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An outline of oxidative phosphorylation, focusing on the function of the electron transport chain in making water and synthesizing ATP in mitochondria. It includes discussions on the energy of reduced cofactors, the structure of mitochondria, and the importance of proton motive force. Calculations are included to determine the energy available from NADH and FADH2 for ATP synthesis.
What you will learn
Typology: Lecture notes
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GlycogenolysisGlycolysis Other sugarsPasteur: Anaerobic vs Aerobic Fermentations Pyruvate (^) pyruvate dehydrogenase (ox-decarbox; S-ester) Krebs’ CycleHow did he figure it out? Overview8 Steps Citrate Synthase (C–C)Aconitase ( = , -OH) Isocitrate dehydrogenase (ox-decarbox; =O)Ketoglutarate dehydrogenase (ox-decarbox; S-ester) Succinyl-CoA synthetaseSuccinate dehydrogenase (sub-level phos)( = ) FumaraseMalate dehydrogenase ( -OH) (=O) EnergeticsRegulation Summary Oxidative Phosphorylation EnergeticsMitochondria TransportElectron transport Discovery Four Complexes
Exam-1 material Exam-2 material
Oxidative Phosphorylation
Learning goals:
6O 2 6H 2 O
Oxidative Phosphorylation
Energy of the reduced cofactors
Oxidative Phosphorylation
Is there enough energy in NADH & FADH 2 to drive the synthesis of ATP? Each ATP synthesis is about +7.3 kcal/mol (opposite of hydrolysis) We can do this calculation two ways:
D G °^ ’^ = –n F D E °^ ’
7.2 times more energy in 2e– going from NADH to oxygen than needed to drive the synthesis of ATP
D G °^ ’^ = –52.6 kcal/mol D G °^ ’^ = +7.3 kcal/mol
= –(2)(23.06V-1kcalmol -1)(+1.14V)
6.5 times more energy in 2egoing from FADH – than needed to drive the^2 to oxygen synthesis of ATP
Structure of Mitochondria
Oxidative Phosphorylation
Double membrane leads to fourdistinct compartments:
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cow artery endothelial cell
cow heart muscle
cow liver
D! ≈ –0.06 V
Oxidative Phosphorylation
This antiporter works muchlike GLUT1. The import of ADP and export of ATP isfavored by 1) the [ATP] concentrations, and 2) thecharge difference.
0
This symporter has to combatthe charge difference of P to a more negative space, but its i^ going favored by the overwhelminghigh [H +] and [P i ] on the outside.
14% of protein in theinner membrane is the ADP/ATP translocase
Energy required to pump a single proton against a pH gradient
[H +in]
[H +out ] H +in ⇌ H +out
So, if its more negative And, if its more positive
As a consequence, it will take ~3 protons per ATP.
Oxidative Phosphorylation
D G^ ’^ = RT ln ____[H^ + z F D"
pHin ≈ 7.
pHout ≈ 6.
ln[H +]out = 2.3log[H +]out = -2.3 pH (^) out ln(1/[H +]in) = 2.3-log[H +]in = +2.3 pH (^) in
= RT2.3(pH (^) in – pH (^) out ) = 5.9(7.5 – 6.75) = 5.9(0.75) = 4.4 kJ/mol = 1.0 kcal/mol
= z F D" = (+1)(96480) D" = (+1)(96480)(+0.06) = 5.8 kJ/mol = 1.4 kcal/mol
Switch the sign herebecause reaction is opposite that of transport
D G^ ’^ = 1.0 + 1.4 = 2.4 kcal/mol
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D" ≈ –0.06 V
Electron Transport Electron-Transport Chain Complexes Contain a Series of Electron Carriers
Big Drop! FAD-E + 2 H^ +^ + 2e– à^ FADH^2 -E^ FeS –0. Big Drop!
Big Drop!
Electron Transport
Cytochromes
Electron Transport Cytochromes
Electron Transport
Cytochrome c