BCMB – 8110 Control of Electron Transfer in Biology 1- Key Concepts -Transfer Potentials -Electron transfer cofactors 2- Overview of the electron transport.

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Presentation transcript:

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

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

Free Energy and Reduction Potential

Transfer Potential

Electron Carriers – Coenzyme Q

Electron Carriers – Iron Sulfur Clusters

Universal, Mobile Electron Carriers – Ferredoxins

Electron Carriers – Low Potential Ferredoxins

Electron Carriers – Rieske Type Iron Sulfur Clusters

Electron Carriers – Cytochromes

Electron Carriers – Blue Copper Proteins

Electron Carriers – Flavoprotein

Electron Storage in Flavins

Complex III

Cytochrome bc 1 Complex (Cont.)

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

Redox Control – Rubredoxin

Redox Control – Nitrogenase

Structural Models of the P-Cluster Peters et al. Biochemistry (1997)

Redox Control – Nitrogenase

E m2 (mV) pH Slope = -53 mV / pH pH-dependence for the P Redox Couple 2+/1+

Model for P-Cluster Redox and Proton Transfer Reactions P 2+ P 1+ (H+) P 2+ (H+) P 1+ PNPN P N (H+) E m2 E m2H E m1 E m1H pK a < -348 mV > -224 mV < 6.0 > mV

Structural Models of the P-Cluster Peters et al. Biochemistry (1997)

e- 8 H + + 8e- + N 2 2 NH 3 + H 2 e- H+H+ P N P 1+ P 2+ pH mV-260 mV P N P 1+ P mV pH 8.0

Cytochrome Oxidase- Proton Transfer

Coupled Proton/Electron transfer – Cytochrome Oxidase

Coupled Proton/Electron transfer – Cytochrome Oxidase

Coupled Proton/Electron transfer – Cytochrome Oxidase

Coupled Proton/Electron transfer – Cytochrome Oxidase

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

Coupled Proton/Electron transfer – Cytochrome Oxidase

Electron Transfer – Theory and Experiment