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
