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Oxygen. Oxygen Terrestrial distribution: 3rd of the most frequently occurring elements: (H, He, O 2 ) 16 8 O (99 %) 18 8 O (izotóp) Bioinorganic importance.

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Presentation on theme: "Oxygen. Oxygen Terrestrial distribution: 3rd of the most frequently occurring elements: (H, He, O 2 ) 16 8 O (99 %) 18 8 O (izotóp) Bioinorganic importance."— Presentation transcript:

1 Oxygen

2 Oxygen Terrestrial distribution: 3rd of the most frequently occurring elements: (H, He, O 2 ) 16 8 O (99 %) 18 8 O (izotóp) Bioinorganic importance of oxygen: O OO ORGANOGENIC element

3 O 2 + oxygen ion: no biological importance O oxygen atom: reactive (decomposition O 3 ) O 2 - superoxide anion: UV, enzyme reactions (xanthinoxidase, NADPH-oxidase) (xanthinoxidase, NADPH-oxidase) O 2 2- peroxide anion: dissociation of H 2 O 2 OH hydroxy free radical: decomposition of H 2 O 2 HO 2  hydroperoxy free radical

4 Activated derivatives Bioinorganic Chemistry

5 1O2 singlet oxygen  *2p x  *2p y, p z  2p y, p z  2p x Ground state Singlet state

6 Enzyme reactions Drugs Inflammation Oxygen Free Radicals Pollutants (O 3, NO 2 ) UV Light Radiation Smoking

7 Oxygen Free Radicals Emphysema Cancer Membrane lipids Nucleic acids Proteins CardiovascularNeurologicalDisorders Aging Cataract

8 Reactive Oxygen Species Cell adhesion DNA damage Inactivation of NO Inflammation Cancer Membrane damage Oxidation of LDL Atherosclerosis Microcirculation injury Hypertension Cell injury (Cancer therapy)

9 Reactive oxygen species and free radicals O 2 ·- Superoxide radical H2O2H2O2H2O2H2O2 Hydrogen peroxide HO· Hydroxyl radical 1O21O21O21O2 Singlet oxygen HOO· Hydroperoxyl radical ROOHAlkylhydroperoxide ROO· Alkylperoxyl radical RO · Alkoxyl radical CIO - Hypochlorite ion Fe 4+ O Ferryl ion Fe 5+ O Periferryl ion NO· Nitric oxide

10 Reduction of O 2 to H 2 O  °(v)

11 dioxygenase 1.Oxygenases monoxygenase 2.OxydasesO 2 -, H 2 O 2 or 2H 2 O 2.Oxydases O 2 -, H 2 O 2 or 2H 2 O electron acceptor Activator enzymes:

12 Protection from superoxide and peroxide 1. Superoxide dismutase systems 2. Catalase (heme) 3. Peroxidase systems (heme) A

13 Superoxide Dismutase SOD-Cu2+ + O2.-  SOD-Cu1+ + O2 SOD-Cu1+ + O2.- + 2H+  SOD-Cu2+ + H2O2

14 Catalase catalyzes the breakdown of hydrogen peroxide, (H 2 O 2 ) a toxic by product of metabolic reactions, to the harmless substances, water and oxygen. Proteins with catalytic behaviours - Enzymes

15 Catalase

16 O 2 + free electron O 2 - superoxide radical H2OH2O H2O2H2O2 H2OH2O GSH GSSG H2OH2OH 2 O + O 2 H 2 O 2 + O 2 - superoxide radical O 2 + OH - + · OH hydroxyl radical H 2 O 2 + Fe 2+ Fe 3+ + OH - + ·OH hydroxyl radical Fenton’s reaction Haber-Weiss’ reaction Pathological state superoxide dismutase catalase glutathion peroxidase Physiological state

17 MACROPHAG Bakterie O2O2 O 2 (Superoxid) H2O2H2O2 Respiratory burst Myeloperoxidase Superoxid dismutase NADPH Oxidase NADP + Cl - Fe 2+ Fe 3+ OH - HOCl Bak terie Bakt erie Bacterium Phagolysosom Oxygen radical production by phagocytes

18 Biochemistry Reactive Oxygen Species O2-O2- H2O2H2O2 XO NOX Fenton LOOH Aconitase inhibition COX LipOX MAPK NFkB p53 Antimicrobial Peroxidases NO 2 Cl - HOCl HOBr Br - NO 2 - NOS unc


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