Lipids and Related

Substances

Collective term for fixed oil, fats

and waxes.
Lipids
• Are heterogeneous group of compounds
(fats, oils, steroids, waxes and related
compounds), that are related more by
their physical than by their chemical
properties.
• Common properties:
▫ Relatively insoluble in water
▫ Soluble in non-polar solvents
 Properties of Lipids
• Greasy to touch, leaves a permanent oily stain on
paper;
• Lighter than water;
• Soluble in organic solvent, insoluble in water;
• When pure, colorless with bland odor and taste;
• Yellow color in fat is due to carotene
(provitamin A);
• When heated strongly, undergoes decomposition
forming acrid flammable vapors and when
ignited, they burn with a sooty flame.
Lipids
• Important dietary constituents
▫ High energy value
▫ Contains fat-soluble vitamins and essential
fatty acids
▫ Essential Fatty Acids (EFA’s)
 Are necessary fats that humans cannot
synthesize, and must be obtained through
diet.
 Are long-chain polyunsaturated fatty acids
derived from linolenic, linoleic, and oleic
acids.
Biomedical Importance
Major Roles of
Biological Lipids
• They serve as structural components of
biological membranes;
• They provide energy reserves, predominantly
in the form of triacylglycerols;
• Both lipids and lipid derivatives serve as
vitamins and hormones; and
• Lipophilic bile acids aid in lipid solubilization.
 IMPORTANCE OF LIPID
BIOCHEMISTRY
• Obesity, Diabetes mellitus,
Atherosclerosis
• Role of various polyunsaturated fatty acids
in nutrition and health
Classification of Lipids
• 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, cerumen,
carnauba oil, and lanolin.
Classification of Lipids
Classification of Lipids
Classification of Lipids
Precursor and Derived Lipid –
product of simple and compound lipid upon
hydrolysis.
• Fatty acids • Micronutrients
• Glycerol • Hormones
• Acylglycerols, cholesterol,
• Steroids and cholesteryl ester are
• Other alcohols uncharged, so are termed
• Fatty aldehydes NEUTRAL
• Ketone bodies LIPIDS
• Hydrocarbons
• Lipid-soluble vitamins
 Fatty Acids
• Are aliphatic carboxylic acids that occurs in
plants and animal foods;
• Occur mainly as esters of natural fats and oils
but do occur in the unesterified form as free
fatty acids (transport form found in the
plasma)
• In natural fats, they are usually straight-chain
derivatives containing an even number of
carbon atoms.
 Fatty Acids
 SATURATED – no double bonds
 UNSATURATED – containing one or
more double bonds

• What is the general formula for:

▫ Saturated fatty acids: ________
▫ Unsaturated fatty acids: _______
Structure of Fatty Acids
Structure of Fatty Acids
Structure of Fatty Acids
 Geometric isomerism in
unsaturated fatty acid
• cis
▫ The acyl chain are
on the same side of
the bond
▫ Oleic acid
• trans
▫ The acyl chain is on
the opposite side
▫ Elaidic acid
NOMENCLATURE
 NOMENCLATURE
• Adjacent to carboxyl C as 2, 3 and 4 are also
known as , , and  carbons, respectively
• Terminal methyl C is known as  or n-carbon
•  is used conventionally to indicate the number
and position of the double bond, eg., 9, double
bond between C-9 and C-10
PHYSICAL and PHYSIOLOGIC
PROPERTIES OF FATTY ACIDS
 SATURATED FATTY ACIDS
COMMON # OF C
OCCURENCE
NAME ATOMS
Major end product of carbohydrate
Acetic 2
fermentation by rumen organism
Butyric 4 lIn certain fats in small amounts

Valeric 5 (butter)
lEnd product of carbohydrate
Caproic 6 fermentation by rumen organisms
Spermaceti, cinnamon, palm kernel,
Lauric 12
coconut oils, laurels, butter
Nutmeg, palm kernel, coconut oils,
Myristic 14
myrtles, butter
Palmitic 16
Common in all animal and plant
Stearic 18
UNSATURATED FATTY ACIDS
PROSTANOIDS
 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
• The letter component identifies the functional
groups of the cyclopentane ring
▫ PGE – keto group in 9 position
▫ 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)
 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:
 Zyflo – Zileuton
 Accolate – Zarfirlukast
 Singulair - Montelukast
 Omega – 3 Fatty acids

• Anti-inflammatory
• Health benefits among patient who has:
▫ CVDs
▫ Chronic degenerative diseases: Cancer, RA,
Alzheimer’s disease
• Refer to figure 21-5 for the structure of LT and
LX
 TRIACYLGLYCEROLS
(TRIGLYCERIDES)
• Main storage forms of fatty acids
• They are formed by esterification of glycerol with
three fatty acids
• Depending on the content of unsaturated fatty
acids, triglycerides can be solids (fats) or liquids
(oils)
▫ Oils have highly unsaturated fatty acid chains and
are liquid at room temperature
PHOSPHOLIPIDS
• 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
PHOSPHATIDYLCHOLINE
(Lecithin)
DIPALMITOYL LECITHIN
• Major constituent of the surfactant preventing
adherence, due to surface tension, of the inner
surfaces of the lungs.
• Absence from the lungs of premature infants
causes respiratory distress syndrome
PHOSPHATIDYLETHANOLAMINE
(Cephalin)
• Ethanolamine replaces choline.
• A lipid found in biological membranes.
• Cephalin is found particularly in nervous tissue
such as the white matter of brain, nerves, neural
tissue, and in spinal cord.
• Cephalin is the principal phospholipid in bacteria.
 PHOSPHATIDYLSERINE
• Found in most tissues.
• Has a role on “apoptosis”
• US-FDA “qualified claim”
states that:
▫ "Consumption of
phosphatidylserine may reduce
the risk of dementia in the
elderly" and;
▫ "Consumption of
phosphatidylserine may reduce
the risk of cognitive dysfunction
in the elderly".
PHOSPHATIDYLINOSITOL

• Precursor of second messenger

• Inositol is present as stereoisomer, myoinositol
• Phosphoinositides: minor component of CM
 cell signaling and membrane trafficking
• Phosphatidylinositol 4,5-biphosphate
important constituent of the cell membrane
phospholipids and cleaved into diacylglycerol
and inositol triphosphate (internal signals or
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 complexes important to the
electron transport chain
 LYSOPHOSPHOLIPIDS
• Are intermediates in the metabolism of
phosphoglycerols
• Important in the metabolism and
interconversions of phospholipids
(lysophosphatidylcholine)
• Found in oxidized lipoproteins and can
promote atheroschlerosis
 PLASMALOGENS
• 10% of the phospholipids
of the brain and (heart)
muscle
• Resemble
phosphatidylethanolamine
(ether linked)
• Alkyl radical is an
unsaturated alcohol
• Choline, serine or inositol
---- may be substituted for
ethanolamine
 SPHINGOMYELINS
• An example of sphingolipid; present in large
quantities in brain and nerve tissues
• Yields fatty acid, phosphoric acid, choline, and
a complex amino alcohol, sphingosine

SPHINGOSINE
(the atoms in red are derived from glycerol)
 CERAMIDE
• Sphingosine plus amino acid
• Structure found in glycosphingolipids

"n" indicates any fatty acid

may be N-acetylated at this
position
 GLYCOLIPIDS
(GLYCOSPHINGOLIPIDS)
• Distributed in every tissue of the body
▫ Nervous tissues (brain)
▫ Plasma membrane – cell surface
carbohydrates

• Glycosphingolipids
▫ Major glycolipids in animal tissues
▫ Ceramide + sugar
 GLYCOLIPIDS
(GLYCOSPHINGOLIPIDS)
• Galactosylceramide
▫ Major sphingolipid of brain & other nervous
tissue, C24 fatty acids
• Sulfatide is _______
• Glucosylceramide- predominant simple
glycosphingolipids of extraneural tissues
 GLYCOLIPIDS
(GLYCOSPHINGOLIPIDS)
• 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.
• Functions: (1) cell to cell recognition and
communication (2) as receptors both for
hormones and some toxins
 GLYCOLIPIDS
(GLYCOSPHINGOLIPIDS)
• GM3 – contains (1) ceramide (2) one molecule of
glucose (3) one molecule of galactose and (4)
one molecule of NeuAc
▫ The simplest gangliosides in tissues
Nomenclature:
GM3
GM1: derived from GM3, has significant
biological interest  receptor for human cholera
toxin
 STEROIDS

Phenanthrene
rings

Cyclopentane ring

• 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
 Steroids
•The carbon skeleton
of steroids is bent to
Cholesterol
form 4 fused rings

Cholesterol is Estrogen
the “base Testosterone

steroid” from
which your
body produces
other steroids
Estrogen & testosterone are also steroids
 CHOLESTEROL
• Associated with atherosclerosis & heart disease
• Biochemical significance
▫ Precursor of bile acids, adrenocortical
hormones, sex hormones, Vit. D, cardiac
glycosides, sitosterols and alkaloids
• Major constituent of the plasma membrane and
of plasma lipoproteins
• Cholesteryl ester
▫ – OH at 3 position is esterified with long chain
fatty acid
▫ Occurs in animals but not in plants, bacteria
 ERGOSTEROL
• Precursor of vitamin D2
• 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
POLYPRENOIDS
 LIPID PEROXIDATION
• Lipids exposed to oxygen (Auto-oxidation).
• A chain reaction providing a continuous
supply of free radicals (ROS)
• Effects of peroxidation include:
▫ deterioration of food (rancidity)
▫ damage of tissue (cancer, inflammation,
atheroschlerosis and 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;
▫ Oxysterols – formed from cholesterol
▫ Isoprostanes - prostanoids
 ANTIOXIDANTS
• Control and reduce lipid peroxidation
• Antioxidants for food are propyl
gallate, BHA, BHT
• Naturally occuring antioxidants
include;
▫ Vitamin E (tocopherol) is lipid soluble
▫ Vitamin C and urate are water soluble
▫ Beta-carotene
 CLASSES OF ANTIOXIDANTS
• Preventive antioxidants – reduce the rate of
chain initiation.
▫ Catalases and Peroxidases
▫ -Gluthathione 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
 AMPHIPHATIC LIPIDS
• Contain predominantly nonpolar groups plus a
polar group.
• Molecule is partly hydrophobic and hydrophilic.
• Include fatty acids, phospholipids, sphingolipids,
bile salts, and cholesterol.
• Oriented at oil:water interfaces with the polar
group in water phase and the nonpolar group in
the oil phase.
• Basic structure of biologic membranes (bilayer).
AMPHIPHATIC LIPIDS