1

 The shelf life of food products:

 Microbial spoilage
 Browning reaction
 Oxidative degradation

 Lipid oxidation:
 Development of off-flavors and odors
 Changes in texture (reaction of lipid oxidation products
with proteins)
 Loss of nutritive value (vitamins, AA, EFA)
 Development of diseases

2
 II. ANTIOXIDANTS
3

 Retard the lipid oxidation reaction

 Are used to stabilize fats and oils, high fat
foods, cereals, product containing small
amount of lipids
 III. DEFINITION
4

According to Food and Drug Administration

 Substances used to preserve foods by retarding
deterioration, rancidity, or discoloration due to
oxidation
 IV. LIPID OXIDATION
5

 Oxidation of highly unsaturated fats resulting in

polymeric end products
 Oxidation of moderately unsaturated fats resulting
in rancidity, reversion, and other type of off-flavors
and odors
V. MECHANISM OF LIPID PEROXIDATION
6
Unsaturated
Fats
Oxidation of
Free Radicals pigments,
flavors,
vitamins
Hydroperoxides

Breakdown products Polymerization Insolubilization of

(including rancid off- (Dark color) proteins
flavor compounds) (Possibly toxic)
such as ketone,
aldehyd, alcohols,
hydrocarbons, acids,
epoxides
 VI. CLASSIFICATION
7

 Based on function, antioxidants are classified as:

1. Primary or chain breaking antioxidants
2. Synergist or secondary antioxidants

 Primary antioxidants terminate the free radical chain

reaction by acting as hydrogen or electron donors to free
radicals, resulting in the formation of more stable
products

 Synergist antioxidants: oxygen scavengers, chelators,

regenerating the primary antioxidants, providing acidic
medium to improve the stability of primary antioxidants
VII. PRIMARY ANTIOXIDANTS
8

 Phenols: gallates, hydroquinone,

trihydroxybutyrophenone, nordihydroquairetic acid

 ‘Hindered’ Phenols: BHA, BHT, TBHQ, tocopherols,

gum guaiac, ionox series

 Miscellaneous primary antioxidants: ethoxyquin,

anoxomer, trolox C
 VIII. SYNERGIST ANTIOXIDANTS
9

 OXYGEN SCAVENGERS: react with free oxygen and can

remove it in closed system
 Examples: ascorbic acid, ascorbyl palmitate, sulfites,
erythrobates

 CHELATING AGENTS: are not antioxidants but they are

highly effective as synergists with both primary
antioxidants and also oxygen scavengers
 Form complex with prooxidant metals like iron and
copper
 Examples: EDTA, citric acid, and phosphates
 10

 SECONDARY ANTIOXIDANTS: decompose the lipid

peroxides into stable end products
 Examples: thiodipropionic acid, dilauryl esters,
distearyl esters

 MISCELLANEOUS ANTIOXIDANTS: nitrites,

amino acids, spice extracts, flavonoids, vitamin A, 
carotene, tea extracts
 IX. SOME NATURALLY OCCURING
ANTIOXIDANTS
11
 Amino acids  Phenolic acids
 Beta carotene  Phytic acid
 Lecithins  Rosmarinic acid
 Vitamin E  Spice extract
 Vitamin C  Tannins
 Soy protein hydrolysate  Flavonoids
 Vanillin  Uric acid
 Saponins  Nordihydroguairetic acid
X. ANTIOXIDANTS PERMITTED FOR USE IN FOOD
12
 L-ascorbic acid, Na, Ca salts  Glycine
 Ascirbyl palmitate and  Gum guaiac
stearate  Ionox 100 (2,6-di-ter-butyl-
 Butylated hydroxyanisole 4-hydroxymethylphenol)
 Butylated hydroxytoluene  Lecithins
 Citric acid, citrates  Polyphosphates
 Erythorbic acid and Na  Tartaric acid
erythorbate (not in EEC)  Tertiary butyl hydroquinone
 Ethoxyquin (not in EEC)
 EDTA, Ca disodium salt  Trihydro xy butyrophenone
 Propyl, octyl, dodecyl  Thiuodipropionic acid,
gallates dilauryl and distearyl esters
 Tocopherols
 XI. SAFETY REQUIREMENTS
13
 Soluble in fats
 Impart no foreign color, odor, and flavor
 Effective for at least one year
 Heat stable
 Safety conditions:
 LD50 must not less than 1000 mg/kg body weight
 Should not have any significant effect on the growth of
experimental animals in long studies at a level 100 times
the level proposed for human consumption
 Approval of antioxidant for food use also requires
extensive toxicological studies including mutagenic,
teratogenic, and carcinogenic studies
XII. PRIMARY ANTIOXIDANTS
14

A. Phenols
B. Hindered Phenols
C. Miscellaneous Primary Antioxidants
15
 A. PHENOL
16

a. Gallates (PG, OG, DG)

b. Hydroquinone (HQ)
c. Trihydroxy butyrophenone (THBP)
d. Nordihydroguairetic acid (NDGA)
 a. Gallates
17

 Comprise the propyl (PG), octyl (OG), and dodecyl

(DG) esters of gallic acid (3,4,5-trihydroxy benzoic
acid)
 PG is the most effective and widely used in animal fats,
vegetable oils, spices, meat products, and snacks
 PG
 Melting point 148C, unsuitable for frying oil
 Used in combination with BHA, BHT
 Sparingly soluble in oil, and soluble in water
 PG chelates iron, discoloration, used in combination
with citric acid
 OG and DG, soluble in oil
Propyl Gallate
18
Octyl Gallate
19
Dodecyl Gallate
20
 21

 ADI 0-0.2 mg/kg bw

 OG and DG: adverse effect on reproduction
 70% PG is absorbed in gastrointestinal tract,
hydrolyzed to alcohol (Krebs cycle) and gallic acid
(secreted in urine)
 Acute toxicity:
 PG LD50 3600-3800 mg/kg bw
 OG LD50 4700 mg/kg bw
 DG LD50 6500 mg/kg bw
 b. Hydroquinone (HQ)
22

 High level of toxicity

 LD 50 less than 1000 mg/kg bw
 Considered as harmful and deleterious substances
for addition to food
 At present, used as stabilizer in polymers
Hydroquinone
23
 c. Trihydroxy Butyrophenone (THBP)
24

 As GRAS by FDA for addition for foods and food

packaging materials
 THBP is only used in food packaging material
 Sparingly soluble in water and soluble in oil
 Produces light tan and brown color in the presence
of organic metal salts
 LD50 3200-6400 mg/kg bw
 No adverse effects
Trihydroxy Butyrophenone
25
 d. Nordihydroguairetic Acid (NDGA)
26

 Occurs naturally and commercially synthesized

 Effective in oils, fats, and fat containing foods
 Removed from the list of GRAS compounds due to
its toxicity at high dose levels
 No longer used as a food antioxidant in many
countries
Nordihydroguairetic Acid
27
 B. HINDERED PHENOLS
28

a. Butylated Hydroxyanisole (BHA)

b. Butylated Hydroxytoluene (BHT)
c. Tertiary Butyl Hydroquinone (TBHQ)
d. Tocopherols
e. Gum guaiac
f. Ionox series
 a. Butylated Hydroxyanisole (BHA)
29

 Used in fats, oils, fat-containing foods, confectionery.

Essential oils, food coating materials, waxes
 A mixture of two isomers: 2-BHA and 3-BHA
 Soluble in oil and insoluble in water
 ADI 0-0.5 mg/kg bw
 BHA is readily absorbed in gastrointestinal tracts,
metabolized, and completely excreted
 No evidence of tissue accumulation
 LD 50 2200-5000 mg/kg bw
BHA
30
 b. Butylated Hydroxytoluene (BHT)
31

 The most extensively used antioxidants in food

industries
 Used in low fat food products, fish products,
packaging materials
 Widely used in combination with BHA, PG, and citric
acid
 Soluble in fats and insoluble in water, steam volatile
 ADI 0 – 0.125 mg/kg bw
 LD 50 in rats 1700-1970 mg/kg bw
 In high level has toxic and mutagenic effect
BHT
32
BHT
33
 c. Tertiary Butyl Hydroquinone (TBHQ)
34

 Moderately soluble in fats and slightly soluble in water

 Used for the stabilization of fats and oils, confectionery,
fried foods
 Regarded as the best antioxidant for frying oil and fried
products
 Not permitted in Japan and EEC
 ADI 0-0.2 mg/kg bw
 Does not form complex with iron and copper
 Rapidly absorbed and nearly 80% is excreted in the urine
 LD50 700-1000 mg/kg bw
 Not teratogenic and slightly mutagenic at level dose
TBHQ
35
TBHQ
36
 d. Tocopherols
37

 Synthetic products are  tocopherol and 

tocopheryl acetate
 Major lipid soluble antioxidant
 ADI 0.15-2 mg/kg bw
 LD50 is not known
 High level: hypervitaminosis E
 Show inhibitory action against carcinogens
Tocopherol
38
 e. Gum guaiac
39

 From wood of Guajacum officinale

 Commercial gum guaiac consists of  and 
guaiconic acid (20%), guairetic acid (10%), and
guaiac yellow (15%)
 An effective antioxidant but no longer used due to
availability and undesirable color
 LD50 >5000 mg/kg
 No adverse effect
Guaiac gum
40
 f. Ionox series
41

 Consists of Ionox 100, Ionox 220, Ionox 312, and

Ionox 330
 Derivatives of BHT
 Ionox 100 is approved for use in food products
 Ionox 330 is appoved for incorporation into food
packaging materials
 Ionox 100 is completely absorbed, rapidly
metabolized, and quantatively eliminated
 Ionox 100: LD50 7 g/kg bw
 Ionox 330: LD50 >5000 mg/kg bw
Ionox 220
42
Ionox 100
43
C. MISCELLANEOUS PRIMARY ANTIOXIDANTS
44

a. Ethoxyquin
b. Anoxomer
c. Trolox-C
 a. Ethoxyquin
45

 Effective antioxidant for feed to stabilize carotenoids,

fish meals, and fish oils
 Readily undergoes oxidation to form a stable free
radical ethoxyquin nitroxide which is more effective
antioxidant than ethoxyquin
 ADI 0-0.06 mg/kg bw
Ethoxyquin
46
 b. Anoxomer
47

 Synthetic phenolic polymer

 A condensation product of divinyl benzene,
hydroxyanisole, TBHQ, and ter-butyl ohenol
 Highly effective in frying oils and fried products
 ADI 0-8 mg/kg bw
 Very poorly absorbed and metabolized because of
large molecular size
 No adverse effects
Anoxomer
48
 c. Trolox C
49

 A synthetic derivative of alpha tocopherol

 Resemble alpha tocopherol structurally
 Two to four times the antioxidant activity of BHA
and BHT, more actove than tocopherol, PG, and
ascorbyl palmitate
 Colorless, tasteless, sparingly soluble in oils
 Not being used commercially at present
 LD50 1630 mg/kg bw
 XIII.
SYNERGISTIC/SECONDARY
ANTIOXODANTS
50

A. Oxygen Scavengers
B. Chelating Agents
C. Secondary Antioxidants
D. Miscellaneous Antioxidants
A. OXYGEN SCAVENGER
51

a. Sulfites
b. Ascorbic Acid and Sodium Ascorbate
c. Ascorbyl Palmitate
d. Erythorbic Acid and Sodium Erythorbate
 a. Sulfites
52

 Represent a group of compounds comprising SO2,

Na2SO3, sodium metabisulfite (Na2S2O5), and
sodium bisulfite (NaHSO3)
 Antimicrobial and antioxidant, prevent enzymatic
browning and preserve freshness
 ADI 0 -0.7 mg/kg
Sulfite
53
 b. Ascorbic Acid and Sodium Ascorbate
54

 L-ascorbic acid or vitamin C and sodium ascorbate

are used as oxygen scavengers also as synergist in a
wide variety of food products
 White, odorless, soluble in water and insoluble in
fats
 Undergoes oxidation to form dehydroascorbic acid
 ADI not limited
 LD 50 >5000 mg/kg bw
Ascorbic acid
55
 c. Ascorbyl palmitate
56

 Ester of ascorbic acid and palmitic acid

 Highly effective in frying fats, oils, and fried products
 Ascorbyl palmitate is better than BHA or BHT
 In combination with other antioxidants it improves
the shelf life of vegetable oils
 ADI 0-1.25 mg/kg bw
 LD50 25 g/kg bw
Ascorbyl palmitate
57
 d. Erythorbic Acid and Sodium Erythorbate
58

 D isomer of ascorbic acid

 No vitamin C activity and does not occur naturally
 Effective in the stabilization of nitrite or nitrate-cured meat
products, dehydrated fruit and vegetable products
 As synergist for tocopherols in fats and oils
 In combination with citric acid, is an effective alternative to
use of sulfites in frozen seafood, vegetables, and fruits
 More rapidly oxidized as compared to ascorbic acid
 Highly soluble in water
 Not permitted in EEC
Erythorbic acid
59
Sodium Erythorbate
60
B. CHELATING AGENTS
61

a. Polyphoshpates
b. EDTA
c. Citric Acid
d. Citrate Esters
e. Phytic Acid
f. Lecithin
 a. Polyphosphates
62

 Phosphates used as chelators include sodium and

potassium orthophosphates (Na2HPO4, NaH2PO4,
K2HPO4, KH2PO4), sodium pyrophosphates (Na4P2O7,
Na2P2H2O7), sodium tripolyphosphate (Na5P3O10) and
sodium hexametaphosphates (NaPO3)n
 Sodium pyrophosphate and sodium tripolyphosphate are
the most effective chelators
 Phosphoric acid also functions as a synergist with other
antioxidants in vegetable shortening
 ADI 0-70 mg/kg bw
 No adverse effects in low dosages
Polyphosphates
63
 b. EDTA
64

 Ethylenediamietetraacetic acid (EDTA) and its salt

are used as chelating agents
 Highly effective in a wide variety of food products
 EDYA forms stable water soluble complexes with
many di- or polyvalent metal ions
 Maximum chelating efficiency occurs at higher pH
values where the carbonyl groups are dissociated.
 White crystalline powder sparingly soluble in water
 ADI 2.5 mg/kg bw
 LD50 2000-2200 mg/kg bw
EDTA
65
 c. Tartaric Acid
66

 Occurs naturally in many fruits and is a by product of

wine making
 Tartaric acid and its salts are used as synergist and
acidulants in a number of products such as
confectionary, bakery products, and soft drink
 Colorless, odorless, crystalline, soluble in water
 ADI 0-30 mg/kg bw
 LD50 4360 mg/kg bw
Tartaric acid
67
 d. Citric Acid
68

 Citric acid and its salts are widely used as chelators

and acidulants
 Used as a synergist both with primary antioxidants
and oxygen scavengers at levels of 0.1-0.3%
 In fats and oils, citric acid chelates metal ions at
levels of 0.005-0.2%
 White, odorless, highly soluble in water
 ADI not limited
 Low order of toxicity
Citric Acid
69
 e. Citrate Esters
70

 Esters of citric acid like isopropyl citrate mixture and

stearyl citrate
 Readily soluble in fats and oils
 LD50 of isopropyl citrate is 2800-2250 mg/kg bw
 LD50 of stearyl citrate is >5400 mg/kg bw
 f. Phytic Acid
71

 Potential chelating agent

 At low pH, it precipitates Fe3+
 At intermediate and high pH, it forms insoluble
complexes with all polyvalent cations
 Phytic acid also prevents browning by inhibiting
polyphenol oxidase activity
 LD50 450-500 mg/kg bw
 g. Lecithin
72

 Phosphadityl choline functions as potent synergist in

fats and oils with a range of primary antioxidants
and oxygen scavengers
 Highly effective in ternary mixture with vitamin E
and vitamin C; or a mixture comprises of ascorbyl
palmitate, alpha tocopherol, and lecithin
 The mechanism of acton of lecithin is not clear
 ADI not limited
 XIV. SECONDARY
ANTIOXIDANTS
73

Thiodipropionic Acid (TDPA)

Dilauryl Thiodipropionate (DLTDP)
Distearyl Thiodipropionate (DSTDP)
 74

 TDPA has the ability to chelate metal ions and also

functions to decompose alkyl hydroperoxides into
more stable compounds
 DLTPD was oxidized to sulfoxide and prevent the
oxidation of cholesterol
 TDPA has beed approved for food use
 ADI 0-3 mg/kg bw
Thiodipropionic acid
75
XV. MISCELLANEOUS
ANTIOXIDANTS
76

a. Nitrates and Nitrites

b. Amino Acids
c. Spice Extract
d. Flavonoids
e. Vitamin A
f. Beta Carotene
g. Tea Extract
 a. Nitrates and Nitrites
77

 Nitrates and nitrites probably function as antioxidants

by converting heme proteins to inactive nitric oxide
form and by chelating metal ions
 Nitrosylmioglobin reacts with peroxy radicals
terminating the oxidative chain reaction
 Nitrites and nitrates form nitrosamines in food or
body
 Nitrosamines are powerful carcinogen, mutagen,
teratogenic properties
 ADI 0-5 mg/kg bw for sodium nitrates and 0-0.2
mg/kg bw for sodium nitrites
 b. Amino Acids
78

 As primary antioxidant and as synergist

 At lower concentrations most of AA have antioxidant
properties, but at higher concentrations they
function as prooxidants
 At low pH, most AA are prooxidants, while higher
pH favors antioxidant activity
 Glycine, tryptophan, methionine, histidine, proline,
and lysine are effective in fats and oils
 Glycine has been listed as GRAS for addition to fats
and oils
 c. Spice Extract
79

 Potential naturally occurring antioxidants

 Effective in fats, baked goods, and meat products
 Vanillin, eugenol from cloves, cucurmin from
tumeric
 Limited use due to color, odor, and taste
 d. Flavonoid
80

 Naturally occurring phenolics in common edible

plants
 Functions as primary and chelator antioxidants
 Not being used commercially due to insufficient or
adverse toxicological effects
 e. Vitamin A
81

 Very limited used as antioxidant because of its high

susceptibility to oxidation on exposure to light and
air, conditions under which vitamin A becomes
prooxidant
 Retinol is effective in fats and oils when kept in the
dark
 f.  carotene
82

 Mainly used as food colorant

 Effective quenchers of singlet oxygen
 Has been chemically synthesized
 Insoluble in water and slightly soluble in vegetable
oils
 Very sensitive to oxidative decomposition when
exposed to air and light
Oksigen singlet
83
Fotooksidasi
84
 g. Tea Extract
85

 Potential source of natural antioxidants for food

products
 Extracts of black and green tea are highly effectove in
fats and oils
 Polyphenols present in tea have antioxidant
properties
 Latihan
86
1. Suatu perusahaan makanan akan mengembangkan sirup
jahe. Permasalahan yang timbul pada saat riset adalah
selama penyimpanan sirup jahe mengalami perubahan
warna menjadi coklat. Apa penyebabnya? Bagaimana
cara mengatasinya? Apakah diperlukan antioksidan?
2. Antioksidan apa yang sesuai untuk produk berikut,
jelaskan alasannya:
a. Permen susu
b. Margarin
c. Minyak goreng
d. Roti
e. Keripik kentang
 87

Thank You