AUTOOXIDATION of LIPIDS

Activation Energy for Food Chemical Reactions

Reactions Activation Energy

(Kcal/Mole)

Nonenzymatic Browning Reaction 50

Enzyme Catalyzed Reaction 10-15
Singlet Oxygen Oxidation 1-2
 Oxidation of Foods
• Flavor Quality Consumer Acceptance

• Nutritional Quality Essential Fatty Acids

Essential Amino Acids
Vitamins
• Health Risks Growth Retardation
Heart Diseases
Carcinogens
 Oxygen History
• 1772 Scheele & Priestley
Discovered Oxygen
 
• 1811 Avogadro
Oxygen is a diatomic molecule
 
• 1848 Faraday
Oxygen is a paramagnetic molecule
 
• 1934 Herzberg
Discovered singlet oxygen
 
• 1964 Foote & Wexler
Singlet oxygen in photooxidation
 
Mechanisms of Oxidation in Foods

• Triplet oxygen oxidation

• Singlet oxygen oxidation

Molecular Orbital of Triplet Oxygen
Molecular
*
Atomic Atomic
* *
 
2Px 2Py 2Pz 2Pz 2Py 2Px


Energy *
2S  2S

*
1S 1S

 Molecular Orbital of Singlet Oxygen
Molecular
*
Atomic Atomic
* *
 
2Px 2Py 2Pz 2Pz 2Py 2Px

Energy
*
2S 2S


*
1S 1S

 Comparison of 3O2 and 1O2

3
O2 1
O2

ENERGY LEVEL 0 22.5 Kcal

NATURE DIRADICAL NO RADICAL

REACTION RADICAL ELECTRON-RICH

Molecular Orbital of Triplet Oxygen
Molecular
Atomic * Atomic

* *

 
2Px 2Py 2Pz 2Pz 2Py 2Px


E *

2S
2S


*

1S 1S
 General Mechanisms of Autoxidation
14 13 12 11 10 9
CH3 (CH2)3 CH2 CH CH CH2 CH CH CH2 R

INITIATION - H
(METAL)
12 11 10 9
C H3 (C H 2) 4 C H C H C H CH CH C H2 R


+ O2

12 11 10 9
CH3 (CH2)4 CH CH CH CH CH CH2 R
O
PROPAGATION O
 + H
 12 11 10
CH3 (CH2)4 CH CH CH CH CH CH2 R

O
HYDROPEROXIDE
DECOMPOSION O -  OH

H
12 11 10 9
CH (C H ) CH CH CH CH CH CH R
3 2 4 2

O


O 12 11 10 9
C H3 (C H 2) 3 C H2

+ C CH CH CH CH C H2 R
H
TERMINATION
+ H

C H3 (C H 2) 3 C H 3 (PENTANE)
Major Chemical Mechanisms of Lipid Oxidation

A. Initiation - The formation of free alkyl radical

B. Propagation - The chain reaction of free alkyl radicals
and peroxy raidcals
C. Termination - The formation of nonradical products
Factors Affecting Autoxidation
1. Energy in the form of heat and light
2. Catalysts (Metal)
3. Double bonds
4. Enzymes
5. Chemical oxidants
6. Oxygen content and types of oxygen
7. Natural antioxidants
8. Phospholipids
9. Fatty acids
10. Mono- and Di- glycerides
11. Polymers
 Mechanisms of Oxidation
1. Initiation RH R + H 
R  + O2 ROO 

2. Propagation ROO  + R1H ROOH + R1 

3. Termination R + R RR

ROO  + ROO  ROOR + O2

RO  + R ROR

ROO  + R  ROOR

2RO  + 2ROO  2ROOR + O2

 Oxidation of Mono-Olefines
Oleic acid - 4 Hydroperoxides
Double bond shifts to
11 10 9 8 7 11 10 9 8 7
C C C C C C C C C C C C 9
8
O O
O O
H H

12 11 10 9 8 7
12 11 10 9 8 7
C C C C C C 11 C C C C C C
O 10
O
O O
H H
Hydroperoxides from Linolenate
16 15 14 13 12 11 10 9
C C C C C C C C
O 9
O
H

16 15 14 13 12 11 10 9
C C C C C C C C 12
O
O
H

16 15 14 13 12 11 10 9

C C C C C C C C
O 13
O
H

16 15 14 13 12 11 10 9
C C C C C C C C 16
O
O
H
Peroxide Decomposition
H
H
R C R1
R C R1  OH
O +
O O
H
+  R'

R C R1 + R'H
+ R'H
O
O

R + R1 C H1

or H
O R C R1 + R' 
R C H +  R1 OH

 R' +  OH ROH
Effects of Metal on Peroxide Decomposition

Cu+ + ROOH RO + OH- + Cu++

++
Cu + ROOH ROO  + H+ + Cu+

2 ROOH RO  + ROO  + H+ + OH-

H2O
Formation of C C
H H
C H3 (C H 2 )7 C C C H2 (C H 2 )6 CO O R

H H
C H3 (C H 2 )7 C C CH (CH 2) 6 C O OR
O
O
H

H H
C H3 (C H 2 )7 C C
 H H
C H3 (C H 2 )7 C C

+ RH +  OH Termination

Propagation H H
CH3 (CH2)7 C C OH
H H
H H
CH3 (CH2)7 C CH
CH3 (CH2)7 C C O
+ H
Disproportionation
R H H
+ CH3 (CH2)7 C C

H H
CH3 (CH2)7 C CH
+
CH3 (CH2)7 C CH
 Hydroperoxide Decomposition
O H H H H H H
C C C C C C C R
H H O
O
B
A H

O O
C CH2 C
O H H
C CH 3
H CH2 CH2 CH CH R

O H H H
O H H H H C R
C C C
C C C C C R H H
H