ANTIOXIDANT

Antioxidants

The chemical compounds which can delay the start or slow

the rate of lipid oxidation reaction in food systems.

Mechanism of Antioxidant
14

CH3
Initiation

13

12

11

10

(CH2)3 CH2 CH CH CH2 CH CH

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

(K= 10o M-1sec-1)

+ H from RH (triglyceride)

R.

(K= 107 M-1sec-1)

OH
C(CH 3 )

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

Most reactive oxygen species

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

Are you ready to fight the attack of prooxidants?

Antioxidant
Prooxidant Jail

R, RO,
ROO,
O2, O-2,

-OH, H2O2,
Cu, Fe

O-2, 1O2, .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

Singlet Oxygen Quenching Mechanism of

Carotenes
1

O2 + 1-CAROTENE

-CAROTENE

RADIATIONLESS

O2 + 3-CAROTENE

-CAROTENE

Prooxidant Activities of Transition Metals

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 -

Activation of molecular oxygen for singlet oxygen formation.

Fe2+

O2

Fe3+

+ O2-

O2

Radical Scavenging Antioxidant

Vitamin C
Tocopherol
Quercetin
Anthocyanin
Radical scavenging antioxidants break free radical
chain reaction by donating hydrogen to free radicals

Standard One-Electron Reduction Potential

Compounds

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

Resonance Stabilization of Antioxidant Radicals

OH
C(CH3)3

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)

(K= 107 M-1sec-1)

RH , ROH , ROOH

Minimization of Lipid Oxidation

If a compound inhibits the formation of free alkyl radicals
in the initiation step, or if the chemical compound interrupts
the propagation of the free radical chain, the compound can
delay the start or slow the chemical reaction rate of lipid
oxidation.
The initiation of free radical formation can be delayed by
the use of metal chelating agents, singlet oxygen inhibitors,
and peroxide stabilizers.
The propagation of free radical chain reaction can be
minimized by the donation of hydrogen from the
antioxidants and the metal chelating agents.

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

Hydrogen donation to free radicals by antioxidants.

Formation of a complex between the lipid radical
and the antioxidant radical (free radical acceptor).

Reaction of antioxidants with radicals

R

AH

RH

RO

AH

ROH +

ROO +

AH

ROOH +

RA

RO

ROA

ROO +

ROOA

Antioxidant + O 2

Oxidized Antioxidant

Stable Resonance Formation of BHA

OH
C (C H 3 ) 3

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

Tocopherol and Oxygen Reaction

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

Mechanisms of Metals in Accelerating Lipid Oxidation

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 -

Activation of molecular oxygen for singlet oxygen formation.

Fe2+

O2

Fe3+

+ O2-

O2

Kinds of Metal Chelators

Metal chelators deactivate trace metals that are free or salts of fatty
acids by the formation of complex ion or coordination compounds.
1. Phosphoric acid
2. Citric acid
3. Ascorbic acid
4. Ethylene-Diamine-Tetra-Acetate (EDTA)

Metal Ions EDTA Complex Formation

O
C

O
O
O

O O
CH2
C CH2
N
CH2
M
N CH2
O

CH2

CH2
C
O

Synergism in Lipid Oxidation

Synergism occurs when mixtures of antioxidants
produce a more pronounced activity than the sum of
the activities of the individual antioxidants when
used separately.
To have maximum efficiency, primary antioxidants
are often used in combination with (1) other
phenolic antioxidants, or with (2) various metal
chelating agents.

Factors Affecting the Efficiency of Antioxidant

1. Activation energy of antioxidants to
donate hydrogen should be low
2. Oxidation potential should be high
3. Reduction potential should be low
4. Stability to pH and processing.
5. Solubility in oil should be .

Antioxidant Safety

Food Additive, Meat Inspection, and Poultry Inspection Acts.

Total concentration of authorized antioxidants added singly or in

mbination, must not exceed 200 parts per million by weight
on the basis of fat content of the food.

Possible Future Antioxidants

1. Polymeric antioxidant.
2. Antioxidant attached to the packaging materials.
3. Development of new, non-absorbable polymeric
antioxidants for use in foods.

Long-Term Safety of Monomeric Antioxidants

Pathological effect.
Carcinogenic potential
Interactions with enzymes
Effects of reproduction
The exact nature of the metabolism rate in man.

Isolation and Identification of Oxidation Product of

2,6-Di-(Tert-Butyl)-4-Methylphenol

HO

C H2

C H2

OH

3,3' ,5,5'-Tetra-Bis-( Tert-Butyl)-4,4'-Dihydoxyl-1,2-Diphenylethane

CH

CH

3,3',5,5'-Tetra-Bis-( Tert-Butyl)- Stillbenequinone

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

Biochemical Control of Lipid Oxidation

Biochemical Control of Lipid Oxidation in Mayonnaise

Composition of Mayonnaise
Soybean oil
Whole egg
Water
Vinegar
Egg yolk
Glucose
Fructose
Salt
Natural Flavor

Composition (%)
77.0
7.0
7.0
3.0
2.0
1.0
1.0
0.9
0.1
100%

Glucose oxidase/catalase Reaction Mechanism.

Glucose oxidase/catalase reaction:
Glucose Oxidase
2 Glucose + 2O 2 + 2H2O
Catalase

2H2O2

2 Gluconic acid + 2H 2O2

2H2O + O2

The net chemical reaction is:

Glucose Oxidase
2 Glucose + O2

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

Antioxidants for Different Food Systems

A small surface-to-volume ratio PG and TBHQ

A large surface-to-volume ratio BHA and BHT

Application of Antioxidants to Foods

Direct addition of antioxidants to oil or melted fat.

Addition of antioxidants to the food after they are
diluted in oil.
Spraying antioxidant solution in oil on the food or
dipping food into antioxidant solution.