Chapter 8

Lipids

Chemistry 106
M. Todd Tippetts, Ph.D.
 Lipids
 Biological compound soluble in non-polar solvent
 Chemically heterogeneous: Simple or Complex
 Simple Lipid: alcohol + one or more fatty acids
 Complex lipid: alcohol + fatty acid + something
else
Classification of Lipids
 Fatty Acids
 Linear Molecules 10-20 carbons in length
 Even number of carbons
 No other functional groups but carboxyl
 Sometimes alkene groups C=C
 Saturated vs. unsaturated
 Water Solubility
 Hydrophobic part of molecule dominates: very
insoluble in water
 Forms micelles in water
* *
*
*

*
*

*
 saturated Fatty Acids to Know

Fatty Acid # of Carbons # of C=C

lauric 12 0

myristic 14 0

palmitic 16 0

stearic 18 0
 Unsaturated Fatty Acids to Know

Fatty Acid # of Carbons # of C=C

oleic 18 1

linoleic 18 2

linolenic 18 3

arachadonic 20 4
 Melting Points
 Increases with size (lesser effect)
 Decreases with unsaturation (greater effect)
 Cis vs Trans Fatty Acids
 Cis fatty acids occur naturally
 Trans fatty acids occur during hydrogenation
reactions
H H
C C

CH3CH2CH2CH2CH2CH2 CH2CH2CH2CH2COOH

H
CH2CH2CH2CH2COOH
C C

CH3CH2CH2CH2CH2CH2 H
Alternate View of Fatty Acids

COOH

COOH
 Triglycerides: Fats and Oils

 Glycerol + 3
Fatty Acids
 Connected
by ester
bonds
 Triglyceride

CH2 OH
O
CH OH + 3 HO C
CH2 OH

CH2 O C
O

CH O C
O

CH2 O C
 Draw a triglyceride made from stearic, palmitic
and myristic acid
O

CH2 O C
O

CH O C
O

CH2 O C

CH2 O C (CH2)14 CH3

O

CH O C (CH2)12 CH3
O

CH2 O C (CH2)16 CH3

 Fat or Oil
 Depends on melting point- solid or liquid at
room temperature
 Depends mostly on degree of unsaturation
 Animal Fats more saturated, plant oils more
unsaturated
 Dietary Fatty Acids

 Saturated fats associated with Heart Disease

 Promotes higher levels of blood cholesterol
 Animal fats also contain cholesterol, plants have
no cholesterol
 Chemical Properties of Triglycerides
1. Reaction with I2

H H H H

+ I2 R2 R1
R2 R1
I I

•Used to quantitate unsaturation in fats

•Product is colorless, I2 is colored
•Iodine number = grams I2 reacting with 100 g fat
 Chemical Properties of Triglycerides
2. Hydrolysis of Ester: catalyzed by acid or enzyme
O

CH2 O C (CH2)16-CH3
O

CH O C (CH2)16-CH3
+3 H2O
O

CH2 O C (CH2)16-CH3

H2C OH
O
HC OH +3 CH3 (CH2)16 C OH

H2C OH
 Chemical Properties of Triglycerides
3. Saponification with NaOH
O

CH2 O C (CH2)16-CH3
O

CH O C (CH2)16-CH3
+3 NaOH
O

CH2 O C (CH2)16-CH3

H2C OH
O
- +
HC OH +3 CH3 (CH2)16 C O Na

H2C OH
 Saponification Reaction produces Soaps
 Hydrophilic and hydrophobic regions
 Hydrophobic dissolved in oils
 Hydrophilic stays on the surface
 Insoluble salts form with hard water
O
- +
C O Na

Sodium stearate
O
- +
O S O Na

Sodium dodecyl sulfate

 Chemical Properties of Triglycerides
4. Hydrogenation

H H H H

+ H 2 Pt R2 R1
R2 R1
H H

• Reacts with alkene

• Partial or complete hydrogenation
• Produces more saturated fat
• Changes plant oil to margarine
Review of Chemical Reactions
 Artificial Fats
 Simpless: micro-particles of proteins
 Smooth cream texture
 Not heat stable
 1.3 Cal/gram vs. 9 Cal/gram for fats

 Olestra: polymer of sucrose and fatty acids

 Not digestable
 Taste and texture of fats
 Causes loss of fat soluble vitamins and other side
effects
 Waxes

 Long chain fatty acid + long chain fatty

alcohol

CH3 (CH2)14 C O CH2 (CH2)12 CH3

Myristyl palmitate
Wax Block Diagram
 Phosphoglycerides
 Glycerol, 2 fatty acids, phosphate + another
alcohol

Fatty Acid
Glycerol

Fatty Acid

Phosphate 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
 Phosphatidyl Choline (lecithin)
O

CH2 O C (CH2)16-CH3
O

CH O C (CH2)16-CH3
O CH3

CH2 O P O CH2CH2 N+ CH3

O- CH3

• Lectithin used as emulsifier

• Dipalmitoyl phosphatidyl choline formed as
surfactant in lung cells
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-
 Sphinglipids: Sphingosine + fatty acid
+ something else
OH

CH2 CH2 CH2 CH2 CH2 CH2 CH CH CH2

H3C CH2 CH2 CH2 CH2 CH2 CH2 CH CH OH

NH2

CH3 (CH2)12 CH CH CH OH Sphingosine

CH NH2

CH OH
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
Sphingomyelin: sphingosine, fatty acid,
phosphate and choline

Sphingomyelins
found in myelin
sheath around
neurons
 Sphingomyelin

Fatty acid

CH3 (CH2)12 CH CH CH OH O

CH NH C (CH2)14 CH3

O CH3

CH O P O CH2CH2 N+ CH3

O- CH3

phosphate choline
 Glycolipid: Lipid + Carbohydrate
Cerebroside: Sphingosine +
fatty acid + carbohydrate

CH3 (CH2)12 CH CH CH OH O

CH NH C (CH2)14 CH3

H2C OH

O HO
H2C O
OH

OH
Lipid Storage Diseases
 Biological Membranes
 Separates cell interior from exterior,
or cellular organelles from cytoplasml
 About 60% lipid and 40% protein

 Lipid mostly phosphoglyceride,

sphingomyelin and cholesterol
 Found as Lipid Bilayer
Lipid Bilayer
Blood Type Antigens

Glc = glucose
Gal = galactose
GalNAc =
N-acetylgalactosamine
Fuc = fucose
 Steroids
 Non-saponifiable lipids derived from
cholesterol

Steroid Ring System

 Cholesterol
CH3 CH3

CH (CH2)3 CH CH3

CH3

HO

Found in Diet (animal fats)

Endogenous synthesized in liver
 Cholesterol
 Essential component of cell membranes
 Used as raw material for sex hormones
and adrenocorticoid hormones
 Used to make bile salts
 High blood levels also associated with
heart disease, atherosclerosis, arterial
plaques
Cholesterol transported as Lipoprotein complex
(LDL)
Lipoproteins classified by Density
 HDL: High-density Lipoprotein
 LDL: Low-density Lipoprotein
 VLDV: Very low-density Lipoprotein
 Triglycerides and cholesterol
 Chylomicron
 Mostly triglycerides
Biological flow of Cholesterol
 Bile Salts: Glycocholate
CH3 O
OH CH2
CH3 C
CH2
NH CH
C O
CH3
O-

HO OH

Act as emulsifying agents to digest fats

Method for excreting cholesterol- bile is
emulsion of cholesterol and bile salts
Gall stones form when cholesterol gets too
concentrated
 Adrenocorticoid hormones
 Glucocorticoids:
 regulate blood glucose levels
 Cortisol and Cortisone
 Also regulate inflammation, used to treat
inflammatory diseases
 Mineralcorticoids:
 influences blood Na+ and Cl- levels
 Aldosterone most important
 CH2OH CH2OH

CH3 C O CH3 C O
HO OH O OH
CH3 CH3

O O

cortisol cortisone

O CH2OH

CH C O
HO OH
CH3 aldosterone

O
 Male Sex Hormones
 Testosterone
 Produced by testes
 Male genitals and secondary sex characteristics
 Muscle growth
 Anabolic Steroids (fake testosterone)
 Intended to prevent muscle atrophy
 Used by athletes, widely banned
 Bad side effects
 Female Sex Hormones
 Estrogen(estradiol, estrone) and
progersterone
 Produced by ovaries
 Reproductive cycle and secondary female
characteristics
 Mimicked by birth control pills
 Prostaglandins
 Hormone like action
 Regulates fever, contractions, inflammation
 Induces labor, and asthma
 Made from arachadonic acid
 Synthesis inhibited by aspirin and
cyclooxygenase inhibitors
HO

COOH

CH3
HO
HO
Classification of Lipids