by

controlling the concentration of Na+ and K+ in
body fluids. ERGOSTEROL
• Cortisone and cortisol serve as anti-inflammatory
agents, which also regulate carbohydrate • Precursor of vitamin D2
metabolism. • Occurs in plants and yeast
• It is turned into viosterol by UV light, and is then
converted into ergocalciferol (a form of Vitamin
D)
• Acquires antirachitic properties when irradiated
with UV light
• A component of fungal cell membranes, serving
the same function that cholesterol serves in
animal cells • Prostaglandins are responsible for inflammation.
• Aspirin and ibuprofen relieve pain and
Vitamin E inflammation by blocking the synthesis of these
molecules.
• is an antioxidant, protecting unsaturated side
• Prostaglandins also decrease gastric secretions,
chains in fatty acids from unwanted oxidation.
inhibit blood platelet aggregation, stimulate
• Deficiency of vitamin E causes numerous
uterine contractions, and relax smooth muscles.
neurological problems, although it is rare.
• There are two different cylcooxygenase enzymes
responsible for prostaglandin synthesis called
COX-1 and COX-2.
• COX-1 is involved in the usual production of
prostaglandins.
• COX-2 is responsible for additional
prostaglandins in inflammatory diseases like
arthritis.
Vitamin K • Nonsteroidal anti-inflammatory drugs (NSAIDs)
• regulates the synthesis of clotting proteins like aspirin and ibuprofen inactivate both COX-1
(prothrombin), and deficiency of this leads to and -2, but increase risk for stomach ulcer
excessive or fatal bleeding. formation.
• Drugs sold as Vioxx, Bextra, and Celebrex block
only the COX-2 enzyme without affecting gastric
secretions.

Asthma and Leukotrienes

 Asthma is characterized by chronic

inflammation, so inhaled steroids to reduce
this inflammation are commonly used.
Prostaglandins and Leukotrienes  Leukotrienes are molecules that contribute to
the asthmatic response by constricting
• Prostaglandins and leukotrienes are two types of smooth muscle of the lung.
eicosanoids.  New asthma drugs act by blocking the
• All eicosanoids are very potent compounds, synthesis of leukotriene C4 , which treat the
which are not stored in cells, but rather disease instead of just the inflammation
synthesized in response to external stimulus. symptoms.
• Unlike hormones they are local mediators,
performing their function in the environment in POLYPRENOIDS
which they are synthesized
• Not steroids, but synthesized like cholesterol.
Prostaglandins
UBIQUINONE-
- Prostaglandins are carboxylic acids that contain a o participates in respiratory chain in
five-membered ring and have a wide range of mitochondrion.
biological activities. DOLICHOL
o takes part in glycoprotein synthesis
by transferring carbohydrate residues
to asparagine residues of polypeptide
 ISOPRENOID AMPHIPHATIC LIPIDS
 rubber, camphor, fat soluble- Vit A, D, E &
– Contain predominantly nonpolar groups
K and -carotene (provitamin A)
plus a polar group.
LIPID PEROXIDATION – Molecule is partly hydrophobic and
hydrophilic.
• Lipids exposed to oxygen (Auto-oxidation).
– Include fatty acids, phospholipids,
• A chain reaction providing a continuous supply of
sphingolipids, bile salts, and cholesterol.
free radicals.
– Oriented at oil:water interfaces with the
Effects of peroxidation include:
polar group in water phase and the
o deterioration of food (rancidity)
nonpolar group in the oil phase.
o damage of tissue (cancer,
– Basic structure of biologic membranes
inflammation, atheroschlerosis and
(bilayer).
aging) caused by free radicals
containing methylene-interrupted
double bonds

PEROXIDATION

• Catalyzed in vivo by heme compounds and by

lipoxygenases (platelets and leukocytes)
• Other products of auto-oxidation (or enzymatic
oxidation) of physiologic importance include;
o Oxysterols – formed from cholesterol
o Isoprostanes – prostanoids

ANTIOXIDANTS

• Control and reduce lipid peroxidation

• Antioxidants for food are propyl gallate, BHA,
BHT
• Naturally occuring antioxidants include;
o Vitamin E (tocopherol) is lipid soluble
o Vitamin C and urate are water
soluble
o Beta-carotene

CLASSES OF ANTIOXIDANTS

• Preventive antioxidants
o reduce the rate of chain initiation.
 Catalases and Peroxidases –
 glutathione peroxidase
(reacts with ROOH) –
 Selenium – EDTA, DTPA
(Chelators of metal ions)

• Chain-breaking antioxidants

– interfere with chain propagation

 Superoxide dismutase
 trap superoxide free radicals
 Urate
 Vitamin E – lipid phase trap ROO
radicals