non-metalic elements. bulk elements trace elements for some species periodic table

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Non-metalic Non-metalic Elements Elements

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Non-metalic ElementsNon-metalic Elements

bulk elements

trace elements

for some species

Periodic Table

Halogenes

Fluorine (F)

Source1 mg F-L seawater CaF2 Na3AlF6 in soil

Absorption passive diffusion

plasma 015-020 mgLtissues 03-05 mgkgbones accumulation ()increases resistance to dental caries

[Ca8(HPO4)2(PO4)4]Ca(OH)2 + 2F- [Ca8(HPO4)2(PO4)4]CaF2 + 2OH-

Hydroxyapatite Fluorapatite 95 5

enamel

Chlorine (Cl)

Cl- (predominant anion)- osmoregulation 115-120 mmolL- granulocytes

H2O2 + Cl - ClO - + H2O

H2O2 + ClO - 1O2 + H2O + Cl-

Iodine (I)

Uptake I - I2 Thyreoglobulineperoxydase

T4T3

-Hypothyreosis goiter

- Hyperthyreosis

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

bulk elements

trace elements

for some species

Periodic Table

Halogenes

Fluorine (F)

Source1 mg F-L seawater CaF2 Na3AlF6 in soil

Absorption passive diffusion

plasma 015-020 mgLtissues 03-05 mgkgbones accumulation ()increases resistance to dental caries

[Ca8(HPO4)2(PO4)4]Ca(OH)2 + 2F- [Ca8(HPO4)2(PO4)4]CaF2 + 2OH-

Hydroxyapatite Fluorapatite 95 5

enamel

Chlorine (Cl)

Cl- (predominant anion)- osmoregulation 115-120 mmolL- granulocytes

H2O2 + Cl - ClO - + H2O

H2O2 + ClO - 1O2 + H2O + Cl-

Iodine (I)

Uptake I - I2 Thyreoglobulineperoxydase

T4T3

-Hypothyreosis goiter

- Hyperthyreosis

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Halogenes

Fluorine (F)

Source1 mg F-L seawater CaF2 Na3AlF6 in soil

Absorption passive diffusion

plasma 015-020 mgLtissues 03-05 mgkgbones accumulation ()increases resistance to dental caries

[Ca8(HPO4)2(PO4)4]Ca(OH)2 + 2F- [Ca8(HPO4)2(PO4)4]CaF2 + 2OH-

Hydroxyapatite Fluorapatite 95 5

enamel

Chlorine (Cl)

Cl- (predominant anion)- osmoregulation 115-120 mmolL- granulocytes

H2O2 + Cl - ClO - + H2O

H2O2 + ClO - 1O2 + H2O + Cl-

Iodine (I)

Uptake I - I2 Thyreoglobulineperoxydase

T4T3

-Hypothyreosis goiter

- Hyperthyreosis

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Chlorine (Cl)

Cl- (predominant anion)- osmoregulation 115-120 mmolL- granulocytes

H2O2 + Cl - ClO - + H2O

H2O2 + ClO - 1O2 + H2O + Cl-

Iodine (I)

Uptake I - I2 Thyreoglobulineperoxydase

T4T3

-Hypothyreosis goiter

- Hyperthyreosis

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Iodine (I)

Uptake I - I2 Thyreoglobulineperoxydase

T4T3

-Hypothyreosis goiter

- Hyperthyreosis

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

O CH2 C

H

NH3+

COO-HO

I I

I

O CH2 C

H

NH3+

COO-HO

I I

II

Thyroid hormones

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

NONMETALLIC ELEMENTS

Boron (B)

Borates in plants

- normal growth- infection resistance-accumulated in algae in sponges

Arsenic (As)

Arsenic (III) oxide - poison carcinogenic

Organic form of arsenic compounds are less toxic

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Sulfur (S)

Summary of sulfur functions

1 Good attacking and leaving group as RndashS(-) (catalysis)

2 Polymerizes to ndashSndashSndash

3 As a base RS(-) S2- forms complexes with transition metals

4 Thioethers cyclic thioether formation

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Selenium (Se)

Oxidation states -2 -1 0 +2 +4 +6

Similar to S

1 Toxic (accumulation in plants)2 Protective function Pb2+ Hg2+ Cd2+

3 Essential microelementGlutation peroxydase EndashSendashH

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

E ndash Se- E ndash SeOH

E ndash Se ndash S ndash G

ROH

G ndash SH

H2OG ndash SH

H+ G ndash S ndash S ndash G

ROOH H+

The catalytic cycle of GSH peroxidase

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Deficiency symptoms

- muscular degeneration

- Keshan disease weakness of heart muscle

Glutathion peroxidase

ROOH + 2G SH G S S G + H2O + ROH

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Silicon (Si)

Terrestrial distribution

The most abundant element (next to oxygen)

In vivo distribution

Data on its physiology are LIMITED

Trace element in - most higher animals- man

Major element in - many unicellular org- in plants (grasses)

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Si

HO

O

OH

OOH

OH

HO

HO

Si

OHOH

hellip ndash Gly ndash Ser ndash Ser ndash hellip

hellip ndash Gly ndash Ser ndash Ser ndash hellip

SILICOSIS (lungs) possible cross-linking of proteins

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

(CH2)2

CH2

CH2

NH2

CH2

HC

(CH2)2

OH

NH2

(CH2)2

CH2

CH2

NH2

CH

HC

(CH2)2

OH

O

(CH2)2

CH2

CH2

N

CH

HC

(CH2)2

OH

(CH2)2

CH2

CH2

NH

CH2

C

(CH2)2

O

Cross-linking between collagen chains in lung tissue

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Hypothetical model of silification

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Nitrogen

Occurrence

1 ~ 80 atmosphere2 NaNO3 salpeter3 Living 14 (human body)

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

Biological Nitrogen Comes from N2

1011 kg of N2 fixed annually

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

1 Nitrogenase dinitrogenase 12 - 14 mol ATP reductase

2 Ferredoxin (electron carrier)

Mo - Fe - protein+2 Fe - protein NITROGENASE

N2 + +6H + 2 NH6e- nitrogen

Fe3+ Mo 3+ 3ase

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

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)

Protection from superoxide and peroxideProtection 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

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

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

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)

Protection from superoxide and peroxideProtection 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

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

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

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)

Protection from superoxide and peroxideProtection 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

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

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)

Protection from superoxide and peroxideProtection 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

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

Protection from superoxide and peroxideProtection 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

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

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