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OXPHOS. Electron transport chain Oxidative phosphorylation. The tale thus far…. From one glucose molecule we have ATPs NADHs FADH 2 s 6CO 2. (4). (10). (2). (ATP). Redox reactions. Reduction—gains electrons Oxidation—loses electrons
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OXPHOS Electron transport chain Oxidative phosphorylation
The tale thus far…. • From one glucose molecule we have • ATPs • NADHs • FADH2s • 6CO2 (4) (10) (2) (ATP)
Redox reactions • Reduction—gains electrons • Oxidation—loses electrons • In biological systems, protons often accompany the electrons.
Reduction Potentials High Eo' indicates a strong tendency to be reduced Go' = -nFEo' Eo' = Eo'(acceptor) - Eo'(donor) Electrons are donated by the half reaction with the more negative reduction potential and are accepted by the reaction with the more positive reduction potential: Eo’ positive, Go' negative See table 14-2, pg. 429
Example: Half reactions: NAD+ NADH 2 electrons Eº'= -0.32 volts O2 H20 2 electrons Eº'= +0.816 volts Which will be the electron acceptor? Oxygen Eo' = Eo'(acceptor) - Eo'(donor) Eo'= 0.816-(-0.32)= 1.136 V Go' = -nFEo' Go' = -2(23,062 cal/mol-V)(1/136 V) Go' = -52.4 kcal/mole
NADH vs. FADH2 Half reactions: NAD+ NADH 2 electrons Eº'= -0.32 volts FAD FADH2 2 electrons Eº'= -0.18 volts O2 H20 2 electrons Eº'= +0.816 volts Is more energy or less released in the reoxidation of FAD than NAD+? Less, so fewer ATP's are ultimately made
The tale thus far…. • From one glucose molecule we have • A proton gradient • 6CO2 • 6H2O (ATP)
The Chemiosmotic Theory • Peter Mitchell (1961) • Proton gradient drives ATP synthese • Thus, electron transport is "coupled" to ATP synthesis by the proton gradient
Evidence • Electron transport pumps protons • Complexes are asymmetric in membrane • Membranes with complexes I-IV will do electron transport, but….. • Need an intact membrane for oxphos • Decoupling reagents allow electron transport but not oxphos • Proton gradient is steep enough to drive ATP synthesis (I.e., there's enough energy) • Artificial proton gradients work just fine
How? • F1/Fo ATPase • Makes ATP from ADP and Pi • Can also do the reverse reaction • ATPase activity Early evidence ….
Grand Totals (in theory) • From one glucose molecule we have • 4 ATPs • 10 NADHs 30 ATPs • 2 FADH2s 4 ATPs Total = 38 ATP/glucose But in reality
Proton gradient used for many things
Reality ~ 30 ATP/glucose