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Oxygen
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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
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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
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Activated derivatives Bioinorganic Chemistry
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1O2 singlet oxygen *2p x *2p y, p z 2p y, p z 2p x Ground state Singlet state
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Enzyme reactions Drugs Inflammation Oxygen Free Radicals Pollutants (O 3, NO 2 ) UV Light Radiation Smoking
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Oxygen Free Radicals Emphysema Cancer Membrane lipids Nucleic acids Proteins CardiovascularNeurologicalDisorders Aging Cataract
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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)
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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
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Reduction of O 2 to H 2 O °(v)
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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:
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Protection from superoxide and peroxide 1. Superoxide dismutase systems 2. Catalase (heme) 3. Peroxidase systems (heme) A
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Superoxide Dismutase SOD-Cu2+ + O2.- SOD-Cu1+ + O2 SOD-Cu1+ + O2.- + 2H+ SOD-Cu2+ + H2O2
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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
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Catalase
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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
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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
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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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