What are Lipids?

- Are heterogenous class of Biomolecules Include fats and oils, waxes, phospholipids, steroids
(like cholesterol) and some other related molecules

3 major roles
1. STORES energy within fat cells
2. Part of the MEMBRANES
3. As CHEMICAL MESSENGERS

Classification by Structure
A. SIMPLE LIPIDS
B. COMPLEX LIPIDS
C, STEROIDS
D. PROSTAGLANDINS, THROMBOXANES, & LEUKOTRIENES

Classification based on composition

1. Fatty acids
2. Lipids containing glycerol
a. Triglycerides or neutral fat
b. Phosphoglycerides or phospholipids
c. Cardiolipin or diphosphatidyl glycerol
3. Lipids not containing glycerol
a. Sphingolipids
b. Waxes
c. Terpenes
d. Steroids
4. Lipids combined with other compounds

1. Fatty acids
*With type formula of RCOOH
*Maybe saturated (all single bonds) or unsaturated (with double or triple
bonds)
*Solubility in water decreases with increasing carbon chain
Notes on Systematic Naming of Fatty Acids
* For saturated FA's, change the ending -e of alkanes to -oic acid
* If unsaturated, change the -e ending to -enoic acid
* C atoms are numbered from the carboxyl C designated as C- 1; C’s adjacent to it are
numbered 2,3,4,etc. and are also known as a. β .y respectively and the terminal methyl C is
known as the ω or omega-carbon
* The position of the double bond is indicated by Δ n
* ω 9 (omega-9) indicates a double bond on the ninth carbon counting from the ω -carbon, most
common are ω 9, ω 6, and ω 3 families

Essential fatty acids

1. Linoleic acid
2. Linolenic acid
3. Arachidonic acid

Triglycerides or neutral fats

*Are esters of glycerol (a triol) and three fatty acids
*“Saponification”
*In the body, triglycerides are hydrolyzed by lipases; excess amounts are stored in adipose
tissues (serves as component of fat storage cells)

Common among fatty acid component of TAG

1. Practically, all FAs are UNBRANCHED carboxylic acids

2. Size ranges from 10 to 20 C's

3. They contain an EVEN number of C atoms (body builds them from acetate units so 2 C
atom's are added at a time)

4. No other functional groups apart from — COOH, although USFA has double bonds

5. For USFA present, the cis configurations predominates

Physical properties of TAG
1. Animal fats are solid at room temperature while plant oils are liquid at room temperature
2. HYDROGENATION
FAwith C to C double bonds can be reduced to single bonds by treating them with H, and a
catalyst (a simple process); converts unsaturated liquid oils to fat
3. SAPONIFICATION
Process of alkaline HOH of fats/oils producing soap and glycerol
Phospogylcerides or phospolipids
*Parent compound is "phosphatidic acid"
*Considered as a COMPLEX lipid
*2 types: Glycerophospholipids that contain glycerol and Sphingolipids that contain sphingosine
*Are “amphiphatic” or “amphiphilic” molecule
*Are well-adapted in the cell membrane

Classes of phospolipids
The nitrogen-containing compound attached will identify a particular phospholipids
- Lecithin = glycerol + FA + P O−3
4 + choline (major component of egg yolk; an excellent
emulsifier and used in mayonnaise)
- Cephalin = glycerol + FA+ P O−3
4 + ethanolamine
- Phosphatidyl serine = glycerol + FA+ P O−3
4 + serine
- Phosphatidyl inositol = glycerol + FA + P O−3
4 + inositol {integral part of cell membrane and
signaling molecules)
Cardiolipid or diphosphatidyl glycerol
*Glycerol + 2 moles of phosphatidic acid
*A constituent of the mitochondrial membranes and used in the serological diagnosis of syphilis
(a sexually transmitted disease caused by the bacterium - “Treponema pallidum”)

LIPIDS NOT CONTAINING GLYCEROL

Sphingolipids
Discovered by Johann Thudichum and named after the Sphinx

Parent compound is called “ceramide” made up of sphingosine and fatty acid

Esterification of ceramide with phosphoryl choline yields “Sphingomyelin” (the major

phospho-sphingolipid and found in myelin sheaths}

If ceramide is linked to simple sugars (either glucose or galactose), a “Glycosphingolipid” is

formed

Types of glycosphingolipids
- Cerebrosides or neutral glycosphingolipids
- Ganglioside or acidic glycosphingolipids
Lipid storage diseases
Characterized by defective or missing enzymes needed to decompose the complex lipids

— RESULT: accumulation of complex lipids

— The best way to prevent is GENETIC COUNSELLING

Waxes
- Esters of fatty acids and long-chain monohydric alcohol
- Includes cetyl palmitate, beeswax, lanolin (from lamb's wool), carnauba wax (from
Brazilian palm tree}, spermaceti (from whales)
- Paraffin wax and earwax are peculiar waxes

Terpenes
Polymers of isoprene units and give rise to rubber, steroids and carotenoids

Steroids
- Contain the Perhydrocyclopentanophen anthrene (CPPP) or steroid nucleus
- Includes cholesterol, the bile acids (fat emulsifiers), the adrenocortical hormones, the
sex hormones (androgens, progesterone, and estrogen), prostaglandins (lipids _ like
hormones}, and squalamine
Cholesterol
- The most abundant steroid in the human body; a sterol since OH or alcohol. group is
attached to c-3 of ring A in the CPP nucleus
- Component of most animal membranes and Q precursor in the synthesis of bile acids,
steroid or sex hormones, and Vitamin D

Blood Cholesterol Test

- Liebermann - Burchard Test . is a chemical estimation of cholesterol. The cholesterol is
react as a typical alcohol with a strong .concentrated acids: the product are colored
substances.
- Acetic anhydride are used as solvent and dehydrating agents. and the sulfuric acid is
used as dehydrating and oxidizing agent .
- A positive result is observed when the solution becomes red or pink . then purple . blue.
and finally bluish “green color.
Perceived as “bad” despite its essential role in biological processes
— Amounts in the body is regulated when serum cholesterol exceeds 150 mg/100 mL
— High levels in the blood is not directly related to high risk of heart disease; HDL to LDL ratio
is more directly linked to heart disease

LPP carriers of cholesterol

HDL or High Density Lipoprotein — Labelled as “Good cholesterol”
LDL or Low Density Lipoprotein (“Bad” cholesterol)
- Deposits cholesterol along the arteries producing — cholesterol “plaque” decreasing the
diameter of the arteries increasing the blood pressure
HDL/LDL ratio = if high (lower risks of heart disease; if low (higher risks of heart disease -
ATHEROSCLEROSIS)

Dynamics of cholesterol and diet

*serum cholesterol level controls the amount of cholesterol synthesized in the liver
*Diet low in cholesterol and SFA usually reduce serum cholesterol
*“Statin” drugs inhibit cholesterol synthesis in the liver
— MOA: Inhibit the enzyme HMG-CoA reductase
*Premenopausal women have more HDL than men;
HDL levels can be increased by exercise and weight loss

Steroid hormones
Cholesterol is the starting material for the synthesis of steroid hormones
— Aliphatic side chain on the D-ring is shortened by the removal of a 6-C unit and the
secondary alcohol on C3 is oxidized to a ketone producing PROGESTERONE

Adrenocorticoid hormones (ACTH)

Secreted by the adrenal glands
2 groups:
— (1) MINERALOCORTICOIDS —- regulating ions concentrations particularly Na+ and K+ and

— (2) GLUCOCORTICOIDS - controls CHO metabolism

Aldosterone
— Increased secretion enhances reabsorption of Na+ and Cl- ions

Cortisol
— The major glucocorticoid; INCREASES glucose and glycogen concentration in the body

Sex Hormones
Testosterone
— Promotes growth of male genital organ, development of secondary male sex characteristics
during puberty (deep voice, facial and body hair)
Estradiol
— The most important female sex hormones: together with its precursor progesterone,
regulates menstrual cycle

Progesterone
— Essential for implantation of the fertilized ovum, so blocking its action terminates pregnancy
— Prevents ovulation during pregnancy

Bile Salt
Are oxidation products of cholesterol
Are POWERFUL DETERGENTS
Are eliminated in the feces
LIPIDS COMBINE WITH OTHER COMPOUNDS

Lipoproteins
Are lipids bound to proteins; transports cholesterol & fats

Classified based on the difference in density

1. Chylomicrons — carry dietary lipids synthesized in the intestines
2. Very Low-Density Lipoprotein (VLDL) -— mostly carries TAG synthesized by the liver
3. Intermediate Density Lipoprotein (IDL)
4. Low-Density Lipoprotein (LDL)
5. High-Density Lipoprotein (HDL)

Proteolipids
Are proteins bound to lipids

Prostaglandis
— Lipid-like hormones synthesized in the body from ARACHIDONIC ACID catalyzed by
cyclooxygenase (COX)
— Have a variety of functions like stimulating uterine contraction and induce labor (PGE2 and
PGF2), lowers BP (PGE2- used to treat asthma in aerosol form), as decongestant (PGE1)-all
catalyzed by COXx-1
-— COX-2 produces prostaglandins in response to inflammation; NSAIDs such as aspirin inhibit
both COX's

Thromboxanes
- INDUCES PLATELET AGGREGATION and is inhibited by aspirin and other NSAID's
- Rationale in giving low dose of aspiring (81 mg) for people at risk for heart attack or
stroke as well as forbidding the patient to take aspirin and other NSAID one week prior to
a planned surgery
- NSAID like iburpofen and indomethacin (powerful painkillers) inhibit aspirin action while
acetaminophen and diclofenac do not

Leukotrienes
- Present mainly wbc (leukocytes) but are present also in other tissues
- Produce long-lasting muscle contraction, especially in the lungs
- With prostaglandin, causes inflammation and fever
- Anti-leukotrienes or anti-asthmatic drugs include Zafirlukast (Accolate) and zileuton
(Zyflo)