Chemistry details describe acids p.2
Chemistry details describe acids p.2
Chemistry details describe acids p.2
College of Pharmacy
Biochemistry (1)
1st Semester 2024/ 2025
Lipid chemistry
▪By contrast, they are easily dissolved in organic non-polar solvents such as methanol, acetone, chloroform, and
benzene.
▪Their low water solubility is due to a lack of polarizing atoms (O, N, S, & P)
▪Functions of lipids:
1. High source of energy (9 Kcal/gm)
• Fats are said to be protein sparing because their availability in the diet reduces
the need to burn proteins for energy.
The most commonly fatty acids have even numbers of carbon atoms in an unbranched
chain of 12 to 24 carbons; they are either saturated or unsaturated (one or more double
bonds).
The configuration of the double bonds in most unsaturated fatty acids is cis.
Trans fatty acids correlate with increased blood levels of LDL (bad cholesterol) and
decreased HDL (good cholesterol).
Short chain and unsaturation enhance the fluidity of fatty acids and their derivatives by
lowering the melting temperature.
Fatty acids that contain multiple sites of unsaturation are termed polyunsaturated fatty
acids (PUFAs). The double bonds are separated by at least one methylene group.
1. Simple lipids Example : Fatty acids(FAs)
▪They are present in all organisms as components of fats and membrane lipids. In these
compounds, they are esterified with alcohols.
▪However, fatty acids are also found in small amounts in unesterified form. In this case, they
are known as free fatty acids (FFAs).
▪They usually contain an even number of carbon atoms (because they are synthesized from
two carbon units, acetyl-CoA)
▪They are either saturated (containing no double bonds) or unsaturated (containing one or more
double bonds usually in the cis configuration)
▪Double bonds lower the melting temperature and make FA more fluid
Classification of lipids
1. Simple Lipids
They are esters of fatty acids with various alcohols.
If the alcohol is glycerol, then they are called fats or neutral fats and are also called
triglycerides as all the three hydroxyl groups of the glycerol are esterified.
If all the three fatty acids are same, then they are called simple triglycerides.
If the fatty acids are different, then they are called mixed triglycerides.
Fatty Acids
-Fatty acids in nature as such are not very abundant but are present as ester.
-Fatty acids are represented by general formula R—COOH.
-A fatty acid is a long chain aliphatic carboxylic acid.
General points about them.
1. They are monocarboxylic acids.
2. Number of carbon atoms are even, though odd NO. fatty acids exist but are very rare.
3. They may be saturated or may be unsaturated.
If unsaturated they can be monounsaturated or poly-unsaturated acids.
- Fats obtained from animals are generally saturated and those from plants are commonly
polyunsaturated.
However, these are some exceptions: coconut, palm oils are highly saturated.
Fatty acids in Food: Saturated vs Unsaturated
▪The incidence of cardiovascular disease is correlated with diets high in
saturated FA or trans-form of unsaturated FA
▪Some Vegetable oils (Palm and coconut oils) are rich in saturated FA
▪Margarine made from vegetable oils (by hydrogenation) is much lower in saturated fatty
acids than is butter, which is made from milk fat.
▪In 1869, Mouriès (French chemist) won a prize from Napoleon III for developing a substitute
for butter Margarine
▪However, margarine may present its own cardiovascular risks. Its fatty acids contain
trans-double bonds
▪The effects of trans fatty acids on LDL, HDL, and cholesterol levels are similar to those of
saturated FA (increase the cholesterol)
1. Simple lipids Example : Fatty acids(FAs
▪In Fatty acids, the carbon atoms are numbered from the carboxylic end, which
is known as carbon number 1
▪The carbon atom adjacent to the carboxyl group is known as carbon number
2 or α-carbon, and the next carbon as carbon 3 or β- carbon and the next
carbon 4 or γ-carbon, …etc.
▪The methyl carbon at the other end of fatty acid is known as omega carbon
(ώ-carbon).ώώώ
- The most common (Non – essential ) among the saturated fatty acids are
palmitic acid (C16), stearic acid (C18) but among the unsaturated fatty acid, oleic
acid (C18).
- Unsaturated fatty acids have lower melting point than saturated fatty acids of
same chain length.
- Fatty acids with odd number carbon atoms occur in trace amounts in
terrestrial and marine animals.
- Fatty acids with one to eight carbons are liquids at room temperature while
those with more carbon atoms are solids.
The most common( Non-essential ) fatty acids in neutral fats are:
Functions of EFA
- Although linolenic acid (Omega-3 fatty acid) and arachidonic acid are synthesized by the
body from linoleic acid (Omega-6 fatty acid) but they are synthesized in insufficient
quantity for our needs.
Essential fatty acids are needed for:
ω-3 Eicosapentaenoic (EPA) 20:5; 5,8,11,14,17 Fish oils, cod liver, mackerel, menhaden, salmon oils
family
Docosahexaenoic (DHA)
Fish oils, phospholipids in brain
22:6; 4,7,10,13,16,19
ω-6
Linoleic 18:2; 9,12 Corn, peanut, cottonseed, soybean and many plant oils
family
Arachidonic
Dr. Yasser Kandil acid 20:4; 5,8,11,14
(20) Animal fats and in peanut oil
Essential Fatty acids
1. Simple lipids Example : Triglycerides (TAGs)
▪TAGs are the major energy reserve and the principal neutral derivatives of
glycerol found in animals.
▪If all 3-fatty acids are the same, the molecule is called a simple TAG
▪If the molecule contains 2-3 different fatty acids, called mixed TAG
▪TAGs in animals are found primarily in the adipose tissue (body fat), which
serves as a depot or storage site for lipids.
▪Monoacylglycerols and diacylglycerols also exist, but are far less common than
the TAGs.
1. Simple lipids Example : Triglycerides (TAGs)
1. Simple lipids Example : Triacylglycerols
Also referred to as triglycerides, fats, or neutral fats.
Triacylglycerols are fatty acid esters of glycerol. They are composed of
3 fatty acids each in ester linkage with a single glycerol.
Triacylglycerols containing only saturated fatty acids
Simple triacylglycerols contain only one type of fatty acids;
Mixed triacylglycerols, two or three types.
Triacylglycerols are primarily storage fats; they are present in many foods
In some animals, triacylglycerols stored under the skin serve not only as energy
stores but as insulation against low temperatures.
Neutral lipids : The lipids which are uncharged are referred to as neutral lipids
e.g. triacylglycerols
1. Simple lipids Example : Triglycerides (TAGs)
Simple TAG
Mixed
TAG
Triacylglycerols as stored fuels
▪ The snakes venoms act on both Lecithin and Cephalin to produce Lysolecithin and
Lysocephalin
▪Both Lysolecithin and Lysocephalin act as detergent and dissolves the membranes of RBCs,
causing hemolysis and death.
Proteolipids
▪This is a group of lipid surrounds the protein, making the molecule insoluble in water but
soluble in fat solvents.
▪Proteolipid combinations abundant in brain tissue, but also present in a wide variety of
animal and plant tissues.
▪The protein moiety has a high content of hydrophobic amino acids.
▪They are completely differ from lipoproteins in which the protein surrounds the lipid, making
the molecule soluble in water. They are:
1. Chylomicrons (CM)
2. Very Low Density Lipoproteins (VLDL)
3. Low Density Lipoproteins (LDL)
4. High Density Lipoproteins (HDL)
Lipoproteins (Lipid transport to tissues)
▪Lipids are hydrophobic and insoluble in aqueous environments. Therefore,
special methods are needed to transport them round the body.
▪ Lipoproteins: Macromolecular complexes of lipids and proteins. They are transport fat
molecules, such as triglycerides, phospholipids, and cholesterol within the water-based
solution of the bloodstream to all the cells and tissues of the body.
▪ Five types of lipoproteins:
1. Chylomicrons, transport dietary lipids (exogenous( from intestine to peripheral tissues.
2. Very low density lipoproteins (VLDL), transport the lipids (endogenously synthesized)
mainly TG from liver to peripheral tissues.
3. Low density lipoproteins (LDL) ("bad" cholesterol), transport cholesterol from liver to
peripheral tissues.
4. High density lipoproteins (HDL) ("good" cholesterol), carry cholesterol from
peripheral tissues to liver.
5. Intermediate density lipoproteins (IDL).
3. Derived Lipids
1. Steroids are :
• Animal or human like Cholesterol
• Plant like Ergosterols
▪They contain:
2) 27 carbon atoms
▪The remaining two thirds exists as cholesterol esters in which a long-chain fatty acid
(usually linoleic acid) is attached by ester linkage to the OH group at C3 of the A-ring
Cholesterol Structure
Bile acids
Bile acids are polar derivatives of cholesterol that stored in the
gallbladder after secretion by the liver, and then release into small
intestine to aid in the processes of digestion and absorption of fats
(emulsifying dietary fats to make them more readily accessible to
digestive lipases).
Orientation amphipathic lipids
Micelles
Lipid bilayer
liposome
lipid bilayer
▪The central feature of biological membranes is a double layer of
lipids, which are composed of lipids and proteins
▪Many membrane proteins contain covalently attached
oligosaccharides.
▪ Plasma membrane glycoproteins are always oriented with the
carbohydrate-bearing domain on the extracellular surface.
▪Some of the roles of oligosaccharides in the cell surface:
• Viruses that infect animal cells, such as the influenza virus, bind
to cell surface glycoproteins as the first step in infection.
•Bacterial toxins, such as the cholera and pertussis toxins, bind to
a surface glycolipid before entering
Eicosanoids
▪ Eicosanoids are formed from C20 polyunsaturated essential FAs (In the body, they produce
hormone-like substances that regulate a wide range of functions, including blood pressure,
blood clotting, blood lipid levels, the immune response, and the inflammation response to injury
infection).
Arachidonate and some other C20 essential Fatty acids give rise to eicosanoids which
includes:
1. Prostaglandins (PG),
2. Thromboxanes (TX) ,
3. Leukotrienes (LT) ,
4. Lipoxins.
Eicosanoids
- They serve as mediators of the inflammatory response.
The dietary precursor of the eicosanoids is the essential fatty acid, linoleic
acid(18:2; 9,12 present in corn, peanut, cottonseed, soybean and many plant
oils) using NADH2 to form NAD+ to form Arachidonic acid which is the
predominate precursor of prostaglandin.
Prostaglandins are synthesized from essential fatty acids such as linoleic acid,
linolenic acid and arachidonic acid.
Five type of rings are found in the naturally occurring prostaglandins giving rise
to:
Prostaglandins of A, B, E, F and G or H series.
The prostaglandins which are widely distributed in the body are
PGE1, PGE2, PGE3, PGF1α, PGF2α and PGF3α.
- Synthesis of the PG and TX begins with the oxidative cyclization of free arachidonic
acid to yield PGH2 by prostaglandin endoperoxide synthase—an endoplasmic reticulum
(ER) membrane protein that has two catalytic activities: fatty acid cyclooxygenase
(COX-1&2) and peroxidase.
• Opposing effects of PGI2 and TXA2 limit clot formation.
• There are 2-isozymes of the synthase: COX-1 (constitutive) & COX-2 (non-constitutive).
• Non-steroidal anti-inflammatory drugs (NSAIDs) inhibit both enzymes COX-1 & COX-2.
1- Aspirin inhibits COX-1 & COX-2 irreversibly.
2- But phenylbutazone and indomethacin inhibit COX-1 & COX-2 reversibly
2- Eicosanoids synthesized by 5-lipoxygenase pathway.
Once formed, free radicals attack cell structures within the body.
a. Primary antioxidants: They prevent the formation of new free radical species,
e.g. superoxide dimutase, glutathione peroxidase, ceruloplasmin, transferrin, ferritin.
b. Secondary antioxidants: They remove newly formed free radicals before they can initiate
chain reactions.
These chain reactions can lead to cell damage and further free radical formations, e.g. vitamin
E, vitamin C, β-carotene, uric acid, bilirubin, albumin.
c. Tertiary antioxidants: They repair cell structures damaged by free radicals attack, e.g.
DNA repair enzymes, methionine sulphoxide reductase.
Process of Lipid Peroxidation
- This process is responsible for rancidity of food.
-
This process involves:
i. Initiation
ii. Propagation
iii. Termination.
Deficiency in the antioxidant system can develop for a number of reasons:
a. Low intake of dietary antioxidants
c. Decreases that reduce the absorption of antioxidant nutrients from food, e.g.
Crohn’s disease
d. Renal dialysis
-In these situations the antioxidant system struggles to protect the body from free
radical attack and as a result the risk of free radical-mediated disease increases.
Increased antioxidant status by supplementation may indeed reduce the risk of
certain diseases.
i. High intake of vitamin E has been associated with reduced risk of mortality
from ischemic heart disease.
ii. High incidence of vitamin C and β-carotene have been associated with a
reduced incidence of some cancers.