Lipids

- Insoluble in H2O, but soluble in ether, chloroform and other fat solvents.

- Are esters of fatty acids or are capable of forming esters.

- They contain C, H and O, and some have also P and N.

- found in all animal and plant matter, and at least some of them appear to be an essential
constituent of protoplasm.

- In the animal body, they form the main store of reserve food supply, being derived from the fat
and carbohydrate of the diet.

Classification:

I. Simple Lipids – esters of fatty acids and alcohols.

1. Fats and Oils – esters of fatty acids and glycerol.

2. Waxes – esters of long-chain fatty acids and long-chain monohydric alcohols or sterols.

II. Compound Lipids – esters of fatty acids and alcohols in combination with other compound.

1. Phospholipids – fat like compounds containing phosphoric acid and a nitrogen base.

2. Glycolipids – compound containing a fatty acid, a carbohydrate, a complex alcohol, and nitrogen, but
no phosphorus.

III. Derived Lipids – compounds that simple and compound lipids give on hydrolysis.

1. Fatty Acids

2. Alcohols

3. Sterols

TABLE 5

THE FATTY ACIDS FOUND IN LIPIDS

Name Formula Occurrence

I. Saturated Acids

1. Butyric C3H7COOH Butter

2. Caproic C5H11COOH Butter

3. Caprylic C7H15COOH Coconut

4. Capric C9H19COOH Palm nut

5. Laurie C11H23COOH Laurel and coconut oils

6. Myristic C13H27COOH Nutmeg and mace

7. Palmitic C15H31COOH Palm oil and lard

8. Stearic C17H35COOH Tallow

9. Arachidic C19H39COOH Peanut

10. Behenic C21H43COOH Ben oil

11. Lignoceric C23H47COOH Peanut

12. Cerotic C25H51COOH Waxes

13. Melissic C29H59COOH Waxes

II. Unsaturated Acids

1. Oleic C17H33COOH 1 = Olive oil

2. Linoleic C17H31COOH 2 = Corn oil

3. Linolenic C17H29COOH 3 = Linseed oil

4. Arachidonic C19H31COOH 4 = Lecithin and cephalin

5. Clupanodonic C21H33COOH 5 = Fish oils

III. Hydroxy Acids

1. Ricinoleic C17H32(OH)COOH Castor oil

2. Cerebronic C23H46(OH)COOH Phrenosin

3. Dihydroxystearic C17H33(OH)2COOH Castor oils

IV. Cyclic Acids

1. Hydnocarpic C15H27COOH Chaulmoogra oil

2. Chaulmoogric C17H31COOH Chaulmoogra oil

I. Saturated Fatty Acids

- Butyric, Caproic, Caprylic, and Capric Acids are volatile when are subjected to steam distillation.
The longer-chained fatty acids. Are solid at 20⁰C and are nonvolatile.

- Palmitic and stearic acids are the most important of the saturated fatty acids. They are found in
most of the common fats and oils.
II. Unsaturated Fatty Acids

- occur as glycerides especially in oils.

- Oils are liquids, largely because of the unsaturated fatty acids present.

III. Hydroxy Acids

IV. Cyclic Acids

INSOMERISM IN THE FATTY ACIDS

1. Position Isomerism

CH3(CH2)7CH=(CH2)7COOH à CH3(CH2)7COOH Pelargonic Acid

Oleic Acid +

COOH(CH2)7COOH Azelaic Acid

2. Geometric Isomerism

CH3(CH2)7CH CH3(CH2)7CH

|| à ||
HNO2 HC(CH2)7COOH Elaidic Acid (trans)
HOOC(CH2)7CH Oleic Acid (Cis)

3. Optical Isomerism

- D- or L- form

SOAPS – metallic salts fatty acids.

Ex: Na, K, Ca, Mg, Zn

GLYCEROL

- Common constituent of all fats and oils.

- A trihydric alcohol

- Since it is a trihydric alcohol, it will form triple esters with fatty acids.

CH2OH
|
CHOH
|
CH2OH

Glycerol

O O
|| ||
CH2OH HO-C- C17H35 CH2-O-C-C17H35
| O O
CHOH || ||
| + HO-C- C17H35 à CH2-O-C-C17H35
CH2OH O O
|| ||
HO-C-C17H35 CH2-O-C-C17H35
+3H2O Tristearin
Glycerol Stearic Acid

Fats and Oils

Fats – if the glyceride is solid at room temperature.

Oils – if the glyceride is liquid at room temperature

Long-chain Saturated fatty acid with high melting point.

Short-chain Unsaturated fatty acid are associated with a low melting point.

Chemical Structure

1. Simple glyceride – Tristearin

2. Mixed glyceride

H O
| ||
α H-C-O-C-C17H33
| O
||
β H-C-O-C-C17H35
| O
||
α1 H-C-O-C-C15H31
|
H

α-Dleo- α1-palmito- β-stearin

Animal Fats

- Fats of animal of different species are often quite different in composition.

- As a rule, the fats in the more active parts of the body are more unsaturated and have lower
melting points than those stored in fatty tissue for future use.
- Unsaturated fats are more easily oxidized than saturated ones, a fact w/c may account for the
prominence of the unsaturated fats in tissues where metabolism is active.
Ex:
Lard, melting pt. 28⁰C
Beef Tallow, melting pt. 46⁰C
Sheep Fat, melting pt. 51⁰C

Vegetable Oils
- Most of the glycerides found in the vegetable kingdom are oils rather than fats.

Classification of Vegetable Oils

1. Nondrying Oils, containing large quantities of oleic acid.
2. Semidrying Oils, containing mainly oleic and linoleic acids.
3. Drying Oils, containing mainly linoleic and linoleic acids.

Hydrogenation of Oils
- Conversion of an oil into a fat, that hydrogen may be added to an unsaturated molecule,
converting it into a saturated one.
Drying Oils
- The property of combining with oxygen of the air and changing to resinous solids.

Drying Process:
1. Oxidation
2. Polymerization

Hydrolysis of Fats and Oils:

- Fat is broken down into glycerol and fatty acids.
1. H2O will hydrolyze fats in extremely long periods of time.
2. With superheated steam the reaction will take place in a few hours.
3. Twitchell’s reagent hydrolyzes fats rapidly when the mixture is heated w/ steam at 100⁰C.
4. Heating in the presence of alkali.
- If the alkali is used in alcoholic solution, the reaction is more rapid than if it is used in water
solution.
5. Lipase – is a fat-splitting enzyme.
Ex: pancreatic lipase
Steapsin

Rancidity:
1. Hydrolytic Rancidity
2. Oxidative Rancidity
Kreis Test – A delicate test for oxidative rancidity.
- In this test the fat to be examined is treated with ether, phloroglucinol, and HCI; a positive
results is indicated by a red color. This test is due to the presence of the epihydrine aldehyde, w/c is one
of the products of fat oxidation.

The Analysis of Fats

Fatty acids into the four groups

Fatty Acids

Distill

Volatile Nonvolatile

Filter Treat with ether and lead acetate and filter

Soluble Insoluble Unsaturated Saturated

volatile volatile fatty acids, fatty acids,
fatty fatty lead salts lead salts
acids acids soluble insolbule
Physical Constants
1. Specific Gravity
2. Refractive index
3. Viscosity
4. Melting Point
5. Solidification Point – Titer Test

Chemical Constants
1. Saponification Number
- Is define as the number of milligrams of KOH necessary to neutralize that fatty acids in 1 gram
of fat.
- Includes both free fatty acids and those combined w/ glycerol.
- It is a measure of the size of the fat molecule, or more specifically the size of MW of the fatty
acids in the fat.
- A high saponification number means a low MW, and a low saponification numbers means a high
MW.

2. Acid Number
- Value of the how much free fatty acid there is in a fat.
- A high acid number would be expected in rancid fat.

3. Ester Number
= Saponification No. – Acid No.
- A pure fat should have no acid number, and the ester and saponification numbers should be the
same.

4. Acetyl Number
- Is a measure of the number of OH groups present in a fat or oil.

5. Iodine Number
- Is defined as the number of grams of iodine absorbed by 100 grams of fat or oil.
- Since iodine is absorbed at the double bonds in the molecule, the iodine number is a measure
of the degree of unsaturation of the fat or oil.

6. Unsaponifiable Matter
- Is meant that part of a fat or oil that is insoluble in water or incapable of forming a soluble soap
with alkalies.
- Pure edible fats and oils usually contain only about 1 or 2 percent of unsaponifiable matter.

7. Reichert – Meissl Number

- Is a measure of the amount of volatile soluble fatty acids present in a fat or oils.
8. Polenske Number
- Is a measure of volatile insoluble fatty acids present in a fat or oil.

*Physiological Importance of Fats and Oils*

- For the body to maintain a reserve energy supply.

Waves
- Are more difficult to saponify than fats.
- When waves are saponified the fatty acids from water-soluble soaps. The long-chain alcohols
formed, being insoluble in water, appear in the “unsaponifiable matter” fraction.
- Waves contain from 31 to 55% of unsaponifiable matter, whereas fats and oils contain from 1 to
2%.

Physiological Importance:
1. Protective agent on the surfaces of animals and plants.
2. The waxy coating on the surface of plants protects the plant from becoming infected with fungi
and bacteria w/c cause disease.

Phospholipids or Phosphatides
- Lipids that yield on hydrolysis an alcohol, fatty acid, phosphoric acid and a nitrogen base.

Types:
1. Lecithin – which contains choline
Ex. Found in egg yolk and brain

O
||
CH2-O-C-C17H35
| O
||
CH- O- C- C17H33
| OH
|
CH2-O - P-O-CH2-CH2
|| |
O N ≡ (CH3)3
|
OH

Lecithin
α – Lecithin – If the H3PO4 is tied to the end carbon of glycerol
β – Lecithin – If the H3PO4 is at the central carbon atom.
Lysolecithin – This is a lecithin in w/c the unsaturated fatty acids has been removed by hydrolysis
Ex. Snake venom
- Lecithins are insoluble in H2O but have a strong affinity for it, readily forming emulsions. This
affinity for water makes lecithin such an important constituent of protoplasm.
- It aids in the organization of the cell structure.

Choline – hydroxyethyltrimethylammonium hydroxide

CH2CH2OH
| CH3
N CH3
CH3
-OH

Choline

- Supports several vital bodily functions and may offer a wide range of other health benefits, such
as:
• Importing memory and cognition. Choline is a an essential nutrient for brain development
• Protecting heart health
• Boosting metabolism
• Reducing the risk of pregnancy complications.

2. Cephalins – which contain hydroxyethylamine or serine

- are found in all tissues of the body but are especially prominent in the brain.
Functions:
- They have a role in the blood coagulation
- They accelerate blood clotting because they enter in the structure of thromboplastin, w/c is
essential for blood clotting.

3. Sphingomyelin
- It differs chemically from lecithins and cephalins in two important aspects:
1. In place of glycerol its nucleus is sphingosinol, a dihydric amino alcohol with one double bond.
2. It contains one molecule of fatty acid usually lignoceric, tied to the amino group rather than
being in ester information with an alcohol group of sphingosinol. Phosphoric Acid and Choline are present,
linked to sphingosinol through an alcohol group.

Glycolipids or Cerebrosides
 - Are lipids with a carbohydrate attached by a glycosidic bond. Their role is to maintain the stability
of the cell membrane and to facilitate cellular recognition, w/c is crucial to the immune response and in
the connections that allow cells to connect to one another to form tissues.
Ex.
Phrenosin – yields on hydrolysis galactose, sphingosinol and long-chain hydroxyl acid called phrenosinic
acid.
Kerasin – has lignoceric acid in the molecule as the fatty acid.

Sterols
- Sterol means solid alcohol
Types:
1. Sterols proper
2. Bite acids
3. Genins
4. Sex and adrenal hormones
5. Vitamin D