- They contain many nonpolar C C and C--H bonds

and few polar bonds resulting in their water

M2: LIPIDS insolubility.
Book: Chapter 21
- Are heterogeneous group of compounds (fats, oils,
steroids, waxes and related compounds), that are
related more by their physical than by their
L1: Introduction to Lipids: Structure, Properties, chemical properties.
and Classification Common properties:
- (1) Relatively insoluble in water
Lipids are a heterogeneous group of molecules, and
- (2) Soluble in non-polar solvents
classified according to insolubility or immiscibility with water.
Lipids do not have building blocks.
Properties of lipids
Sterol
- Greasy to touch ( Grease spot test) leaves a
Phytosterol- from plants
permanent oily stain on paper;
Ergosterol- fungi or protozoa
- Lighter than water;
Cholesterol- mamalia
- Soluble in organic solvent, insoluble in water;
When pure, colorless with bland odor and taste;
Introduction:
- Yellow color in fat is due to carotene (provitamin A)
- This module focuses on lipids, which are
- When heated strongly, it undergoes decomposition
biomolecules that are insoluble in water but readily
forming acrid flammable vapors (acrolein test) and
soluble in organic solvents, such as chloroform or
when ignited, they burn with a sooty flame.
acetone.
Acrolein chemically is propenal
- Lipids occur frequently in nature. They are found in
places as diverse as egg yolks and the human
nervous system and are an important component
of plant, animal, and microbial membranes.
- In terms of chemistry, lipids are a mixed bag of
compounds that share some properties based on
structural similarities, mainly a preponderance of
non-polar groups.

- Egg contains lecithin

Major Roles of Biological Lipids

1. They serve as structural components of biological
membranes.
Classified 2. They provide energy reserves, predominantly in the form
according to their chemical nature, lipids fall into two of triacylglycerols.
main groups: 3. Both lipids and lipid derivatives serve as chemical
I. Hydrolyzable lipids messengers.
● triacylglycerols 4. Lipophilic bile acids aid in lipid solubilization.
● waxes
● phospholipids. Biomedical Importance
II. Fused-ring compounds/ Non-hydrolyzable •Fat stored in adipose tissue serves as thermal insulator in
lipids the subcutaneous tissues and around certain organs;
● steroids • Nonpolar lipids act as electrical insulator, allowing rapid
● fat-soluble vitamins propagation of depolarization waves along myelinated
● eicosanoids nerves;
• Lipoproteins occur in both cell membrane and
Lipids mitochondria, and also serve to transport lipid in the blood.
Introduction to Lipids HDL, LDL and VLDL
- Lipids are biomolecules that are soluble in organic
solvents and insoluble in water. Lipids
- They are not defined by a particular functional • Important dietary constituents
group, thus they have a variety of structures and - High energy value
functions. - Contains fat-soluble vitamins and essential fatty acids
- Essential Fatty Acids (EFA's) Formula: CH3(CH2- twice the number of double
• Are necessary fats that humans cannot synthesize, and bond)nCOOH
must be obtained through diet. •As the number of double bonds in the fatty acid increases,
• Are long-chain polyunsaturated fatty acids derived from the melting point decreases.
linolenic, linoleic, and oleic acids. - increases and decreases is inversely related
with one another
I. CLASSIFICATIONS OF LIPIDS •Stearic acid (mp 71 °C) is a saturated fatty acid
Classification of Based on the "alcohol component"
• Simple lipid: Ester of fatty acid and low molecular
monohydric alcohol
Liquid at room temperature except for vegetable oil
specifically the cocoa butter (solid)
• Fats/fixed oil - ester of fatty acid and glycerol •Oleic acid (mp 16 °C) is an unsaturated fatty acid.
Semi solid except for liquid animal fat which is the Cod liver
oil (source of oleio Vit. A and B)
- Triglycerides (trihydric alcohol)- 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 (yellow wax) ,
head oil of sperm whale (spermaceti), cerumen,carnauba oil,
and lanolin.
Additional notes: Ambergris is an expensive oil coming from
the excrete waste material of sperm whales.

Lipids can be categorized as:

1. Hydrolyzable lipids can be converted into smaller
molecules by hydrolysis.
● triacylglycerols
● waxes
● phospholipids.
2. Nonhydrolyzable lipids cannot be cleaved into smaller
molecules by aqueous hydrolysis.
● steroids
● fat-soluble vitamins
● eicosanoids

Fatty Acids
•Hydrolyzable lipids are derived from fatty acids. - Kinking or kink of fatty acids happens because of
•Fatty acids are carboxylic acids (RCOOH) with long C double bond.
chains of 4-36 C atoms.
•An example is CH (CH2)14COOH (palmitic acid):

Number of C=C’s
Fatty Acids 0 saturated
•Naturally occurring fatty acids have an even number of C 1 monounsaturated
atoms. 2 polyunsaturated
•Saturated fatty acids have no double bonds in their long
hydrocarbon chains. Formula, Suffix FATTY ACIDS: NOMENCLATURE
Formula: CH3(CH2)nCOOH
•Unsaturated fatty acids have 1 or more double bonds • Simplified: Chain length : Double bonds (e.g., 16:0, 18:1)
(generally cis) in their long hydrocarbon chains. Formula, •Carboxyl carbon: C1
Suffix
•Delta: Positions of any double bond: A (specified relative to • POLYUNSATURATED (polyethenoid, polyenoic) acids
C1 by a superscript number indicating the lower-numbered C containing two or more double bonds
in the double bond) • EICOSANOIDS Derived from eicosa- (20 carbon) polyenoic
fatty acids
Arachidonic acid is the major precursors:
• Prostanoids
• Leukotrienes (LTs )
• Lipoxins (LXs)

1. PROSTANOIDS
• Are part of a family of biologically active lipids derived from
the twenty-carbon essential fatty acids or eicosanoids;
• Relates to the products of the cyclooxygenase (COX)
pathway
- Cis because of same side and if it is Trans • Prostanoic acid as the central structural element (parent)
opposite sides (if pababa)
Three main groups
• Prostaglandins (PGS)
• Prostacyclins (PGIs)
• Thromboxanes (TXs)

A. PROSTAGLANDINS (PG)
- Terminal end is the omega carbon *pic*
● Omega-n Nomenclature: alternative - Behave as lipids but act as local
nomenclature applied in human nutrition hormones
- n = the carbon at which the first double bond occurs in the - Synthesized from polyunsaturated
carbon chain (beginning at the end of the chain containing eicosanoic acids (arachidonic acid) to
methyl group) form cyclopentane ring
•Linolenic acid is called an omega-3 acid, because of the - PG1,PG2,PG3 is based on the double
position of the first C=C in the nonpolar chain. bonds in the side chain
- Letters: functional groups
- PGE: keto on the 9th position
- PGF: hydroxy on the 9th
position

B. THROMBOXANES (TX)
Fatty Acids *pic*
•Humans require omega-3 linolenic acid - Cyclopentane ring interrupted with an
•Essential FA O2 atom
•Precursor in the synthesis of eicosapentaenoic acid (EPA) - TX A2 and B2
and docosahexaenoic acid (DHA) - Role in clot formation (thrombosis)
- Antithrombotic (thromboxane
PHYSICAL and PHYSIOLOGIC PROPERTIES OF FATTY inhibitors): clopidogrel, aspirin
ACIDS
2. LEUKOTRIENES and LIPOXINS
• MELTING POINT of even numbered carbon fatty - Formed via the lipooxygenase (LOX) pathway
acids: - Has 3 (leukotrienes) to 4 (lipoxins) conjugated or
• increases with chain length alternating double bonds
• decreases according to unsaturation (Iodine test) - Leukotrienes: proinflammatory agents and causes
• TRIACYLGLYCEROL containing three saturated fatty bronchoconstriction (asthma)
acids of 12 C or more is solid at body temperature Leukotriene inhibitors:
• 18:2 fatty residues are liquid at body temperature - Zyflo- Zileuton
to below 0° c - Accolate- Zafirlukast
• MEMBRANE LIPIDS - must be fluid at all environmental - Singulair- Montelukast
conditions
• More unsaturated than storage lipids SIMPLE LIPIDS

UNSATURATED FATTY ACIDS

• MONOUNSATURATED (Monoethenoid, monoenoic) acids A. WAXES
containing double bond ● are esters formed from a fatty acid and a high
molecular weight alcohol (water insoluble)
 - General Structure:
- Esterification:
- Eg. spermaceti wax which is isolated from the
heads of sperm whale (Physeter macrocephalus) ‘
- cetyl ester wax (synthetic form: prep of cold cream
aka petrolatum rosewater ointment)
- long nonpolar C chains= hydrophobic
- form protective coatings on bird’s feathers and
sheeps wool; also makes up beeswax/yellow wax
(myricyl palmitate)
- yellow wax when bleached becomes white wax
- myricyl palmitate is an ester of mycricyl alcohol
and mycrilic acid
- waxes are hydrolized with water in the presence
of acid or base to re-form carboxylic acid and
alcohol they came from
B. TRIACYLGLYCEROLS (FATS AND OILS)
● 3 esters formed from glycerol and 3 molecules
of fatty acids
- Main storage forms of fatty acids
- Block diagram
*pics*
● Simple triacylglycerols: 3 identical fatty acid
chains
Ex. tristearin
● Mixed triacylglycerol: 2 or 3 different fatty acids
Ex. oleopalmitostearin
General Features:
Saturated triacylglycerol: contain only one saturated fatty
acids; make up most animal fat; solid at room temp
● Absent double bond
● High molecular weight
Unsaturated triacylglycerols: at least 1 unsaturated fatty
acid; make up most vegetable oils; liquid at room
temperature (except cocoa butter or Theobroma cacao)
○ Increase double bonds= decrease MP
(bc of decreased Van der Waals forces
which also decrease MW)
○ Unsaturated triacylglycerols: lowers the
risk of heart disease, decreasing
cholesterol in the blood
○ Omega-3 fatty acids lowers risk of herat
attack
○ Trans fats: synthesized fats increase
cholesterol levels, benefits are lost
● Fats have higher MP; solid at room temp
○ Animal fats, lard, tallow
○ Derived from fatty acids with few double
bonds
● Oils are liquid at room temp, lower MP
○ Derived from FA with larger number of
double bonds
○ “Natutulog na mantika”= more
unsaturated FA)
Fats and oils in Diet
● Fats: used to build cell membranes,
insulate the body, store energy for later
use (adipose)
● No more than 20-35% of a caloric
intake should come from lipids.
● High intake of saturated triacylglycerol=
heart disease
● Saturated fats stimulate cholesterol
synthesis> build up of cholesterol
paques in arteries (atherosclerosis)
HBP, heart attack, stroke
Hydrolized with water in the presence of acid, base, or
enzymes (metabolism)
- If saturated fatty acids are hydrolized it will
contribute more to cholesterol biosynthesis> risk of
CVDs
Metabolism in Human body
● Adipose: Cushion to internal organs
● Muscle wasting: swelling or shrinking of adipose
cells during weight gain/loss, but they do not
increase or decrease in number
● Metabolize triacylglycerols for energy; esters are
hydrolyzed by lipases (enzyme)
● Complete metabolism yields CO2, H2O, and great
deal of energy
COMPOUND LIPIDS
● Esters of fatty acids, alcohols and another
compounds
A. PHOSPHOLIPIDS:
- Fatty acid and alcohol plus a phosphoric
acid residue
- Frequently nitrogen-containing bases
and other substituents,
(glycerophospholipids the alcohol is
glycerol; sphingophospholipids the
alcohol is spingosine)
● Lipids that contain a P atom
● Common Types:
○ Phosphoacylglycerols
○ Spingomyelins
*block diagram*
● Derivatives of phosphatidic acid: intermediate in
the synthesis of triacylglycerols
● Products of hydrolysis: phosphatidic
acid,phosphate group, glycerol, FA
Phosphoacylglycerol: Main component of most cell
membrane (phospholipids)
● Resembles triacylglycerol but the 3rd fatty acid is
replaced with phosphodiester bonded to an
alcohol.
● Two FA: non polar tails
● Phosphate group: polar head
● Main types:
 ○ cephalin (phosphatidylethanolamine)
○ Lecithin (phosphatidylcholine)
Lecithins (phosphatidylcholines)
- Most abundant phospholipids of cell membrane;
large portion of the body’s storage of choline
- Found on egg yolk
- Lipid lowering
● Choline: important in nervous transmission
(acetylcholine); storage of labile methyl group
● Dipalmitoyl lecithin: surface-active agent major
constituent of surfactant preventing adherence
due to surface tension (inner surface of the lungs);
absence leads to RDS or respiratory distress
syndrome
Phosphatidylethanolamine (cephalin) and
phosphatidylserine (tissues)
- Ethanolamine or serine replaces choline
Phosphatidylinositol (IPC)
- Precursor of 2nd messenger
- Inositol is present as a stereoisomer, myoinositol
- Phosphatidylinositol 4,5-biphosphate
constituent of cell membrane phospholipids and
cleaved into diacylglycerol and inositol
triphosphate (internal signals or 2nd messenger)
- Structure found in glycospingolipids
B. GLYCOLIPIDS
● Glycosphingolipids: FA + sphingospine +
carbohydrate
- Found in evrey tissue of the body (Nervous
tissues-brain, plasma membrane-cell surface
carbohydrates)
- major lipids in animal tissues; ceramide + sugar
● Galactosylceramide: major sphingolipid of brain
and other nervous tissue, C24 fatty acids
● Ganglioslides: complex glycoshingolipids
derived from glucosylceramide that contain an
addition one or more molecules of a sialic acid
○ Neuraminic acid: principal sialic acid
analog found in human tissues
○ GM3: contains ceramide,one molecules
of glucose, galactose and NeuAc;
simplest gangliosides in tissues
DERIVED LIPIDS
:

Cardiolipin
- Major lipid of mitochondrial membrane
- Lysophospholipid
- Intermediates in the metabolism of
phosphoglycerols
- Lysophophatidylcholine: important
inthe metabolism and interconventions
of phospholopids
- Found in oxidized lipoproteins and Derived Lipid - product of simple and compound lipid
can promote atherosclerosis upon hydrolysis.
Plasmalogens
- Phospholipids of the brain and muscle (10%)
- Resemble phosphatidylethanolamine
(ether-linked)
- Alkyl radical: unsaturated alcohol
- choline , serine , or inositol may be substituted for
ethanolamine
NONHYDROLYZABLE LIPIDS
Spingomyelins
- Does not contain a STEROIDS
glycerol backbone, - lipids whose C skeleton contain several fused rings
instead they have a -CPPP nucleus
sphingosine
backbone
- Does not contain
ester, their single FA is
bonded through an
amide bond.
- Found in large amounts in brain and nerve tissues
- Produces FA, phosphoric acid, choline, complex
amino alcohol, spingosine
Ceramide
- Spingosine + amino acid
CHOLESTEROL
- Most prominent steroid, synthesized in the
liver, found in almost all body tissues
•All eicosanoids are very potent compounds, which are not
stored in cells, but rather synthesized in response to external
stimulus.
•Unlike hormones they are local mediators, performing their
function in the environment in which they are synthesized.

*no systemic effect

Prostaglandins
•Prostaglandins are carboxylic acids that contain a
five-membered ring and have a wide range of biological
activities.

STEROIDAL HORMONE
- Hormone: a molecule synthesized in one part of
an org then elicits a response at a different site
- Classes of steroidal hormone: sex hormone,
adrenal cortical steroids
- Female sh:
estrogen
Prostaglandins
- Estradiols and estrone: secondary sex
- Prostaglandins are responsible for inflammation.
charactreistics, mens cycle, made in
- Aspirin and ibuprofen relieve pain and
ovaries
inflammation by blocking the synthesis of these
progestins
molecules.
- “Pregnancy hormone”
- Prostaglandins also decrease gastric secretions,
- Male:
inhibit blood platelet aggregation, stimulate uterine
Androgens: testosterone and androsterone (made
contractions, and relax smooth muscles.
in the testes)
- There are two different cyclooxygenase enzymes
responsible for prostaglandin synthesis called
- ANABOLIC STEROIDS: promote muscle growth;
COX-1 and COX-2.
cannot metabolize as quickly; can cause
physical/psych problems
Selective: either COx-1 or Cox-2 lang
- ADRENAL CORTICAL STEROIDS:
COXIBS: block only the COX-2 enzymes without affecting
- aldosterone(regulates BP),
gastric secretions (ex. Celecoxib, Vioxx, Bextra, Celebrex)
- cortisone & cortisol (anti-inflammatory
unlike aspirin, ibuprofen which should be taken with meal.
agents/regulate carbohydrate
metabolism)
- COX-1 is involved in the usual production of
- Side effects: Bone loss and high bp
prostaglandins.
- Prednisone: synthetic alternative for
- COX-2 is responsible for additional prostaglandins
anti-inflammatory
in inflammatory diseases like arthritis.
- Nonsteroidal anti-inflammatory drugs (NSAIDs)
FAT-SOLUBLE VITAMINS
like aspirin and ibuprofen inactivate both COX-1
- A,D,E,K
and -2, but increase risk for stomach ulcer
- Found in fruits, vegetables, fish, liver,
formation.
dairy products
- Drugs sold as Vioxx, Bextra, and Celebrex block
- Stored in adipose cells
only the COX-2 enzyme without affecting gastric
secretions.
ERGOSTEROL
Asthma and Leukotrienes
- Precursor of vit D2
- Asthma is characterized by chronic inflammation,
- Occurs in plants and yeast
so inhaled steroids to reduce this inflammation is
- Turned into viosterol, converted to ergocalciferol
commonly used.
(form of vit D)
- Leukotrienes are molecules that contribute to the
- Antirachitic properties when irradiated w/ UV
asthmatic response by constricting smooth muscle
light
of the lung.
- Component of fungal membranes
- New asthma drugs act by blocking the synthesis of
leukotriene C., which treat the disease instead of
Focus on Health & Medicine
just the inflammation symptoms.
Prostaglandins and Leukotrienes
•Prostaglandins and leukotrienes are two types of
* Leukotrienes: must be inhibited bc it causes
eicosanoids.
bronchoconstriction (asthma)
POLYPRENOIDS
- Not steroids, but synthesized like cholesterol.
- UBIQUINONE- participates in the respiratory chain
in mitochondrion.
- DOLICHOL - takes part in glycoprotein synthesis
by transferring carbohydrate residues to
asparagine residues of polypeptide
- ISOPRENOID - rubber, camphor, fat soluble- Vit A,
D, E & K and B-carotene (provitamin A).
-
LIPID PEROXIDATION
- Lipids exposed to oxygen (Auto-oxidation).
- A chain reaction providing a continuous supply of
free radicals.
- 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 - Contain predominantly nonpolar groups plus a
polar group.
* use antioxidant to retard the effects - Molecule is partly hydrophobic and
ANTIOXIDANTS hydrophilic.
- Control and reduce lipid peroxidation - Include fatty acids, phospholipids,
- Antioxidants for food are propyl gallate, sphingolipids, bile salts, and cholesterol.
BHA, BHT - Oriented at oil:water interfaces with the polar
- Naturally occuring antioxidants include; group in water phase and the nonpolar group
● Vitamin E (tocopherol) is lipid soluble in the oil phase.
● Vitamin C and urate are water soluble - Basic structure of biologic membranes
● Beta-carotene (bilayer).
PEROXIDATION
- Catalyzed in vivo by heme compounds and by C. OTHER COMPLEX LIPIDS
lipoxygenases (platelets and leukocytes) - Sulfolipids and aminolipids
- Other products of auto-oxidation (or enzymatic - Lipoproteins
oxidation) of physiologic importance include;
● Oxysterols - formed from cholesterol
● Isoprostanes - prostanoids
*Butylated hydroxyanisole, hydroxytoluene
CLASSES OF ANTIOXIDANTS
● Preventive antioxidants - 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