Modul 5

ANTIOXIDANT

ITP-IPB/BTP

Agenda
y

Oksidasi lipid:
Faktor-faktor Faktor faktor yang mempengaruhi Mekanisme reaksi Teknik mencegah oksidasi lipid

Definisi antioksidan yJ Jenis-jenis j antioksidan y Mekanisme antioksidasi y Regulasi penggunaan antioksidan

y
ITP-IPB/BTP

Lipid Oxidation
Effects of Lipid Oxidation
Flavor Quality Loss
Rancid R id flavor fl Changes of color and texture Consumer Acceptance Economic loss Essential Fatty Acids Vitamins Growth Retardation Heart Diseases

Nutritional Quality Loss Health Risks

ITP-IPB/BTP

Faktor yang Mempengaruhi Kerusakan Pangan

Air (Aw, RH, Kadar Air) Suhu pH Oksigen Cahaya Waktu MUTU - Mutu Gizi, - Warna, - Tekstur, - Mikroorganisme, Mik oo ganisme - Dll

Tekanan

Gesekan

Katalis Inhibitor

Benturan/ stres fisik Interaksi eksternal

Interaksi internal

ITP-IPB/BTP

Effects of Air, 100 % Nitrogen, and the mixture of 95% Nitrogen + 5 % Hydrogen on the Oxidation of Dry Milk
10 )
20
Air nitrogen

Total vo olatile compounds (

15
Nitrogen and hydrogen

10

0 0 12 24 36 48 60 72 84

Time (hr)

ITP-IPB/BTP

Effects of Air, 100 % Nitrogen, and the mixture of 95% Nitrogen + 5 % Hydrogen on the Carbon Dioxide and Brown Color of Dry Milk

20
Air

50 45

Carbon dioxide ( 10 )

Brown color (%)

15

nitrogen Nitrogen and hydrogen

40 35 30 25 20 15 10 5

Air nitrogen Nitrogen and hydrogen

10

0 0 12 24 36 48 60 72 84

0 0 12 24 36 48 60 72 84

Time (hr)

Time (hr)

ITP-IPB/BTP

Activation Energy for Chemical Reaction

Reactions Activation Energy gy
(kcal/mol)

Protein Denaturation Nonenzymatic Browning Reaction Enzyme Catalyzed Reaction Lipid Oxidation

100 50 10-15 10-15

ITP-IPB/BTP

Mechanism of Lipid Oxidation

Major flavor problems in food during storage are mainly due to the oxidation of lipid. Lipid Oxidation - free radical reactions. 1. 2. 3. Initiation. Propagation. Termination.
ITP-IPB/BTP

Bond Energy of Carbon and Hydrogen

100 CH3

(CH2)3

75 CH2

50 kcal/mol CH CH CH2 CH CH CH2

(CH2)6

COOH

Stearic acid Oleic acid Linoleic acid Linolenic acid

CH3 CH3
CH3 CH3

(CH2)14 CH2 CH2 COOH (CH2)6 CH2 CH CH (CH2)7 COOH

(CH2)4 CH CH CH2 CH CH (CH2)7 COOH CH2 CH CH CH2 CH CH CH2 CH CH (CH2)7 COOH

General Mechanisms of Autooxidation

14 13 12 11 10 9 (CH2)3 CH2 CH CH CH2 CH CH INITIATION (METAL) C H3

CH3

CH2 R

- H 12 11 10 9 C H2 R CH CH

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

+ O2 12 11 10 9 (CH2)4 CH CH CH CH CH O PROPAGATION O

CH3

CH2 R

+H

ITP-IPB/BTP

CH3

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

CH2

O HYDROPEROXIDE DECOMPOSION O H CH (C H )

2 4

12 11 CH CH CH O

10 9 CH CH

CH

O C H3 (C H 2) 3 C H2

+ H

12 CH

11 CH

10 CH

9 CH

C H2

TERMINATION C H3 (C H 2) 3

+ H C H 3 (PENTANE)

ITP-IPB/BTP

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. The propagation of free radical chain reaction can be minimized by the donation of hydrogen from the antioxidants and the metal chelating agents.

ITP-IPB/BTP

Teknik Mencegah Reaksi Oksidasi

y

Jenis pengemas:
P Pengemasan dalam d l kemasan k gelap l (mencegah ( h masuknya k cahaya) Permeabilitas oksigen rendah (mencegah masuknya oksigen)

Menghilangkan oksigen dalam kemasan. Misal pemvakuman k Pengaturan suhu proses/penyimpanan Penambahan antioksidan
ITP-IPB/BTP

y y

Antioxidants
The chemical compounds which can delay the start or slow the rate of lipid oxidation reaction in food systems.

ITP-IPB/BTP

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

ITP-IPB/BTP

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

ITP-IPB/BTP

Kinds of Antioxidants
Natural antioxidants:
1.Tocopherols 1 Tocopherols (delta>gamma>beta>alpha) 2.Nordihydroguaretic Acid (NDGA) 3.Sesamol 4.Gossypol, etc

Synthetic antioxidants:
1.Butylated 1 B t l ted Hydroxy H d o Anisole Ani ole (BHA) 2.Butylated Hydroxy Toluene (BHT) 3.Propyl Gallate (PG) 4.Tertiary Butyl Hydroquinone (TBHQ)

ITP-IPB/BTP

Common Synthetic Antioxidants

OH

BHA
3-tertiarybutyl-4-hydroxyanisole (also, 2-isomer) less steric hindrance forms radicals more readily than BHT

OCH3

BHT
2,6-di-tert-butyl-p-hydroxytoluene more steric hindrance forms a more stable radical than BHA
OH HO OH

OH

CH3

Akyl Gallates
O(CH2)n-CH3 O

Propyl (n = 2), Octyl (n = 7), Dodecyl (n = 11) As n increases, oil solubility increases

Antioxidants
OH OH OH OH C(CH3)3

COOC3H7

OH

PropylGallate

TBHQ

CHO OH OH OH CH CH3 CH3 CH3CH3

OH

CHO OH OH CH

CH3

CH3

Gossypol

ITP-IPB/BTP

Ascorbic Acid and Derivatives

HO HO O

Ascorbic Acid (Vitamin C)

O

HO

OH

good reducing agent and oxygen scavenger water soluble

O H3C-(H2C)14 HO O O

Ascorbyl palmitate
O

fatty acid tail greater oil solubility

HO

OH

10

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). p )

ITP-IPB/BTP

Reaction of antioxidants with radicals

R
RO

+ +

AH AH AH

RH ROH

+ +

A
A A

ROO +

ROOH +

R RO

+ +

A A

RA ROA ROOA Oxidized Antioxidant

ROO +

Antioxidant + O 2

ITP-IPB/BTP

11

Stable Resonance Formation of BHA

OH C (C H 3 ) 3

O C H3

R , RO , or ROO
O

O C (C H 3 ) 3

RH, ROH or ROOH

+
O C H3

.
O C H3

C (C H 3 ) 3

.
O C H3

C (C H 3 ) 3

C (C H 3 ) 3

O CH3

ITP-IPB/BTP

Tocopherol and Oxygen Reaction

CH3 OH CH3 CH3 O H2 H2 CH3 CH3 O2

- tocopherol

( C H 2 ) 3C H ( C H 2) 3 C H ( C H 2 ) 3C H ( C H 3) 2

CH3 O CH2

CH3

CH3

CH3

C H 2C ( C H 2) 3C H ( C H 2) 3 C H ( C H 3) 2 OH

CH3 CH3

- tocoquinone

ITP-IPB/BTP

12

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+ + O 21

O2

ITP-IPB/BTP

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)

ITP-IPB/BTP

13

Metal Ions EDTA Complex Formation

O C

O O C O

O O CH2 C CH2 N CH2 M N CH2 CH2 O C O CH2

ITP-IPB/BTP

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, y, primary p y antioxidants are often used in combination with (1) other phenolic antioxidants, or with (2) various metal chelating agents.
ITP-IPB/BTP

14

Application of Antioxidants to Foods

Direct addition of antioxidants to oil or melted fat. Addition of antioxidants to the food proportionally. p y g antioxidant solution on the food Spraying or dipping food into antioxidant solution.

ITP-IPB/BTP

Factors Affecting the Efficiency of Antioxidant

1 Activation energy of antioxidants to 1. 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 .

ITP-IPB/BTP

15

Antioxidant Safety
Total concentration of authorized antioxidants added singly or in combination, must not exceed 200 parts per million by weight on the basis of fat content of the food.

ITP-IPB/BTP

ADI (acceptable Daily Intake)

Senyawa Ascorbic acid (and its salt) Ascorbyl ester (palmitate, stearate) Erythorbic acid (and its salt) Tocopherol Propyl Gallate BHA BHT TBHQ ADI (mg/kg BB) RDA 0 1.25 0-5 0.15 - 2 0 1.4 0 0.5 0 0.3 0 0.7

ITP-IPB/BTP

16

Contoh Perhitungan Penggunaan Campuran Antioksidan (BHT Dan BHA)

Antioksidan yang digunakan BHA BHT Jumlah Rasio Batas Maksimum (mg/kg) 200 100 Penggunaan (mg/kg) x y Rasio x / 200 y / 100 (x / 200) + (y / 100) 1

Antioxidants Effectiveness
Quantify effectiveness through antioxidant factor (AF)
measures delay in onset of rapid oxidation without antioxidant with antioxidant
Induction time with i h AH AF = IA = Induction time I0 without AH

[ROOH]

I0 IA

time

AF > 1

17

Antioxidant Effectiveness
Induction time with AH AF = IA = Induction time I0 without AH

Given equivalent quantities of AH we can compare: Antioxidant AF -tocopherol 5 -tocopherol 12 BHA 10 BHT 6 BHA + BHT 12 (synergism)

ITP-IPB/BTP

18

Possible Future Antioxidants

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

ITP-IPB/BTP

LongLong -Term Safety of Monomeric Antioxidants

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

ITP-IPB/BTP

19

Ideal Antioxidants
No harmful physiological effects Not contribute an objectionable j 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

ITP-IPB/BTP

20