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Ciclo de krebs

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orgânica / bioquimica

orgânica / bioquimica

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  • 1. Ciclo de KrebsFosforilação Oxidativa PROFESSORA : ADRIANNE MENDONÇA
  • 2. Funções do Ciclo,-Gerar ATP, coenzimas reduzidas-“Gerar” intermediários para vias biossínteses-Ciclo é estágio final de várias vias
  • 3. Complexo piruvato dehidrogenase
  • 4. TPP ↓ Grupo reativo ↓ Grupo reativo ↓ carbanion carbanion
  • 5. Acetyl CoA+Oxaloacetate to Citrate Citrate synthaseEnzyme:Reaction: CondensationAcetyl CoA condenses with oxaloacetate first,to form citryl CoA. Then citryl CoA ishydrolyzed to citrate and CoA.Prosthetic group: No
  • 6. Citrate to cis-AconitateEnzyme: AconitaseReaction: DehydrationCitrate is isomerized to isocitrate by this first dehydration and yields cis-aconitate as an intermediate.Prosthetic group: Fe-S
  • 7. cis-Aconitate to IsocitrateEnzyme: AconitaseReaction: HydrationHydration of cis-aconitate gives the interchange of H atom and OH group from the step 2.Prosthetic group: Fe-S
  • 8. Isocitrate to alpha-KetoglutarateEnzyme: Isocitrate dehydrogenaseReaction: Oxidative decarboxylationDehydrogenation of isocitrate occurs and yields oxalosuccinate as an intermediate.ThenCO2 leaves to have alpha-ketoglutarate.This reaction gives NADH.Prosthetic group: No
  • 9. alpha-Ketoglutarate to Succinyl CoAEnzyme: alpha-Ketoglutarate dehydrogenase complexReaction: Oxidative decarboxylationThis mechanism is almost as same as the reaction of the oxidativedecarboxylation of pyruvate to acetyl CoA by pyruvate dehydrogenase complex.This reaction gives one NADH.Prosthetic group: Lipoic acid, FAD, TPP
  • 10. Succinyl CoA to SuccinateEnzyme: Succinyl CoA synthetaseReaction: Substrate-level phosphorylationThe thioester bond of succinyl and CoA is an energy rich bond. Thus only this step gives ahigh-energy phosphate compound,GTP from the couple reactions of the thioester bondcleavage and the phosphorylation of GDP.Prosthetic group:No GTP + ADP → GDP + ATP
  • 11. Succinate to FumarateEnzyme: Succinate dehydrogenaseReaction: OxidationThe two hydrogens of succinate leave to an acceptor, FAD. Then this reaction yields fumarate andFADH2.Prosthetic group: FAD & Fe-S
  • 12. Fumarato → l-MalatoFumarase
  • 13. Malate to OxaloacetateEnzyme: Malate dehydrogenaseReaction: OxidationMalate is dehydrogenated to form oxaloacetate. The hydrogen acceptor is NAD. So this reactionyields NADH.Prosthetic group: No
  • 14. 1 cal~ 4 Joules
  • 15. Note AcetilCoA é na prática queimado no ciclo,Os intermediários do ciclo não são!!
  • 16. Elementos necessários ao TCA, reações anapleróticas repõem intermediários do Krebs.
  • 17. Repor ciclo para funcionar
  • 18.
  • 19. Bactérias e plantas
  • 20. 2 Ac CoA + NAD+ + 2 H2O  Succinato + 2 CoA +
  • 21. Fosforilação Oxidativa
  • 22. ∆Go = -nℑ∆Eo
  • 23. Fe3+ + e- → Fe2+ 0.771NO3-+2 H++2 e- → NO2-+H2O 0.421Cytochrome f( Fe3+)+ e- → cytochrome f(Fe2+) 0.365Cytochrome a3( Fe3+)+ e- → cytochrome a3(Fe2+) 0.350Cytochrome a(Fe3+)+ e- → cytochrome a(Fe2+) 0.290Cytochrome c( Fe3+)+ e - → cytochrome c(Fe2+) 0.254Cytochrome c1( Fe3+)+ e - → cytochrome c1(Fe2+) 0.220UQH ⋅ + H1 + e- → UQH2 (UQ=coenzyme Q) 0.190UQ + 2 H+ + 2 e- → UQH2 0.060Cytochrome bH(Fe3+) + e - → cytochrome bH(Fe2+) 0.050Fumarate + 2 H+ + 2 e- → succinate 0.031UQ + H+ + e- → UQH ⋅ 0.030Cytochrome b5( Fe3+)+ e - → cytochrome b5(Fe2+) 0.020[FAD]+2 H++2 e- → [FADH2] 0.003-0.091*Cytochrome bL( Fe3+)+ e - → cytochrome bL(Fe2+) -0.100Oxaloacetate + 2 H+ + 2 e- → malate -0.166Pyruvate + 2 H+ + 2 e- → lactate -0.185
  • 24. FAD + 2 H+ + 2 e- → FADH2 -0.219NAD+ + 2 H+ + 2 e- → NADH + H+ -0.320NADP+ + 2 H+ + 2 e- → NADPH + H+ -0.320
  • 25. Figure 21.29 · The structures of several inhibitors of electron transport and
  • 26. F
  • 27. F
  • 28. OBRIGADA !!!