Biochemical Energetics IV – Oxidative Phosphorylation

(a major study in energetic coupling)

Extracting energy from carbon compounds = oxidation

High E Low E
O2 -------------------------------------------------------------------------> H2O

CH3 -----> CH2OH -----------> CHO ------> COOH ----------> CO2

The overall process:

Glucose + 6O2 6CO2 + 6H2O ∆Go = -2878 kJ/mol
nADP + nPi nATP + nH2O ∆Go = +32.5 kJ/mol
What is the maximum n could be if the process was 100% efficient? 88 ATP/glucose
Glycolysis, you remember nets 4 ATP / glucose (5 % effeciency), so the cell would like to do better
– hence oxidative phosphorylation. OxPhos (as it's affectionately know) takes place in the
mitochondrion:

TIBS 25,319-324 (2000)

Inner mitochondrial membrane is 70 % protein, 30 % lipid.

Glycolysis to pyruvate takes place in the cytoplasm, pyruvate moves into the mitochondrial matrix,
where it's converted to acetyl-CoA:

And then fed into the TCA (or “Krebs”)

cycle:

The overall point is to sequentially oxidized

the two carbons entering the system to CO2,
harvesting electrons along the way, and
storing them on NADH (or FADH2).
 +2e-
+H+ -->

Now that we're talking electrons, we need to look an alternative way of expressing free energy
changes for reduction / oxidation (redox) reactions:

Reductant + Oxidant Reductant(ox) + Oxidant(red)

e.g.: Cu+ + Fe3+ <------------> Cu2+ + Fe2+

(red) (ox)

... and introduce our last “State” variable:

∆Eo, the reduction potential (in units of Volts)
∆Eo is proportional to ∆Go (but with the opposite sign!):
∆Go = - nF ∆Eo n = number of electrons
F = Faraday constant (=96,485 J/mol V), for converting units
For example: NAD+ + 2e- + 1H+ <--->NADH, ∆Eo = -0.32V
If ∆Eo > 0, the molecule is a strong electron acceptor (= oxidant)
If ∆Eo < 0, the molecule is a strong electron donor (= reductant)

As with ∆Go, for a series of steps:

∆Eo = Σ∆Eo of each step

Also, for non-standard conditions:

∆E = ∆Eo + (RT/ nF) ln[Acceptor/Donor]
and, by convention:
∆E = ∆Eo + (2.303 RT/ nF) log [Acceptor/Donor]
∆E = ∆Eo + (0.059V/ n) log [Acceptor/Donor]

Back to Oxidative Phosphorylation:

The electrons from NADH and FADH2 are fed into the mitochondrial electron transfer chain, where
they will ultimately be combined with H+ and oxygen to form water:
Problems for Biochemical Energetics IV:

1. For the reaction Cys-S-S-Cys + 2e- +2H+ ---> 2 CysSH, ∆Eo = -0.25V. What is the standard free
energy (∆Go) for disulfide bond reduction in a protein?

2. The average recommended caloric intake for an adult is ~2,000 Cal (=2,000kcal). If ¾ of that is
carbohydrate, and your body used all the carbohydrate to make ATP, how much ATP would that be
(in moles, and in kg)? (the MW of ATP is 505 gm/mole).

3. What ∆Eo between two electron carriers that pump a proton would be needed to drive the
synthesis of 1 ATP using just 1 electron? using 2 electrons?

4. If ∆Eo for electron transfer from A->B (which pumps 1 H+/e-) is 0.059 V, what H+ concentration
gradient across the membrane would be needed to drive reverse electron transfer (from B->A) if ∆ψ
= 0 mV?