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BCMB – 8110 Control of Electron Transfer in Biology 1- Key Concepts -Transfer Potentials

BCMB – 8110 Control of Electron Transfer in Biology 1- Key Concepts -Transfer Potentials -Electron transfer cofactors 2- Overview of the electron transport chain - Complex I -Complex II -Complex III -Complex IV 3- Advanced Concepts in Protein Structure/Function

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BCMB – 8110 Control of Electron Transfer in Biology 1- Key Concepts -Transfer Potentials

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  1. BCMB – 8110 Control of Electron Transfer in Biology 1- Key Concepts -Transfer Potentials -Electron transfer cofactors 2- Overview of the electron transport chain -Complex I -Complex II -Complex III -Complex IV 3- Advanced Concepts in Protein Structure/Function -Mechanisms of redox control -Mechanisms of proton transfer -Mechanisms of electron transfer

  2. Transfer Potential and the Meaning of Life It’s all about energy!

  3. Free Energy and Reduction Potential

  4. Transfer Potential

  5. Electron Carriers – Coenzyme Q

  6. Electron Carriers – Iron Sulfur Clusters

  7. Universal, Mobile Electron Carriers – Ferredoxins

  8. Electron Carriers – Low Potential Ferredoxins

  9. Electron Carriers – Rieske Type Iron Sulfur Clusters

  10. Electron Carriers – Cytochromes

  11. Electron Carriers – Cytochromes

  12. Electron Carriers – Blue Copper Proteins

  13. Electron Carriers – Flavoprotein

  14. Electron Storage in Flavins

  15. Complex III

  16. Cytochrome bc1 Complex (Cont.)

  17. Cytochrome bc1 Complex (Cont.)

  18. Cytochrome bc1 Complex (Cont.)

  19. Controlling Reduction Potentials, ElectronTransfer And Proton Transfer Rule #1, In most cases, especially for complex metallocenters, proton and electron transfer are coupled.

  20. Redox Control – Rubredoxin

  21. Redox Control – Rubredoxin

  22. Redox Control – Rubredoxin

  23. Redox Control – Rubredoxin

  24. Redox Control – Rubredoxin

  25. Redox Control – Rubredoxin

  26. Redox Control – Rubredoxin

  27. Redox Control – Nitrogenase

  28. Redox Control – Nitrogenase

  29. Redox Control – Nitrogenase

  30. Redox Control – Nitrogenase

  31. Structural Models of the P-Cluster Peters et al. Biochemistry (1997) 36 1181-1187

  32. Redox Control – Nitrogenase

  33. -200 -220 Slope = -53 mV / pH -240 -260 (mV) -280 m2 E -300 -320 -340 -360 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 pH 2+/1+ pH-dependence for the P Redox Couple

  34. Model for P-Cluster Redox and Proton Transfer Reactions Em1 Em2 P2+ P1+ PN < -348 mV pKa pKa pKa > 8.5 > 8.5 < 6.0 Em2H Em1H P2+(H+) P1+(H+) PN (H+) > -224 mV -310 mV

  35. Structural Models of the P-Cluster Peters et al. Biochemistry (1997) 36 1181-1187

  36. -310 mV -260 mV pH 7.0 P N P 1+ P 2+ -310 mV -310 mV pH 8.0 P N P 1+ P 2+ e- H+ 8 H+ + 8e- + N2 e- 2 NH3 + H2

  37. Cytochrome Oxidase- Proton Transfer

  38. Coupled Proton/Electron transfer – Cytochrome Oxidase

  39. Coupled Proton/Electron transfer – Cytochrome Oxidase

  40. Coupled Proton/Electron transfer – Cytochrome Oxidase

  41. Coupled Proton/Electron transfer – Cytochrome Oxidase

  42. Coupled Proton/Electron transfer – Cytochrome Oxidase COX + Cyc c + broken beef heart mitochondria. Capitanio et al. Biochemistry 42(16) p.4607-4612

  43. Coupled Proton/Electron transfer – Cytochrome Oxidase

  44. Electron Transfer – Theory and Experiment

  45. Electron Transfer – Theory and Experiment

  46. Electron Transfer – Theory and Experiment

  47. Electron Transfer – Theory and Experiment

  48. Electron Transfer – Theory and Experiment

  49. Electron Transfer – Theory and Experiment

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