OxygenOxygen

OxygenOxygen

Terrestrial distributionTerrestrial distribution

3rd of the most frequently occurring elements (H He O2)

168O (99 ) 18

8O (izotoacutep)

Bioinorganic importance of oxygen ORGANOGENICORGANOGENIC element

OO22++ oxygen ion oxygen ion no biological importanceno biological importance

O oxygen atomO oxygen atom reactive (decomposition Oreactive (decomposition O33))

OO22- - superoxide anionsuperoxide anion UV enzyme reactions UV enzyme reactions

(xanthinoxidase NADPH-oxidase)(xanthinoxidase NADPH-oxidase)

OO222-2- peroxide anion peroxide anion dissociation of H dissociation of H22OO22

OH hydroxy free radicalOH hydroxy free radical decomposition of H decomposition of H22OO22

HOHO22 hydroperoxy free radical hydroperoxy free radical

Activated derivativesActivated derivatives

1O2

O2 O2-O2

+

O + O

O22-

h-e- +e- +e-

Bioinorganic ChemistryBioinorganic Chemistry

11OO22 singlet oxygen singlet oxygen

2p2pxx

2p2pyy p pzz

2p2pyy p pzz

2p2pxx

Ground stateGround state Singlet stateSinglet state

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

OxygenOxygen

Terrestrial distributionTerrestrial distribution

3rd of the most frequently occurring elements (H He O2)

168O (99 ) 18

8O (izotoacutep)

Bioinorganic importance of oxygen ORGANOGENICORGANOGENIC element

OO22++ oxygen ion oxygen ion no biological importanceno biological importance

O oxygen atomO oxygen atom reactive (decomposition Oreactive (decomposition O33))

OO22- - superoxide anionsuperoxide anion UV enzyme reactions UV enzyme reactions

(xanthinoxidase NADPH-oxidase)(xanthinoxidase NADPH-oxidase)

OO222-2- peroxide anion peroxide anion dissociation of H dissociation of H22OO22

OH hydroxy free radicalOH hydroxy free radical decomposition of H decomposition of H22OO22

HOHO22 hydroperoxy free radical hydroperoxy free radical

Activated derivativesActivated derivatives

1O2

O2 O2-O2

+

O + O

O22-

h-e- +e- +e-

Bioinorganic ChemistryBioinorganic Chemistry

11OO22 singlet oxygen singlet oxygen

2p2pxx

2p2pyy p pzz

2p2pyy p pzz

2p2pxx

Ground stateGround state Singlet stateSinglet state

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

OO22++ oxygen ion oxygen ion no biological importanceno biological importance

O oxygen atomO oxygen atom reactive (decomposition Oreactive (decomposition O33))

OO22- - superoxide anionsuperoxide anion UV enzyme reactions UV enzyme reactions

(xanthinoxidase NADPH-oxidase)(xanthinoxidase NADPH-oxidase)

OO222-2- peroxide anion peroxide anion dissociation of H dissociation of H22OO22

OH hydroxy free radicalOH hydroxy free radical decomposition of H decomposition of H22OO22

HOHO22 hydroperoxy free radical hydroperoxy free radical

Activated derivativesActivated derivatives

1O2

O2 O2-O2

+

O + O

O22-

h-e- +e- +e-

Bioinorganic ChemistryBioinorganic Chemistry

11OO22 singlet oxygen singlet oxygen

2p2pxx

2p2pyy p pzz

2p2pyy p pzz

2p2pxx

Ground stateGround state Singlet stateSinglet state

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Activated derivativesActivated derivatives

1O2

O2 O2-O2

+

O + O

O22-

h-e- +e- +e-

Bioinorganic ChemistryBioinorganic Chemistry

11OO22 singlet oxygen singlet oxygen

2p2pxx

2p2pyy p pzz

2p2pyy p pzz

2p2pxx

Ground stateGround state Singlet stateSinglet state

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

11OO22 singlet oxygen singlet oxygen

2p2pxx

2p2pyy p pzz

2p2pyy p pzz

2p2pxx

Ground stateGround state Singlet stateSinglet state

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Enzyme reactionsEnzyme reactions

DrugsDrugs InflammationInflammation

Oxygen Free RadicalsOxygen Free Radicals

PollutantsPollutants

(O(O33 NO NO22))

UV LightUV Light

RadiationRadiation

Smoking

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Oxygen Free RadicalsOxygen Free Radicals

EmphysemaEmphysema CancerCancer

Membrane lipidsMembrane lipids

Nucleic acidsNucleic acids

ProteinsProteins

CardiovascularCardiovascularNeurological Neurological

DisordersDisorders

AgingAging CataractCataract

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Reactive Oxygen SpeciesReactive Oxygen Species

Cell adhesionCell adhesion DNA damageDNA damage

Inactivation of NOInactivation of NO

InflammationInflammation CancerCancer

Membrane damageMembrane damageOxidation of LDLOxidation of LDL

AtherosclerosisAtherosclerosis

Microcirculation Microcirculation injuryinjury

HypertensionHypertensionCell injuryCell injury

(Cancer therapy)(Cancer therapy)

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Reactive oxygen species and free radicalsReactive oxygen species and free radicals

OO22-- Superoxide radicalSuperoxide radical

HH22OO22 Hydrogen peroxideHydrogen peroxide

HOHO Hydroxyl radicalHydroxyl radical11OO22 Singlet oxygenSinglet oxygen

HOOHOO Hydroperoxyl radicalHydroperoxyl radical

ROOHROOH Alkylhydroperoxide Alkylhydroperoxide

ROOROO Alkylperoxyl radicalAlkylperoxyl radical

RORO Alkoxyl radicalAlkoxyl radical

CIOCIO-- Hypochlorite ionHypochlorite ion

FeFe4+4+OO Ferryl ionFerryl ion

FeFe5+5+OO Periferryl ionPeriferryl ion

NONO Nitric oxideNitric oxide

O2 e-

O2- e-

H2O2 H2Oe-

OHe-

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Reduction of O2 to H2O (v) I H+ + O2 + e- HO2

H+ + HO2 + e- H2O2

H2O2 + H+ + e- OH + H2O

H+ + OH + e- H2O

- 032

+168

+088

+274

II 2H+ + O2 + 2e- H2O2

H2O2 + 2H+ + 2e- 2H2O

+068

+177

III 4H+ + O2 + 4e- 2H2O +123

Reduction of OReduction of O22 to H to H22OO deg(v)deg(v)

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

dioxygenasedioxygenase

11 OxygenasesOxygenases

monoxygenasemonoxygenase

22 OxydasesOxydases OO22-- H H22OO22 or 2H or 2H22OO

electron acceptorelectron acceptor

Activator enzymesActivator enzymes

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Protection from superoxide and peroxide

1 Superoxide dismutase systems1 Superoxide dismutase systems

2 Catalase (heme)2 Catalase (heme)

3 Peroxidase systems (heme)3 Peroxidase systems (heme)

2H2O2 2H2O + O2

H2O2 + AH2 2H2O + AA

2O2- + 2H+ O2 + H2O2

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Superoxide DismutaseSuperoxide Dismutase

SOD-CuSOD-Cu2+2+ + O + O22-- SOD-Cu SOD-Cu1+1+ + O + O22

SOD-CuSOD-Cu1+1+ + O + O22-- + 2H + 2H++ SOD-Cu SOD-Cu2+2+ + H + H22OO22

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

CatalaseCatalase catalyzes the breakdown of hydrogen peroxide catalyzes the breakdown of hydrogen peroxide

(H(H22OO22) a toxic by product of metabolic reactions to the ) a toxic by product of metabolic reactions to the

harmless substances water and oxygen harmless substances water and oxygen

Proteins with catalytic behaviours - EnzymesProteins with catalytic behaviours - Enzymes

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

CatalaseCatalase

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

O2 + free electron O2- superoxide radical

H2O

H2O2

H2O

GSH

GSSG

H2O H2O + O2

H2O2 + O2- superoxide radical O2 + OH- + OH hydroxyl radical

H2O2 + Fe2+ Fe3+ + OH- + OH hydroxyl radical

Fentonrsquos reaction

Haber-Weissrsquo reaction Pathological state

superoxide

dismutase

catalaseglutathion peroxidase

Physiological state

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

MACROPHAG

Bakte

rie

Bak

terie

Bakterie

O2

O2bull (Superoxid)

H2O2

Respiratoryburst

Myeloperoxidase

Superoxiddismutase

NADPH

NADPHOxidase

NADP+

Cl -

Fe2+

Fe3+

OH-bullHOCl bull

Bak

terie

BakterieB

acte

rium B

acterium

Phagolysosom

Oxygen radical production by phagocytesOxygen radical production by phagocytes

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc

Biochemistry Reactive Oxygen Species

O2-

H2O2

XO NOX

Fenton

LOOH

Aconitaseinhibition COX

LipOX

MAPKNFkBp53

Antimicrobial

Peroxidases

NO2

Cl-

HOCl HOBr

Br-

NO2-

NOSunc