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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
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II. ANTIOXIDANTS
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 Retard the lipid oxidation reaction
 Are used to stabilize fats and oils, high fat

foods, cereals, product containing small amount of lipids

III. DEFINITION
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According to Food and Drug Administration  Substances used to preserve foods by retarding deterioration, rancidity, or discoloration due to oxidation

LIPID OXIDATION 5  Oxidation of highly unsaturated fats resulting in polymeric end products  Oxidation of moderately unsaturated fats resulting in rancidity.IV. and other type of off-flavors and odors . reversion.

MECHANISM OF LIPID PEROXIDATION Unsaturated Fats 6 Free Radicals Hydroperoxides Oxidation of pigments.V. vitamins Breakdown products (including rancid offflavor compounds) such as ketone. hydrocarbons. epoxides Polymerization (Dark color) (Possibly toxic) Insolubilization of proteins . flavors. acids. alcohols. aldehyd.

VI. regenerating the primary antioxidants. resulting in the formation of more stable products  Synergist antioxidants: oxygen scavengers. CLASSIFICATION 7  Based on function. Synergist or secondary antioxidants  Primary antioxidants terminate the free radical chain reaction by acting as hydrogen or electron donors to free radicals. antioxidants are classified as: 1. Primary or chain breaking antioxidants 2. providing acidic medium to improve the stability of primary antioxidants . chelators.

tocopherols. nordihydroquairetic acid  ‘Hindered’ Phenols: BHA. trihydroxybutyrophenone. PRIMARY ANTIOXIDANTS 8  Phenols: gallates. anoxomer. BHT. ionox series  Miscellaneous primary antioxidants: ethoxyquin. trolox C . TBHQ.VII. hydroquinone. gum guaiac.

VIII. SYNERGIST ANTIOXIDANTS 9  OXYGEN SCAVENGERS: react with free oxygen and can remove it in closed system  Examples: ascorbic acid. 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. ascorbyl palmitate. citric acid. and phosphates .

10  SECONDARY ANTIOXIDANTS: decompose the lipid peroxides into stable end products  Examples: thiodipropionic acid. tea extracts . vitamin A. amino acids. dilauryl esters. flavonoids. distearyl esters  MISCELLANEOUS ANTIOXIDANTS: nitrites.  carotene. spice extracts.

SOME NATURALLY OCCURING ANTIOXIDANTS 11  Amino acids  Beta carotene  Lecithins  Vitamin E  Vitamin C  Soy protein hydrolysate  Vanillin  Saponins  Phenolic acids  Phytic acid  Rosmarinic acid  Spice extract  Tannins  Flavonoids  Uric acid  Nordihydroguairetic acid .IX.

Na. dilauryl and distearyl esters Tocopherols .6-di-ter-butyl       stearate Butylated hydroxyanisole Butylated hydroxytoluene Citric acid. citrates Erythorbic acid and Na erythorbate (not in EEC) Ethoxyquin EDTA. Ca disodium salt Propyl.X. dodecyl gallates 4-hydroxymethylphenol) Lecithins Polyphosphates Tartaric acid Tertiary butyl hydroquinone (not in EEC) Trihydro xy butyrophenone Thiuodipropionic acid. ANTIOXIDANTS PERMITTED FOR USE IN FOOD 12  L-ascorbic acid. octyl. Ca salts  Ascirbyl palmitate and         Glycine  Gum guaiac  Ionox 100 (2.

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. SAFETY REQUIREMENTS 13  Soluble in fats  Impart no foreign color. and carcinogenic studies .XI. teratogenic.

Phenols B. Miscellaneous Primary Antioxidants .XII. Hindered Phenols C. PRIMARY ANTIOXIDANTS 14 A.

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DG) Hydroquinone (HQ) Trihydroxy butyrophenone (THBP) Nordihydroguairetic acid (NDGA) .A. c. PHENOL 16 a. Gallates (PG. b. d. OG.

5-trihydroxy benzoic acid)  PG is the most effective and widely used in animal fats. used in combination with citric acid  OG and DG. discoloration. soluble in oil . spices. unsuitable for frying oil  Used in combination with BHA.4. vegetable oils. and snacks  PG  Melting point 148C. meat products. Gallates 17  Comprise the propyl (PG). octyl (OG). BHT  Sparingly soluble in oil.a. and dodecyl (DG) esters of gallic acid (3. and soluble in water  PG chelates iron.

Propyl Gallate 18 .

Octyl Gallate 19 .

Dodecyl Gallate 20 .

2 mg/kg bw  OG and DG: adverse effect on reproduction  70% PG is absorbed in gastrointestinal tract.21  ADI 0-0.     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 .

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.b. 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 .

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 . fats.d. Nordihydroguairetic Acid (NDGA) 26  Occurs naturally and commercially synthesized  Effective in oils.

Nordihydroguairetic Acid 27 .

f. d. b. Butylated Hydroxyanisole (BHA) Butylated Hydroxytoluene (BHT) Tertiary Butyl Hydroquinone (TBHQ) Tocopherols Gum guaiac Ionox series . e. HINDERED PHENOLS 28 a.B. c.

      Essential oils. and completely excreted No evidence of tissue accumulation LD 50 2200-5000 mg/kg bw . metabolized.5 mg/kg bw BHA is readily absorbed in gastrointestinal tracts. oils. food coating materials.a. fat-containing foods. Butylated Hydroxyanisole (BHA) 29  Used in fats. confectionery. waxes A mixture of two isomers: 2-BHA and 3-BHA Soluble in oil and insoluble in water ADI 0-0.

BHA 30 .

Butylated Hydroxytoluene (BHT) 31  The most extensively used antioxidants in food       industries Used in low fat food products. and citric acid Soluble in fats and insoluble in water.125 mg/kg bw LD 50 in rats 1700-1970 mg/kg bw In high level has toxic and mutagenic effect . fish products. packaging materials Widely used in combination with BHA. steam volatile ADI 0 – 0. PG.b.

BHT 32 .

BHT 33 .

c.        fried foods Regarded as the best antioxidant for frying oil and fried products Not permitted in Japan and EEC ADI 0-0. confectionery. Tertiary Butyl Hydroquinone (TBHQ) 34  Moderately soluble in fats and slightly soluble in water  Used for the stabilization of fats and oils.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 .

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 .d.

Tocopherol 38 .

guairetic acid (10%). Gum guaiac 39  From wood of Guajacum officinale  Commercial gum guaiac consists of  and  guaiconic acid (20%). and guaiac yellow (15%)  An effective antioxidant but no longer used due to availability and undesirable color  LD50 >5000 mg/kg  No adverse effect .e.

Guaiac gum 40 .

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. Ionox series 41  Consists of Ionox 100.f. Ionox 220. and quantatively eliminated Ionox 100: LD50 7 g/kg bw Ionox 330: LD50 >5000 mg/kg bw .

Ionox 220 42 .

Ionox 100 43 .

C. Trolox-C . MISCELLANEOUS PRIMARY ANTIOXIDANTS 44 a. Ethoxyquin b. Anoxomer c.

Ethoxyquin 45  Effective antioxidant for feed to stabilize carotenoids.a. 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 .

    hydroxyanisole. 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 47  Synthetic phenolic polymer  A condensation product of divinyl benzene. TBHQ.b.

Anoxomer 48 .

and ascorbyl palmitate  Colorless.c. PG. tasteless. 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. sparingly soluble in oils  Not being used commercially at present  LD50 1630 mg/kg bw .

SYNERGISTIC/SECONDARY ANTIOXODANTS 50 A.XIII. Secondary Antioxidants D. Miscellaneous Antioxidants . Oxygen Scavengers B. Chelating Agents C.

OXYGEN SCAVENGER 51 a. Ascorbyl Palmitate d. Ascorbic Acid and Sodium Ascorbate c.A. Sulfites b. Erythorbic Acid and Sodium Erythorbate .

7 mg/kg . prevent enzymatic browning and preserve freshness  ADI 0 -0.a. and sodium bisulfite (NaHSO3)  Antimicrobial and antioxidant. Sulfites 52  Represent a group of compounds comprising SO2. sodium metabisulfite (Na2S2O5). Na2SO3.

Sulfite 53 .

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.b. 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 .

25 mg/kg bw  LD50 25 g/kg bw . Ascorbyl palmitate 56  Ester of ascorbic acid and palmitic acid  Highly effective in frying fats.c. 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. oils.

Ascorbyl palmitate 57 .

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. is an effective alternative to use of sulfites in frozen seafood. and fruits More rapidly oxidized as compared to ascorbic acid Highly soluble in water Not permitted in EEC . vegetables. dehydrated fruit and vegetable products As synergist for tocopherols in fats and oils In combination with citric acid.d.

Erythorbic acid 59 .

Sodium Erythorbate 60 .

EDTA c. Citric Acid d. Lecithin . CHELATING AGENTS 61 a. Polyphoshpates b. Citrate Esters e.B. Phytic Acid f.

Na2P2H2O7). K2HPO4. 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 . sodium pyrophosphates (Na4P2O7. NaH2PO4. KH2PO4).a. Polyphosphates 62  Phosphates used as chelators include sodium and     potassium orthophosphates (Na2HPO4.

Polyphosphates 63 .

White crystalline powder sparingly soluble in water ADI 2.5 mg/kg bw LD50 2000-2200 mg/kg bw .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.

EDTA 65 .

and soft drink Colorless. odorless. 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. soluble in water ADI 0-30 mg/kg bw LD50 4360 mg/kg bw . crystalline.c. bakery products.

Tartaric acid 67 .

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. citric acid chelates metal ions at levels of 0.005-0.3% In fats and oils. odorless. highly soluble in water ADI not limited Low order of toxicity .2% White.d.1-0.

Citric Acid 69 .

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 .e.

it forms insoluble complexes with all polyvalent cations  Phytic acid also prevents browning by inhibiting polyphenol oxidase activity  LD50 450-500 mg/kg bw .f. it precipitates Fe3+  At intermediate and high pH. Phytic Acid 71  Potential chelating agent  At low pH.

or a mixture comprises of ascorbyl palmitate. alpha tocopherol.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. 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 .

Vitamin A f. Beta Carotene g. Nitrates and Nitrites b.XV. Spice Extract d. MISCELLANEOUS ANTIOXIDANTS 76 a. Tea Extract . Amino Acids c. Flavonoids e.

2 mg/kg bw for sodium nitrites . teratogenic properties ADI 0-5 mg/kg bw for sodium nitrates and 0-0.a. mutagen. 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.

methionine. and lysine are effective in fats and oils  Glycine has been listed as GRAS for addition to fats and oils . 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. while higher pH favors antioxidant activity  Glycine. proline. most AA are prooxidants. histidine.b. tryptophan.

eugenol from cloves. and taste . Spice Extract 79  Potential naturally occurring antioxidants  Effective in fats. baked goods. odor. and meat products  Vanillin. cucurmin from tumeric  Limited use due to color.c.

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
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 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
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Fotooksidasi
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g. Tea Extract
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 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

jelaskan alasannya: a. Keripik kentang 86 . Permasalahan yang timbul pada saat riset adalah selama penyimpanan sirup jahe mengalami perubahan warna menjadi coklat. Margarin c. Roti e. Apa penyebabnya? Bagaimana cara mengatasinya? Apakah diperlukan antioksidan? 2. Minyak goreng d.Latihan 1. Suatu perusahaan makanan akan mengembangkan sirup jahe. Antioksidan apa yang sesuai untuk produk berikut. Permen susu b.

87 Thank You .