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

2Px 2Py 2Pz

*
*

Atomic

2Pz 2Py 2Px

Energy
2S

2S

*
1S

1S

Molecular Orbital of Singlet Oxygen

Molecular

Atomic

2Px 2Py 2Pz

Energy

Atomic

2Pz 2Py 2Px

*
2S

2S

1S

1S

Comparison of 3O2 and 1O2

O2

ENERGY LEVEL

O2

22.5 Kcal

NATURE

DIRADICAL

NO RADICAL

REACTION

RADICAL

ELECTRON-RICH

Molecular Orbital of Triplet Oxygen

Molecular
Atomic

2Px

2Py

Atomic

*
*

2Pz

2Pz

2Py

*
2S

2S

*
1S

1S

2Px

General Mechanisms of Autoxidation

CH3

(CH2)3

14
13 12 11
10
9
CH2 CH CH CH2 CH CH

INITIATION
(METAL)
C H3

CH2 R

- H
12

11

10

(C H 2) 4 C H C H C H

CH CH

C H2

+ O2
CH3

(CH2)4

12
11
10
9
CH CH CH CH CH
O

PROPAGATION

+ H

CH2 R

CH3

12
11
10
(CH2)4 CH CH CH CH CH

O
HYDROPEROXIDE
DECOMPOSION O

CH2

- OH

H
CH

(C H )

2 4

12
11
CH CH CH

10
9
CH CH

CH

O
C H3

(C H 2) 3

CH2

TERMINATION
C H3

(C H 2) 3

12
CH

11
CH

H
+ H
C H 3 (PENTANE)

10
CH

9
CH

C H2

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

2. Propagation
3. Termination

ROO

ROO + R1H

R + R

ROOH +

R1

RR

ROO + ROO

ROOR

RO + R

ROR

ROO + R

ROOR

2RO + 2ROO

2ROOR +

O2

O2

Oxidation of Mono-Olefines
Oleic acid - 4 Hydroperoxides
11 10

11 10 9

C C C C C C
O
O
H

12 11 10

Double bond shifts to

8

12 11 10

9 8 7

C C C C C C
O
O
H

11

C C C C C C
O
O
H

C C C C C C
O
O
H

10

Hydroperoxides from Linolenate

16

15

14

13

12

11

16

15

14

13

16

15

14

13

C
O
O
H

16

C
O
O
H

15

14

12

11

C
O
O
H

13

12

11

12

10

11

C
O
O
H

10

12

10

13

10

16

Peroxide Decomposition
H
R C R1
O
O
H

H
C

R1

OH

O
+ R'

+ R'H

O
R

+ R1

H1

or

O
R C H +

R1

H
C

R1 +

R'

OH

R' +

OH

ROH

R1 +

R'H

Effects of Metal on Peroxide Decomposition

Cu+ +
++

Cu

ROOH

RO +

ROOH

ROO + H+

2 ROOH

RO +

OH-

+
+

ROO +

Cu++
Cu+
H+ + OHH2O

Formation of C C
C H3

C H3

(C H 2 )7

(C H 2 )7

H H
C C C H2

H H
C C CH
O
O
H

C H3

(C H 2 )7

(C H 2 )6

CO O R

(CH 2) 6

C O OR

H H
C C

C H3

(C H 2 )7

+ RH

H H
C C

OH Termination

Propagation
CH3

(CH2)7

H H
C CH

CH3

(CH2)7

CH3

(CH2)7

Disproportionation

+ CH3

CH3
CH3

(CH2)7

H H
C CH

(CH2)7
+
(CH2)7 C CH

H H
C C

H
C
H
C
H

H
C OH
H
C O

Hydroperoxide Decomposition
O
C
H
A

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

O
C CH2 C

C CH 3
H
O
C
H

CH2
H
C

H H H
C C C R

CH2 CH CH R
H

O
C
H

C
H

H
C

H
C