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Antioxidants
Mechanism of Antioxidant
14
CH3
Initiation
13
12
11
10
CH2 R
Metal
Energy
Reactive oxygen species
Substrate effect
-H
Lipoxygenase
C H3
13
12
11
10
(C H 2) 4 C H C H C H
mv
CH CH
+ O2
3
K=10 /sec
9
C H2
Oxygen consumption,
Conjugated diene
Electron spin resonance
CH3
13
12
11
(CH2)4 CH CH CH
O
Propagation
O
1000mv
10
CH CH
CH2 R
R.
from
C(CH 3 )
OCH3
0 300-500mv
OCH3
13
CH3
12
11
10
(CH2)4 CH CH CH CH CH
CH2
O
Peroxide value
Transition Metal
C H3
(C H )
13
2 4
OH
0mv
12
11
CH CH CH
10
CH CH
C H2
0mv
Termination
C H3
C H3
(C H 2) 4
C HO
Sensory evaluation
(C H )
C H3
Volatile compounds
2 3
Antioxidant
Prooxidant Jail
R, RO,
ROO,
O2, O-2,
-OH, H2O2,
Cu, Fe
R, RO, ROO
Preventive Antioxidants
Superoxide dismutase
Catalase
Glutathione peroxidase
Singlet oxygen quencher
Transition metal chelators (EDTA)
Preventive antioxidants minimize the formation of
initiating radicals
Superoxide dismutase
Superoxide dismutase
2O2
H2O2
2H+
-
Catalase
O2 + H2O
Glutathione Oxidase
2GSH
GSSG + 2H2O
Glutathione Reductase
NADP+
NADPH + H+
NADP+ Reductase
Gluthione
H
O
H
C
CH2
CH2
CH2
SH
HC
NH2
COOH
O
C
H
N
CH2COOH
O2 + 1-CAROTENE
-CAROTENE
RADIATIONLESS
O2 + 3-CAROTENE
-CAROTENE
Formations of alkyl free radical by direct reaction with fats and oils.
Fe3+ +
RH
Fe2+ + R
+ H+
Hydroperoxide decomposition to form peroxy or alkoxy radical.
Fe3+
Fe2+
+
+
ROOH
ROOH
Fe2+
Fe3+
+ ROO + H+
+ RO + OH -
O2
Fe3+
+ O2-
O2
Vitamin C
Tocopherol
Quercetin
Anthocyanin
Radical scavenging antioxidants break free radical
chain reaction by donating hydrogen to free radicals
E (mV)
HO
H+ / H2O
2310
RO
H+ / ROH
1600
HOO.
H+ / ROOH
1300
ROO
H+ / ROOH
1000
H+ / RH
600
Catechol
H+ / Catechol
530
- Tocopheroxyl
H+ / - Tocopherol
500
Ascorbate
H+ / Ascorbate
282
0 300-500mv
OCH 3
.
C(CH )
33
E0=1000mv
R , RO , ROO
O
C(CH )
33
OCH
3
OCH
3
OCH3
C(CH3)3
.
OCH3
C(CH3)
Characteristics of Antioxidants
The major antioxidants currently used in foods are
monohydroxy or polyhydroxy phenol compounds with
various ring substitutions. These compounds have low
activation energy to donate hydrogen. The resulting
antioxidant free radical does not initiate another free
radical due to the stabilization of delocalization of
radical electron.
The resulting antioxidant free radical is not subject to
rapid oxidation due to its stability.
The antioxidant free radicals can also react with lipid
free radicals to form stable complex compounds
Antioxidants
OH
OH
C(CH3)3
OCH3
Butylated Hydroxy Anisole
(CH3)3C
C(CH3)3
CH3
Butylated Hydroxy Toluene
Antioxidants
OH
OH
OH
C(CH3)3
OH
OH
COOC3H7
PropylGallate
TBHQ
CHO OH
OH
CHO
OH
OH
OH
OH
CH3CH3
CH
CH3
CH
CH3
CH3
Gossypol
CH3
Mechanism of Antioxidants
AH
RH
RO
AH
ROH +
ROO +
AH
ROOH +
RA
RO
ROA
ROO +
ROOA
Antioxidant + O 2
Oxidized Antioxidant
O C H3
R , RO , or ROO
O
RH, ROH
or ROOH
O
C (C H 3 ) 3
C (C H 3 ) 3
O C H3
O C H3
.
O C H3
C (C H 3 ) 3
C (C H 3 ) 3
.
O CH3
H2
- tocopherol
OH
H2
CH3
CH3
( C H 2) 3C H ( C H 2 ) 3 C H ( C H 2 ) 3C H ( C H 3) 2
CH3
CH3
CH3
O
CH3
CH2
CH3
C H 2C ( C H 2) 3C H ( C H 2) 3C H ( C H 3) 2
OH
CH3
O
CH3
CH3
- tocoquinone
O2
Formations of alkyl free radical by direct reaction with fats and oils.
Fe3+ +
RH
Fe2+ + R
+ H+
Hydroperoxide decomposition to form peroxy or alkoxy radical.
Fe3+
Fe2+
+
+
ROOH
ROOH
Fe2+
Fe3+
+ ROO + H+
+ RO + OH -
O2
Fe3+
+ O2-
O2
O
O
O
O O
CH2
C CH2
N
CH2
M
N CH2
O
CH2
CH2
C
O
Antioxidant Safety
1. Polymeric antioxidant.
2. Antioxidant attached to the packaging materials.
3. Development of new, non-absorbable polymeric
antioxidants for use in foods.
Pathological effect.
Carcinogenic potential
Interactions with enzymes
Effects of reproduction
The exact nature of the metabolism rate in man.
HO
C H2
C H2
OH
CH
CH
Ideal Antioxidants
No harmful physiological effects
Not contribute an objectionable flavor, odor, or color to the fat
Effective in low concentration
Fat-soluble
Carry-through effect No destruction during processing
Readily-available
Economical
Not absorbable by the body
Composition (%)
77.0
7.0
7.0
3.0
2.0
1.0
1.0
0.9
0.1
100%
2H2O2
Catalase
2 Gluconic acid
Kinds of Antioxidants
Natural antioxidants:
1.Tocopherols (delta>gamma>beta>alpha)
2.Nordihydroguaretic Acid (NDGA)
3.Sesamol
4.Gossypol
Synthetic antioxidants:
1.Butylated Hydroxy Anisole (BHA)
2.Butylated Hydroxy Toluene (BHT)
3.Propyl Gallate (PG)
4.Tertiary Butyl Hydroquinone (TBHQ)
Choices of Antioxidants
Different antioxidants show substantially different antioxidant effectiveness in
different fats and oils and food systems due to different molecular structures.
We should consider the following:
Safety
Antioxidant effectiveness
Off-odor
Off-color
Convenience of antioxidant incorporation to foods
Carry-through effect
Stability to pH and food processing
Availability
Cost
Non-adsorbable, if possible