PRESENTATION OF POLYMER CHEMISTRY

PRESENTED BY: ASMA SOHAIL

ROLL NO: 7152136

Lipids
 Lipids
• Lipids are organic molecules essential for
life that are composed mostly of C, H, O

• 4 types of lipids
– fats (triglycerides)
– phospholipids
– steroids
– waxes
- Family of bimolecules.

- They are not defined by a particular functional

group, thus they have a variety of structures and
functions.

- They are soluble in organic solvents but not in water (nonpolar).

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

bonds and few polar bonds resulting in their water
insolubility.
 Lipids

1. Store energy: fat cells

2. Chemical messengers: find in nerve fibers and hormones.

3. Parts of membranes: insoluble in water

Classification of Lipids
 Lipids

1. Simple lipids: (Waxes, Fats & Oils) Store energy, insulation

2. Complex lipids (Glycerophospholipids) Cell membrane

3. Steroid (Cholesterol & steroid hormones) Chemical messenger

Cell membrane
 Lipids

Lipids can be categorized as:

1. Hydrolyzable lipids can be converted into small molecules

by aqueous hydrolysis.
 Lipids

Lipids can be categorized as:

2. Nonhydrolyzable lipids cannot be cleaved into smaller molecules

by aqueous hydrolysis.
 Fatty Acids & Triglycerides
• glycerol + 3 fatty acids 
triglyceride + H2O
 Hydrolysis

Most hydrolyzable lipids contain an ester.

Hydrolysis: reaction with water.

(breaking a bond and adding the elements of water)

O O
Heat
RCOR' + H2O H+ or enzyme RC- OH + H-OR'
An ester A carboxylic acid An alcohol
 Fatty acids

Hydrolyzable lipids are derived from fatty acids.

Fatty acids are:

COOH Stearic acid
(mp 70°
COOH Oleic acid (
• Long-chain unbranched carbon attached (mp 16°C

to a carboxyl group (-COOH).

COOH Linoleic aci
(mp-5°
• Typically 12-20 carbon atoms.
COOH Linolenic ac
(mp -1
• They have an even number of C atoms.
COOH Steari
(m
• Insoluble in water. COOH Oleic a
(mp
Cis
COOH Linole
 Representative Fatty Acids
C12-C18(also C20) Dietary Fats and Oils
CH3-(CH2)12-COOH (1)
CH3-(CH2)14-COOH (2)
CH3-(CH2)16-CO2H (3)
CH3-(CH2)7-CH=CH-(CH2)7-CO2H (4)
CH3-(CH2)4-CH=CH-CH2-CH=CH-(CH2)7-CO2H (5)
CH3-CH2-CH=CH-CH2-CH=CH-CH2-CH=CH-(CH2)7-CO2H (6)
Name Mp(oC) Class
(1) Myristic acid 58 Saturated C-14
(2) Palmitic acid 63 Saturated C-16
(3) Stearic acid 71 Saturated C-18
(4) Oleic acid 4 Monounsaturated C-18
(5) Linoleic acid - 5 Polyunsaturated C-18
(6) Linolenic acid - 11 Polyunsaturated C-18
 Fatty acids

CH3(CH2)14COOH (palmitic acid)

polar portion = hydrophillic

nonpolar portion = hydrophobic

Hydrophobic portion is much bigger than hydrophilic portion. Insoluble in water

 Saturated and unsaturated Fatty acids

Saturated fatty acids have no double bonds in their long hydrocarbon chains.

Stearic acid: CH3(CH2)16COOH

They are solids at room temperature.

Packed together  Maximum London dispersion forces

COOH
COOH
COOH
COOH
COOH
 Oxidation of Organic Compounds, eg.
fatty acids
O2
-C-C-C-COOH -C-COH-C-COOH
saturated difficult
O2
-C=C-C-COOH -COH-COH-C-COOH
unsaturated easy

oxidation = decomposition = rancidity

more saturated = more stable, ie. longer ‘shelf life’, eg.

commercial baked goods
more unsaturated = faster deterioration, ie. need antioxidants
to protect compounds(in the body?)
Saturated vs. unsaturated
saturated unsaturated
Stearic acid

The packing of fatty

acids depends on their
degree of saturation..

Stearic acid is shown

here in its usual
extended conformation

Saturated fatty acids

are tightly packed and
stabilized by many
hydrophobic
interactions
 Saturated and unsaturated Fatty acids
Unsaturated fatty acids have 1 or more double bonds (generally cis) in their long
hydrocarbon chains.

Oleic acid: CH3(CH2)7CH=CH(CH2)7COOH

They are liquids at room temperature.

They can not pack together  London dispersion forces 

COOH

COOH

COOH
COOH
COOH
Oleic acid

The double bond

(shaded)introduces a
rigid bend in the
hydrocarbon tails
Fatty acids with
one or several such
bends cannot pack
together as tightly
as saturated fatty
acids
 Melting Points
• Increases with size (lesser effect)
• Decreases with unsaturation (greater effect)
 Fatty acids

• The human body is capable of synthesizing most fatty acids from

carbohydrates or other fatty acids.

• Humans do not synthesize sufficient amounts of fatty acids that

have more than one double bond.

• More than one double bond fatty acids are called essential fatty
acids and they must be provided by the diet.

Linoleic acid linolenic acid

 Unsaturated fats
• At room temperature, unsaturated fats are usually liquid.

• Monounsaturated
• Sources: olive, peanut, canola, rape oil, almonds, avocado

• Polyunsaturated
• Sources: sunflower, soybean, corn, and safflower oil, fish oil,
walnuts, sesame seeds, pumpkin seeds, tofu, lard
• Unsaturated fatty acids are sensitive to heat and light damage –
store them in the dark bottles and use for cold or short hot
preparations
 Essential Fatty acids

Omega-n acids n: the position of the first double bond

Linoleic acid is called an omega-6 acid, because of the position

of the first C=C in the nonpolar chain.
 Essential Fatty acids

Linolenic acid is called an omega-3 acid, because of the position of

the first C=C in the nonpolar chain.
Omega-3 and Omega-6 Fatty Acids Compared
 Heart-Healthy
Choices
Cis- and Trans-Fatty Acids Compared
 Waxes

Wax is an ester of saturated fatty acid and long chain alcohol.

Ester bond
Long-chain alcohol Fatty acid

Acid
 Waxes

For example, shown below is the formation of spermaceti wax,

isolated from the heads of sperm whales.

Acid
 Waxes

Because of their long nonpolar C chains, waxes are very hydrophobic.

O
Beeswax CH3(CH2)14 C O(CH2)29CH3
(myricyl palmitate)
hydrophobic hydrophobic
region region

They form protective coatings:

- In plants, they help prevent loss of water and damage from pests.

- In humans and animals, provide waterproof coating on skin and fur.

 Beeswax Carnauba
Coating

Jojoba

Lanolin from wool lotions

 Waxes

Hydrolysis reaction: like other esters, waxes are hydrolyzed.

Heat
 Triacylglycerols (Triglycerides)

Triacylglycerols are:

• Fats and oils (are stored in the body).

• Triesters of glycerol.

• Produced by Fischer esterification.

• Formed when the hydroxyl groups of

glycerol react with the carboxyl groups
of fatty acids.
 Triglycerides: Fats and Oils

• Glycerol + 3
Fatty Acids
• Connected by
ester bonds
 Esterification

glycerol three fatty acids triacylglycerol

O
CH2 OH HO C (CH2)14CH3
O
CH OH HO C (CH2)14CH3
O
CH2 OH HO C (CH2)14CH3 O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3 + 3H2O
Acid

O
CH2 O C (CH2)14CH3
 Triacylglycerols (Triglycerides)

CH2 OH

CH OH Glycerol

CH2 OH

O
G Fatty acid
CH2 O C (CH2)5CH CH(CH2)7CH3
L
O Y
C
CH O C (CH2)5CH CH(CH2)7CH3 Fatty acid
E
O R
CH2 O (CH2)5CH CH(CH2)7CH3 O
C L Fatty acid

Produced by esterification of glycerol (a trihydroxyl alcohol).

 Triacylglycerols (Triglycerides)

Simple triacylglycerols have three identical fatty acid side chains.

Mixed triacylglycerols have two or three different fatty acids.

 Triacylglycerols (Triglycerides)

Saturated triacylglycerols contain only saturated fatty acids.

Monounsaturated triacylglycerols have 1 C=C bond.

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.
 Triacylglycerols (Triglycerides)

Fat: is a triacylglycerol that is solid at room temperature.

Made by more saturated fatty acids (Saturated triacylglycerols).

Meat, milk, butter and cheese (animal sources).

Oil: is a triacylglycerol that is liquid at room temperature.

Made by more unsaturated fatty acids (Unsaturated triacylglycerols).

Corn, cotton seed, safflower and sunflower (plant sources).

 Fat & Health

- Fats are used to build cell membranes, insulate the body, and
store energy for later use.

- It is recommended that no more than 20-35% of a person’s caloric

intake should come from lipids.

- A high intake of saturated triacylglycerols is linked to heart disease.

- Saturated fats stimulate cholesterol synthesis in the liver, which

can lead to cholesterol plaques building up inside arteries.

- The result is high blood pressure, heart attack, and even stroke.

- Unlike other vegetable oils, oils from palm and coconut trees are
very high in saturated fats.
 Fat & Health

- Unsaturated triacylglycerols (omega-3 fatty acids from fish) lower the risk
of heart disease by decreasing the level of cholesterol in the blood.

- However, if the double bond of the unsaturated triacylglycerol is

trans, the beneficial effect is lost.

- Trans fats, which are primarily synthesized instead of naturally

occurring, act like saturated fats and increase the cholesterol levels in the
blood.
 Water in the Camel’s Hump
C54H108O6 + 78O2 54CO2 + 54H2O + zillion Cal (triglyceride
from C18H36O2 x 3 ie glycerol tristearate)
Metabolism requires oxygen, produces energy, carbon dioxide
and water
 Hydrogenation
- Hydrogen adds to the double bonds of unsaturated fats (using transition
metal catalyst such as Ni).
H H H H
Ni
_
C=C + H2 → _C_C_
_

H H
- Melting point is increased.

- Liquid oils are converted to semi-solid fats.

 Hydrogenation

O
CH2 O C (CH2)5CH CH(CH2)7CH3
O Ni
_
CH O C (CH2)5CH _ CH(CH2)7CH3 + 3H2
O
CH2 O C (CH2)5CH CH(CH2)7CH3
O

glyceryl Trioleate CH2 O C (CH2)14CH3

(triolein) O
CH O C (CH2)14CH3
O
CH2 O C (CH2)14CH3

glyceryl tristearate
(tristearin)
 Reactions (“Synthetic”)

Iodine # ( sat. unsat.)

I I
C C C C
I I
C C C C Iodination
H H
C C C C
H H
Hydrogenation

unsaturated saturated
•Used to quantitate
unsaturation in fats
•Product is colorless, I2 is
colored
•Iodine number = grams I2
reacting with 100 g fat
 Hydrolysis

Triacylglycerols are hydrolysis (split by water) in the presence of strong acid

or lipase (digestive enzyme).

O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3 + 3H2O

O
CH2 O C (CH2)14CH3
H
CH2 OH
O
+-
H +Na3H
CH OH O C (CH2)14CH3
H+ or Lipase

H
CH2 OH
Review of Chemical Reactions
 Metabolism of tricaylglycerols

- Humans store energy as triacylglycerols in adipose cells below the

surface of the skin, in the breast area, and surrounding internal organs.

- The number of adipose cells is constant; weight gained or lost causes

them to swell or shrink, but not decrease or increase in number.

- To metabolize triacylglycerols for energy, the esters are hydrolyzed by

enzymes called lipases.

- Complete metabolism of a triacylglycerol yields CO2, H2O, and a

great deal of energy.
 3- Saponification (Basic Hydrolysis)

- Is the process of forming “soaps” (salts of fatty acids).

- Is the reaction of a fat with a strong base (NaOH).

- Splits triacylglycerols into glycerol and the salts of fatty acids.

- With KOH or the oils that are polyunsaturated gives softer soaps
(liquid soaps).

- Soaps are typically made from lard (from hogs), tallow (from cows
or sheep), coconut oil, or palm oil.

- All soaps work in the same way, but have different properties
depending on the lipid source, length of C chain, and degree of
unsaturation.
 3- Saponification (Basic Hydrolysis)
O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3 + 3NaOH

O
CH2 O C (CH2)14CH3
H
CH2 OH

O
Heat
H
CH OH + Na++--O C
3Na (CH2)14CH3
“soap”
Salt of fatty acid
CH2 OH
H
 Soaps

Hydrophobic part: nonpolar

Hydrophilic part: polar (remains in contact with environment)

O
- +
3 RCO N a

Sodium soaps
n)
 Soaps

When soap is mixed with dirt (grease, oil, and …), soap
micelles “dissolve” these nonpolar, water-insoluble molecules.
Soap makes Grease ‘water-soluble’
 Soaps in Hard water
• Curd formation due to insoluble Fe, Ca and
Mg carboxylates
• Water softeners: exchange Na for Fe, Ca
and Mg ions, increasing solubility of the
carboxylates
• Detergents function better in hard water
because sulfonates are soluble
 phospholipids

Phospholipids are lipids that contain a P atom.

Two common types:

 phospholipids

1. Phosphoacylglycerols:

They are the main component of most cell membranes.

Structurally, they resemble a triacylglycerol, except the third fatty acid

has been replaced with a phosphodiester bonded to an alcohol.

Fatty acid

Fatty acid

Amino alcohol
 O

CH2 O C (CH2)16-CH3
O Phosphatidic acid

CH O C (CH2)16-CH3
O

CH2 O P OH

OH
 Alcohols used in phosphoglycerides
CH3
HO CH2 CH2 N+ CH3
CH3

choline

NH2 O

HO CH2 CH C OH HO CH2 CH2 NH2

serine ethanolamine
 phospholipids

1. Phosphoacylglycerols:

There are two types of phosphoacylglycerols:

Ethanolamine Choline
Phosphatidyl serine: a cephalin found in cell
memranes

CH2 O C (CH2)16-CH3
O

CH O C (CH2)16-CH3
O

CH2 O P O CH2 CH NH3+

O- COO-
 phospholipids

2. Sphingomyelins: They differ in two ways:

1. They do not contain a glycerol backbone, they have a sphingosine backbone instead.

sphingosine

2. They do not contain an ester; their single fatty acid is bonded to the backbone
by an amide bond.
Sphingomyelin: sphingosine, fatty acid,
phosphate and choline

Sphingomyelins
found in myelin
sheath around
neurons
 Ceramide: sphingosine + fatty acid

CH3 (CH2)12 CH CH CH OH O

CH NH C (CH2)14 CH3

CH OH

CH3 (CH2)12 CH CH CH OH Sphingosine

CH NH2

CH OH
 phospholipids

2. Sphingomyelins:

The myelin sheath, the coating that surrounds nerve cells, is rich in sphingomyelins.
 phosphoacylglycerols

Nonpolar

O R Polar

Interact with both polar and nonpolar substances.

1. Most abundant lipids in cell membranes (semipermeable).

2. Combine with less polar triglycerides and cholesterol to make them soluble.
 Cell Membrane

Carbohydrate
Phospholipid
bilayer

Nonpolar
Hydrophobic

Polar
Hydrophilic

Semipermeable: selected nutrients can enter and waste products can leave.

Fluid mosaic model

Lecithin(emulsifying agent in egg yolks for
mayonnaise,
candy, cake dough)
The saturated chain is added first, at C1 of glyceryl phosphate.
The reagent is a thiol ester called acyl coenzyme A
This reaction occurs by simple nucleophilic attack on the
carbonyl group of the thiol ester followed by loss of the better
leaving group, the thiolate anion.
The third acylation requires the
phosphate to act as the acylating agent
and a polar alcohol to be introduced to
form a phosphate ester.

The first step is a reaction with cytidine

triphosphate (CTP)
The anhydride is now attacked by an alcohol acting as a
nucleophile.
The attack occurs only at the electrophilic phosphorus centre
further from the nucleotide
(S-Adenosyl
methionine)
 Steroids

Steroids have:

• A steroid nucleus which is

4 carbon rings.

• Attached groups that make the

different types of compounds.

(steroid nucleus)

• No fatty acids.
 Cholesterol

Cholesterol:

• Is the most abundant steroid in the body.

• Insoluble in water (need a water soluble carrier).

• Has methyl CH3- groups, alkyl chain, and -OH

attached to the steroid nucleus.

CH3 CH3
CH3
CH3
CH3

HO
 Cholesterol

Cholesterol:

• Is obtained from meats, milk, and eggs.

• Is synthesized in the liver from fats,

carbohydrates and proteins.

At artery clogged by
• Is needed for cell membranes, brain and cholesterol plaque
nerve tissue, steroid hormones, and
Vitamin D.

• Clogs arteries when high levels form

plaque (because it is insoluble in blood).

• No cholesterol in vegetable and plants.

Gallstones form in gallbladder
 Lipoproteins
Triacylglycerols

Water-soluble form of
lipids
(soluble in blood)

Spherical particles

Polar surface and nonpolar

inner

Transporting lipids through the bloodstream to tissues where they are stored,
Used for energy, or to make hormones.
 Lipoproteins

VLDL: very-low-density lipoprotein Triglycerides and Cholesterol

LDL: low-density lipoprotein (bad Cholesterol) Cholesterol

HDL: high-density lipoprotein (good Cholesterol) Cholesterol

VLDL

Fat storage Heart and

Liver cells muscles
Intestine Energy
and
elimination HDL

LDL
 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.

Two types of steroids hormones:

1. Sex hormones Estrogens & progestins in females

Androgens in males

2. Adrenal Cortical Steroids

 Sex Hormones

Estrogens (Female Sex Hormones):

The estrogens estradiol and estrone control development of secondary

sex characteristics, regulate the menstrual cycle, and are made in the
ovaries.
 Sex Hormones

Progestins (Female Sex Hormones):

The progestin progesterone is called the “pregnancy hormone”; it is

responsible for the preparation of the uterus for implantation of a fertilized
egg.
 Sex Hormones

Androgens (Male Sex Hormones):

Testosterone and Androsterone are androgens made in the testes.

They control the development of secondary sex characteristics in males.

 Sex Hormones

- Synthetic androgen analogues, called anabolic steroids, promote

muscle growth.

- They have the same effect as testosterone, but are more stable, so
they are not metabolized as quickly.

- They have come to be used by athletes and body builders, but

are not permitted in competitive sports.

- Prolonged use of anabolic steroids can cause physical and

psychological problems.
 Sex Hormones

Some examples of anabolic steroids:

(THG or the Clear)

 Adrenal Cortical Steroids

Aldosterone regulates blood pressure and volume by controlling the

concentration of Na+ and K+ in body fluids.

Cortisone and cortisol serve as anti-inflammatory agents, which also

regulate carbohydrate metabolism.

aldosterone
cortisone

cortisol
 Vitamins

They are organic compounds required in small quantities for normal

metabolism.

They must be obtained from the diet (our cells cannot synthesize them).

Vitamins are either water soluble or fat soluble.

The four fat-soluble vitamins (A, D, E, and K) are lipids and

nonpolar.

They are found in fruits, vegetables, fish, liver, and dairy products.

Excess vitamins are stored in adipose cells to be used when needed.

 Vitamins

Vitamin A

It is found in liver, fish, and dairy products, and is made from β-carotene
(the orange pigment in carrots).

It is needed for vision and for healthy mucous membranes.

Vitamin A deficiency causes night blindness and dry eyes and skin.
 Vitamins

Vitamin D

Vitamin D can be synthesized from cholesterol.

It can be obtained in the diet from many foods, especially milk, and
helps regulate Ca and P metabolism.

A deficiency of vitamin D causes rickets (bone malformation).

 Vitamins

Vitamin E

Vitamin E is an antioxidant, protecting unsaturated side chains in

fatty acids from unwanted oxidation.

Deficiency of vitamin E causes numerous neurological problems,

although it is rare.
Antioxidant property of vitamin E
 Vitamins

Vitamin K

Vitamin K regulates the synthesis of clotting proteins (prothrombin),

and deficiency of this leads to excessive or fatal bleeding.