11th World Congress of Food Science & Technology

Slide1 : KoSFoST 11th World Congress of Food Science & Technology FST-OSU

Chemistry and Application of Antioxidants : Chemistry and Application of Antioxidants David B. Min   The Ohio State University Columbus, Ohio, USA

Effects of Lipid Oxidation : Effects of Lipid Oxidation Flavor Quality Loss Rancid flavor Changes of color and texture Consumer Acceptance Economic loss Nutritional Quality Loss Essential Fatty Acids Vitamins Health Risks Growth Retardation Heart Diseases

Activation Energy for Chemical Reaction : Activation Energy for Chemical Reaction Reactions Activation Energy (kcal/mol) Protein Denaturation 100 Nonenzymatic Browning Reaction 50 Enzyme Catalyzed Reaction 10-15 Lipid Oxidation 10-15

Lipid Foods : Lipid Foods

History of Oxygen : History of Oxygen Oxygen - Priestly in 1772. Triplet oxygen - Millikan in 1928. Singlet oxygen - Herzberg in 1934.

Mechanisms of Lipid Oxidation : Mechanisms of Lipid Oxidation Triplet oxygen oxidation Singlet oxygen oxidation

Triplet Oxygen Oxidation : Triplet Oxygen Oxidation

Molecular Orbital of Triplet Oxygen : Molecular Orbital of Triplet Oxygen

Bond Energy of Carbon and Hydrogen : Bond Energy of Carbon and Hydrogen C H C H C H 2 C H C H C H 2 ( C H 2 ) 6 C O O H C H 2 ( C H 2 ) 3 C H 3 100 75 50 C H 3 ( C H 2 ) 14 C O O H C H 3 ( C H 2 ) 6 C H C H ( C H 2 ) 7 C O O H C H 3 ( C H 2 ) 4 C H C H C H 2 C H C H ( C H 2 ) 7 C O O H C H 3 C H 2 C H C H C H 2 C H C H C H 2 C H C H ( C H 2 ) 7 C O O H C H 2 C H 2 C H 2 Stearic acid Oleic acid Linoleic acid Linolenic acid (kcal/mol)

Initiation of Triplet Oxygen Oxidation : Initiation of Triplet Oxygen Oxidation RH R H + Initiation of autoxidation occurs when hydrogen atom at -methylene group in double bonds is removed to form an alkyl radical (R). C H 3 ( C H 2 ) 4 C H C H C H 2 C H C H ( C H 2 ) 7 C O O H

Propagation : Propagation ROO  + RH ROOH + R + + ROOH +  OH RO  RH RO  ROH R  R + 3O2 ROO 

Termination : Termination 2RO  ROOR + + + ROOR RO  ROR ROO  ROOR R  + R-R R  ROO  + R  R  ROO  O2

Pentane from Linoleic Acid by Triplet Oxygen Oxidation : Pentane from Linoleic Acid by Triplet Oxygen Oxidation 14 13 12 11 10 9 · - H + 3O 2 · + H · C H 2 C H C H C H 2 C H C H C H 2 R ( C H 2 ) 3 C H 3 INITIATION (METAL) ( C H 2 ) 4 C H 3 C H C H C H C H C H 2 R C H ( C H 2 ) 4 C H 3 C H C H C H C H C H 2 R C H O O PROPAGATION · R = (CH2)6-COOH 13 12 11 10 9 13 12 11 10 9

Slide15 : 13 12 11 10 9 - OH · + H TERMINATION · (PENTANE) · C H C H C H C H C H C H 2 R ( C H 2 ) 4 C H 3 O O H ( C H 2 ) 4 C H 3 C H C H C H C H C H 2 R C H O C H 3 ( C H 2 ) 3 C H 2 C H 3 ( C H 2 ) 3 C H 3 O C H C H C H C H C H C H 2 R + · R = (CH2)6-COOH 13 12 11 10 9

Singlet Oxygen Oxidation : Singlet Oxygen Oxidation

Molecular Orbital of Singlet Oxygen : Molecular Orbital of Singlet Oxygen 

Singlet Oxygen Formation : Singlet Oxygen Formation 3O2 + Sensitizer H2O2 + OCI- H2O2 + O2 - Ozone Endoperoxides OH- + O2 - Enzymes O2 - + Y+ 1O2 O2 - O2 - + O2 - H2O2+ HO2 - RCOO• + RCOO•

Photosensitizers in Foods : Photosensitizers in Foods Chlorophyll Protoporphyrine Riboflavin Red No. 3

Formation of 1O2 by Sensitizers : Formation of 1O2 by Sensitizers Ground State Excited State hv Fluorescence K= 2108/sec 1Sen 1Sen* K=1- 20108/sec ISC Phosphorescence K=10- 104/sec Singlet Oxygen, 1O2 K=1- 3109/sec 3Sen* 3O2

Reversion Flavor Compounds from Soybean Oil : Reversion Flavor Compounds from Soybean Oil 2-(2-pentenyl)-furan C H 3 C H 2 C H C H C H 2 O C H 3 C H 2 C H C H C H O 2 2-(1-pentenyl)-furan

Reversion Flavor from Linolenic Acid by Singlet Oxygen Oxidation : C H 3 C H 2 C H C H C H 2 C H C H C H 2 C H C O O H ( C H 2 ) 6 C H 2 C H O C H 3 C H 2 C H C H C H 2 C H C H C H 2 C H O C H 3 C H 2 C H C H C H 2 C H O O C H C H 2 C H 1O2 1O2 O • • Reversion Flavor from Linolenic Acid by Singlet Oxygen Oxidation O

Slide23 : 2-(2-pentenyl)-furan - H2O C H 3 C H 2 C H C H C H 2 C H O O C H C H 2 C H • • C H 3 C H 2 C H C H C H 2 C C H 2 O C H 2 C H O C H 3 C H 2 C H C H C H 2 C C H C H C H O H O H C H 3 C H 2 C H C H C H 2 O C H 3 C H 2 C H C H C H 2 C H O O C H C H 2 C H • O H - OH •

Reaction of 3O2 and 1O2 with Linoleic Acid : Reaction of 3O2 and 1O2 with Linoleic Acid R R ' R R ' O O H 3O2 Conjugated Conjugated R R ' R R ' R R ' HOO 3O2 · · - H· R R ' R R ' O O H O O H R R ' 1O2 R ' R H O O R' R H O O Conjugated Nonconjugated

Reaction Rates of Lipid Oxidation : Reaction Rates of Lipid Oxidation R + 3O2 K=109 M-1sec-1 ROO + Oleic Acid K=1 M-1sec-1 ROO + Linoleic Acid K=60 M-1sec-1 ROO + Linolenic Acid K=120 M-1sec-1 ROO + ROO K=105-107 M-1sec-1 R + Antioxidants K= 107 M-1sec-1 RH + 1O2 K=105 M-1sec-1

Relative Reaction Rates of 3O2 and 1O2 with Oleic, Linoleic, and Linolenic Acids : Relative Reaction Rates of 3O2 and 1O2 with Oleic, Linoleic, and Linolenic Acids Singlet oxygen 3 104 4 104 7 104 Triplet oxygen 1 27 77 Oleic Linoleic Linolenic Acid Acid Acid

Lipoxygenase Oxidation : Lipoxygenase Oxidation

Enzymatic Oxidation : Enzymatic Oxidation Hydropeorxide at the -6 position of unsaturated fatty acid Poly unsaturated fatty acids (a cis, cis-1,4-pentadiene unit) Lipoxygenase

Control of Lipid Oxidation : Control of Lipid Oxidation Application of antioxidants Elimination of oxygen by nitrogen flushing or vacuum packaging Elimination of photosensitizers Denaturation of lipoxygenase Low temperature and dark storage

Slide30 : Antioxidants R•, RO•, ROO•, O-2 1O2, -OH, H2O2,Cu, Fe R•, RO•, ROO•, 1O2, O-2, -OH, H2O2, Cu, Fe Prooxidant Jail .

Function of Antioxidant on Lipid Oxidation : Function of Antioxidant on Lipid Oxidation Inhibits or slows the formation of free alkyl radicals in the initiation step Interrupts the propagation of free radical chain Delays the start or slows the chemical reaction rate of lipid oxidation.

Types of Antioxidants : Types of Antioxidants Hydrogen donating compounds Singlet oxygen quenchers Metal chelators Enzymes Oxygen scavengers

Hydrogen Donating Antioxidants : Hydrogen Donating Antioxidants

Hydrogen Donating Antioxidant : Hydrogen Donating Antioxidant Should have lower reduction potential than the reduction potential of polyunsaturated fatty acid (E = 600 mV) Should donate a hydrogen to alkoxyl (E = 1600 mV) or peroxyl (E= 1000 mV) radicals

Standard One-Electron Reduction Potential : Standard One-Electron Reduction Potential Compounds E (mV) HO· , H+ / H2O 2310 RO· , H+ / ROH 1600 ROO· , H+ / ROOH 1000 PUFA· , H+ / PUFA 600 Catechol· , H+ / Catechol 530 - Tocopheroxyl· , H+ / - Tocopherol 500 Ascorbate-· , H+ / Ascorbate 282

Characteristics of Hydrogen Donating Antioxidants : Characteristics of Hydrogen Donating Antioxidants The major hydrogen donating antioxidants are monohydroxy or polyhydroxy phenolic compounds with various ring substitutions. The antioxidant free radical does not initiate another free radical due to the stabilization of radical by delocalization.

Resonance of Antioxidant Radicals : Resonance of Antioxidant Radicals O H C ( C H 3 ) 3 O C H 3 C ( C H 3 ) 3 O C H 3 O . O C H 3 C ( C H 3 ) 3 O . C ( C H 3 ) 3 O C H 3 O . O C H 3 C ( C H 3 ) 3 O . R , RO , ROO RH , ROH , ROOH • • • • • • R , RO , ROO

Effectiveness of Antioxidants : Effectiveness of Antioxidants The difference of one-electron reduction potential between lipid radical and antioxidant radical. 2. The stability of antioxidant radical. The resonance delocalization Further oxidation of antioxidant radicals

Synthetic Antioxidants : Synthetic Antioxidants

Natural Antioxidants : Natural Antioxidants Benefits Health implication Limits Characteristic flavor Safety test required

Tocopherols : Tocopherols O H O R 1 R 2 R 3 C H 3 C H 3 C H 3 C H 3 C H 3 Trivial Name Chemical Name R1 R2 R3 -Tocopherol 5,7,8-Trimethyltocol CH3 CH3 CH3 -Tocopherol 5,8-Dimethyltocol CH3 H CH3 -Tocopherol 7,8-Dimethyltocol H CH3 CH3 -Tocopherol 8-Methyltocol H H CH3

Antioxidant Mechanism of Tocopherol : Antioxidant Mechanism of Tocopherol Transfer of phenolic hydrogen Scavenging of singlet oxygen

Resonance of - Tocopherol Radicals : Resonance of - Tocopherol Radicals O O C H 3 H 3 C C H 3 C 16 H 33 C H 3 R, RO , or ROO  -Tocopherol  O H O C H 3 H 3 C C H 3 C H 3 C H 3 C H 3 C H 3 O C H 3 C H 3 H 3 C C H 3 C 16 H 33 O  O C H 3 H 3 C O C 16 H 33 C H 3 C H 3  O C H 3 H 3 C O C 16 H 33 C H 3 C H 3  RH , ROH , ROOH R, RO , or ROO 

Effects of Diet Tocopherol on the Content of Tocopherol in Egg Yolk : Effects of Diet Tocopherol on the Content of Tocopherol in Egg Yolk

Effects of Tocopherol on the Stability of Egg York : Effects of Tocopherol on the Stability of Egg York 0 5 10 15 20 25 30 35 40 45 0 2 4 6 8 Time (Days) Total Headspace Volatiles ( 1000) 25g Tocopherol / g yolk 45  g Tocopherol / g yolk 50  g Tocopherol / g yolk 75  g Tocopherol / g yolk Control

Ascorbic Acid : Ascorbic Acid Hydrogen donation to lipid radicals Quenching of singlet oxygen Removal of molecular oxygen Regenerate tocopherol radicals Prooxidant Reduce ferric iron to ferrous iron

Ascorbic Acid : Ascorbic Acid O O O H O H C H C H 2 O H O H O O O O H C H C H 2 O H O H L-Ascorbic acid Dehydroascorbic acid - H • - H • • R, RO , ROO  R , RO , ROO 

Ascorbic Acid and Related Compounds : Ascorbic Acid and Related Compounds L-Ascorbic Acid O O H O H C H O C H 2 O H H O H Erythorbic Acid Ascorbic Palmitate O O H O H O H C H C H 2 O H O H O O O H O H O H C H C H 2 O C ( C H 2 ) 14 C H 3 O H

Synergistic Effectof Tocopherol & Ascorbic Acid : Synergistic Effectof Tocopherol & Ascorbic Acid

Slide50 :

Singlet Oxygen Quencher : Singlet Oxygen Quencher

Singlet Oxygen Quenching Mechanism : Singlet Oxygen Quenching Mechanism ISC 3O2 A 1Sen 1Sen* 3Sen* 1O2 AO2 Kq Kox-Q QO2 Kd Q Q 1Sen 1Sen 3O2 3O2 hv

Carotenoids : Carotenoids C H O b - Carotene Apo - 8'- carotenal O Canthaxanthin O b -

Effects of -Apo-8’-Carotenal, -Carotene or Canthaxanthin on the Soybean Oil Oxidative Quality : Peroxide Value (meq/kg oil) Storage Time (hr) Effects of -Apo-8’-Carotenal, -Carotene or Canthaxanthin on the Soybean Oil Oxidative Quality

Singlet Oxygen Quenching Mechanism : Singlet Oxygen Quenching Mechanism ISC 3O2 A 1Sen 1Sen* 3Sen* 1O2 AO2 Kq Kox-Q QO2 Kd Q Q 1Sen 1Sen 3O2 3O2 hv

Quenching Mechanism of b-Carotene on Singlet Oxygen Oxidation : Quenching Mechanism of b-Carotene on Singlet Oxygen Oxidation 1/ Peroxide (1/ M)

Singlet Oxygen Quenching Rates of Carotenoids : Singlet Oxygen Quenching Rates of Carotenoids Carotenoids Number of Conjugated Quenching Rate Double Bonds Constants (M-1sec-1)  -Apo-8’- carotenal 10 2.86  109  - Carotene 11 4.60  109 Canthaxanthin 13 1.12  1010

Singlet Oxygen Quenching Rate of Carotenoids : Singlet Oxygen Quenching Rate of Carotenoids Carotenoids Number of Conjugated Rate Constants Double Bonds (109 M-1sec-1) Astaxanthin 13 9.88 Isozeaxanthin 11 7.31 Zeaxanthin 11 7.03 Lycopene 11 6.89 Lutein 10 5.86

Singlet Oxygen Quenching Rates of Tocopherols : Singlet Oxygen Quenching Rates of Tocopherols Singlet oxygen quenching ability:  >  >  >  - Tocopherol -Tocopherol: 2.70  107 (M-1sec-1)

Singlet Oxygen Quenchers : Singlet Oxygen Quenchers Singlet Oxygen Quencher Quenching Rate (M-1sec-1) -Carotene 4.60  109 Ascorbic acid 1.08  108 -Tocopherol 2.70  107

Metal Chelators : Metal Chelators

Prooxidant Mechanisms of Metals : Prooxidant Mechanisms of Metals Hydroperoxide decomposition to form peroxyl radical and alkoxyl radical. Fe3+ + ROOH Fe2+ + ROO + H+ Fe2+ + ROOH Fe3+ + RO + OH- • •

Prooxidant Mechanisms of Metals : Formations of alkyl free radical by direct reaction Fe3+ + RH Fe2+ + R + H+ Activation of oxygen for singlet oxygen formation Fe2+ + 3O2 Fe3+ + O-2 1O2 Formation of hydroxyl radical Fe2+ + H2O2 Fe3+ + OH- + OH • Prooxidant Mechanisms of Metals •

Metal Chelators : Metal Chelators Phosphoric acid Citric acid Ascorbic acid Ethylene Diamine Tetra Acetate (EDTA) Amino acids and peptides Proteins such as transferrin, ovotransferrin

Mechanism of Metal Chelators : Mechanism of Metal Chelators Formation of complex ions or coordination compounds with metals Prevention of metal redox cycling Formation of insoluble metal complexes Steric hindrance of interactions between metals and lipid intermediates

Interaction of Chealator and Metal : M O C O C H 2 O C O C H 2 N C H 2 C H 2 O O N C O C H 2 C O C H 2 Ethylene Diamine Tetra Acetate (EDTA) Interaction of Chealator and Metal

Enzymatic Antioxidants : Enzymatic Antioxidants

Glucose Oxidase/Catalase : 2 Glucose + 2O2 + 2H2O 2 Gluconic acid + 2H2O2 Glucose Oxidase/Catalase       2 Glucose + O2 2 Gluconic acid 2H2O2 2H2O + O2 Glucose Oxidase Catalase Catalase Glucose Oxidase

Superoxide Anion : Superoxide Anion Superoxide anion participates in oxidative reactions Maintaining transition metals in their reduced active state Promoting the release of metals from proteins Producing singlet oxygen 2O 2 O 2 - + 2H + + H 2 O 2 Spontaneous Dismutation 1

Superoxide Dismutase : Superoxide Dismutase 2O 2 O 2 - + 2H + + H 2 O 2 Superoxide Dismutase + Catalase O 2 2H 2 O 3 2H 2 O 2 Producing triplet oxygen from superoxide anion 3

Glutathione Peroxidase : Glutathione Peroxidase H2O2 + 2GSH 2H2O + GSSG LOOH + 2GSH LOH + H2O + GSSG GSH: Reduced glutathione GSSH: Oxidized glutathione Glutathione Peroxidase Glutathione Peroxidase

Oxygen Scavengers : Oxygen Scavengers

Oxygen Scavengers : Oxygen Scavengers Ascorbic acid Ascorbic palmitate Erythorbic acid Sulfites

Oxygen Scavenger Mechanisms : Oxygen Scavenger Mechanisms C H 3 S H C H 3 S S C H 3 ½ O 2 + O O O O H C H C H 2 O H O H H O 2 + ½ O 2 + H O + H O S O H O H O S O H O O O 2 2

Antioxidant Interactions : Antioxidant Interactions Combination of metal chelator and free radical scavenging antioxidants Combination of different antioxidants like - tocopherol and ascorbic acid

Antioxidant Sources : Antioxidant Sources

Flavonoids : Flavonoids O H O H O H O O O H H O Quercetin Flavonols O O H O O H H O G l u c os i de O H Cyanidin-3-glucoside Anthocyanins

Flavonoids : Flavonoids Secondary products of plant metabolism Metal chelating ability Superoxide anion scavengers Hydrogen donors Anthocyanines, catechins, flavones, flavonols, isoflavone, and proanthocyanidins

Vegetables : Vegetables Cacao beans, Potato, Tomato, Spinach, Legumes, Garlic, and Seaweed Polyphenolic compounds

Fruits : Fruits Wines: Anthocyanin Polyphenolic compounds

Tea : Tea H O O H O O H O H O H Epicatechin H O O H O O H O H O H O H Epigallocatechin

Sesame Seed : Sesame Seed Sesamol O O O H Sesamolinol O O O O O O C H 3 O H

Herb and Spice : Herb and Spice Sage, Ginger, Green pepper, Lavender and Rosemary Carnosoic Acid C O H 3 C C H 3 H O O H C H 3 C H 3 O Carnosol O H O H H O O H O O H O O C Rosemarinic Acid

Reaction Rates of Carnosol and Carnosic Acidand Peroxyl Radical : Reaction Rates of Carnosol and Carnosic Acid and Peroxyl Radical O H H O H H O O C O H O H H O O C • + LOO• LOOH + Carnosic acid 3  107 M-1s-1 O H H O C H O O O H O C H O O + • + Carnosol 2  106 M-1s-1 LOO• LOOH

Soybean : Soybean Chlorogenic acid, caffeic acid, ferulic acid - Metal chelation and singlet oxygen quenching Isoflavones – Metal chelation and hydrogen donation

Soybean : Soybean O O O H O H C O O H O H H O H O Chlorogenic acid Genistein OH OH Daidzein H OH Isoflavones R1 R2 1 2 R

Korean Ginseng : Korean Ginseng

Korean Ginseng : Ferulic acid Caffeic acid Korean Ginseng H O O C H 3 C O O H Vanillic acid O H O O H O H O O H Kaempferol H O O C H 3 C H C H C O O H H O O H C H C H C O O H

Korean Ginseng : Korean Ginseng Singlet oxygen quenchers: Caffeic acid> Kaempferol >Vanillic acid > Salicylic acid > Ferulic acid Linoleic acid in aqueous system under dark: Kaempferol > Maltol > Vanillic acid > Saponin > Salicylic acid > Ferulic acid Metal chelation activity: Kaempferol > Maltol > Vanillic acid > Ferulic acid > Caffeic acid

Maillard Browning Reaction : Maillard Browning Reaction Reducing Sugars and -amino acids N-glycosylamine or N-fructosylamine 1-Amino-1-deoxy-2-ketose (Amadori intermediate) Reductones and dehydroreductones Furans Thiophenes Pyrroles Retroaldol condensation H2S & NH3 Strecker degradation Amino Acids Hydroxyacetone Acetoin Acetylaldehyde Glyoxal Pyruvaldehyde Glycerolaldehyde (Methional, NH3 & H2S) Heterocyclizaion Pyrazines, Pyridines, Thiazoles, Pyrroles & Oxazoles

Antioxidants from Maillard Browning : Antioxidants from Maillard Browning C H 3 C O C O H C O H C H O H C H O H C H 2 O H Reductone Nitrogeneous compounds Ethyl thiol C H 3 S H C H 2

Polarity of Antioxidants : Polarity of Antioxidants Polar antioxidants are more active in bulk oil systems Hydrophobic antioxidants that are located on the interface of lipid/water can protect lipid better than hydrophilic antioxidants

Effects of Antioxidant Polarity in Food Systems : Effects of Antioxidant Polarity in Food Systems Air Oil Water Oil Hydrophobic antioxidant Hydrophilic antioxidant Water Oil

Factors Affecting Partitioning Properties of Antioxidants : Factors Affecting Partitioning Properties of Antioxidants The chemical structure and polarity The types of lipid substrate The presence of surfactants The composition of the phases

Antioxidant Measuring Methods : Antioxidant Measuring Methods

Factors Affecting the Antioxidant Activity : Factors Affecting the Antioxidant Activity Substrates Conditions Analyses Concentrations Calculations

Substrates  : Substrates Substrates relevant to food systems including triacylglycerls and phospholipids Various bulk oil and emulsion system

Conditions  : Test under various oxidation conditions Different temperatures Metal catalysts Simulated real food systems Conditions

Analyses  : Analyses Initial products Peroxide value or conjugated dienes Secondary decomposition products Carbonyls or volatile compounds

Concentrations : Concentrations Compare antioxidants at the same molar concentration of active components using structurally related reference compounds. Consider the concentration ratio of antioxidants/substrates.

Calculations : Calculations Quantify on the basis of Induction period increase percentage Inhibition percentage of peroxide value compared to the control sample Reduction percentage of volatile compounds

Consideration of Antioxidant Selection : Consideration of Antioxidant Selection

Ideal Antioxidants : Ideal Antioxidants   No harmful physiological effects No objectionable flavor, odor, or color Effective in low concentration Fat-soluble Carry-through effect Readily-available Economical Not absorbable by the body

Possible Future Antioxidants : Possible Future Antioxidants Antioxidant attached to packaging material

Slide105 :

Slide106 :

Mechanism of Lipoxygenase in Linolenic Acid : Mechanism of Lipoxygenase in Linolenic Acid H H cis C O O H ( C H 2 ) 6 H C H C C H H C H C C H H H C C (CH 2 ) 4 CH 3 cis cis CH 3 (CH 2 ) 4 C C H H C C H C H H C C H C H ( C H 2 ) 6 C O O H cis H H . C trans H cis H H cis C O O H ( C H 2 ) 6 H C H C C H H C C H C C (CH 2 ) 4 CH 3 H . - H . + 3 O 2 cis cis H C O O H trans H cis H H cis C O O H ( C H 2 ) 6 H C H C C H H C C H C (CH 2 ) 4 CH 3 C

Formation of - Tocopherylquinone : O C H 3 C H 3 H 3 C C H 3 C 16 H 33 O O H O C H 3 C H 3 H 3 C O O H C H 3 C 16 H 33 H2O -Tocopherylquinone O C H 3 C H 3 H 3 C C H 3 C 16 H 33 O + + ROO- O O C H 3 H 3 C C H 3 C 16 H 33 C H 3  ROO  Formation of - Tocopherylquinone

Antioxidant Effectiveness of Tocopherols : Antioxidant Effectiveness of Tocopherols Hydrogen donating ability :  >  >  >  - Tocopherol

Physical Quenching Mechanism of - Carotene on Singlet Oxygen : Physical Quenching Mechanism of - Carotene on Singlet Oxygen 1O2 + 1-Carotene 3O2 + 3-Carotene 3-Carotene 1-Carotene Radiationless Transfer Energy Transfer

Singlet Oxygen Quenching of Tocopherols : Singlet Oxygen Quenching of Tocopherols 1O2 + 1Tocopherol 3O2 + 3Tocopherol 3Tocopherol 1Tocopherol

Reaction Rate of Ascorbic Acid with Singlet Oxygen : Reaction Rate of Ascorbic Acid with Singlet Oxygen Reaction rate (M-1sec-1) 3.08  108 at pH 4.0 1.86  108 at pH 5.6 1.19  108 at pH 7.0

Phospholipids : Phospholipids Phosphatidyl ethanolamine C H 2 O C O R 1 C H O C O R 2 C H 2 O P O O O C H 2 C H 2 N H 2 - Phosphatic acid - C H 2 O C O R 1 C H O C O R 2 C H 2 O P O O O -

Reaction between Metal and Hydroperoxide : Reaction between Metal and Hydroperoxide Copper is 50 faster than ferrous in decomposing hydrogen peroxide Ferrous is 100 faster than ferric iron in decomposing hydrogen peroxide Ferrous is 1010 times more soluble than ferric iron

Amino Acid, Peptide and Protein : Amino Acid, Peptide and Protein Glycine, methionine, and lysine in emulsion system- antioxidant activity at low concentration and high pH. Carnosine inhibits the prooxidant activities of hemoglobin, lipoxygenase, iron, peroxyl, and hydroxyl radical. Ferritin and tranferritin proteins bind iron

Tocotrienols : Tocotrienols O H O R 1 R 2 R 3 C H 3 C H 3 C H 3 C H 3 Trivial Name Chemical Name R1 R2 R3 -Tocotrienol 5,7,8-Trimethyltocotrienol CH3 CH3 CH3 -Tocotrienol 5,8-Dimethyltocotrienol CH3 H CH3 -Tocotrienol 7,8-Dimethyltocotrienol H CH3 CH3 -Tocotrienol 8-Methyltocotrienol H H CH3

Multifunctional Antioxidants : Multifunctional Antioxidants Tocopherol Ascorbic acid

Long-Term Safety of Antioxidants : Long-Term Safety of Antioxidants   Pathological effect Carcinogenic potential Interactions with enzymes Effects of reproduction The exact nature of the metabolism rate in man

Slide119 : Lee, Shin. O. 011-82-31-913-7094 (H), 11- 9496-7094 Hong, Soon. J. 011-652-4576, 063-290-1462 Chun, H. K. 031-299-0550, 02-2051-4050, 016-339-0564(RDA) Kim, H. R (RDA) 02-503-2186, 031-299-0581, 016-303-2186 Chung, Young. J. 016-405-1023, 042-483-2369 Min, M. S. 031-265-6786, Min, B. T. 43-221-9065, 930-6149 (Pil) Kwon, Eun. S. 42-869-4516, Ha, Y. L. 016-587-5471, 55-751-5471 Yeo, W, K, 19-248-6408, 031-330-6007, Choi, Hyang, S, 018-315-0377, Kwon, Oh, N or Chugn Seong K. 011-313-6330, 2-970-6330()) Kim, H, Sook 431-261-2692, 02 6419-9842 Yoon, Suk. H 02-6245-4958, Kim, J. goon011-459-2003, 02-549-2003, 02-3408-3219, 3318,.734-827-2425(Sunghee) 510-332-2262-Moon Martin 293-8039, Korea travel, 1-800-621-5131, Lotte, 422-4152, Yoon Beauty, 262-8999 Lee, S00n. Y. 041-486-5427, Jang K. Ho, Moon Sil, Da Yeon, Seo Young, 205-402-9551 Min, Stephen 547-5824, Kemp, 846-2066, Choe, E. O, 82-32-227-4701 Kang, J. wha 011-82-11-707-6351, 011-82-2-363-6351, Jung, M 82-63-904-1635 (H), 018-396-1635 Kim, Gur W.33-250-8647 , 011-9466-8647 Kim, Oei, S. 82-2-425-0504 (Home) , Sa, Hee Man, 062-682-6421, 011-9603-0421 Kim, Sang Chul, (Gae Po dong) 82-2-3461-3410