Electron Transport and Oxidative Phosphorylation

Lesson Learning Outcomes

Upon completion of this lecture, students should be able to: understand the electron transport chain understand the oxidative phosphorylation

Electron Transport Chain

Carried out by four closely related multisubunit membrane-bound complexes and two electron carriers, coenzyme Q and cytochrome c
in a series of oxidation-reduction reactions, electrons from FADH2 and NADH are transferred from one complex to the next until they reach O2 O2 is reduced to H2O O 2 + 4 H+ + 4 e 2 H2 O as a result of electron transport, protons are pumped across the inner membrane to the intermembrane space

Electron Transport Chain

Proton gradient across inner mitochondrial membrane

Electron Transport Chain

the proton gradient establishes a voltage gradient the proton and voltage gradients together provide the mechanism to couple electron transport with phosphorylation of ADP

ADP + Pi

ATP + H2 O

Electron Transport Chain

Complex I
NADH-CoQ oxidoreductase
electrons are passed from NADH to FMN
O H3 C H3 C N N N NH O H3 C
2 -

2 H+ + 2 eH N N N CH2 H ( CHOH ) 3 CH2 O PO 32 Dihydroflavin mononucleotide (FMNH 2 )

O NH O

CH2 ( CHOH ) 3 C H 2 O PO 3 Flavin mononucleotide (FMN)

H3 C

Complex I
electrons are then passed to the iron-sulfur clusters finally, electrons are passed to coenzyme Q (also called ubiquinone)
O CH3 O CH3 O CH3 CH3
n

(CH2 CH= CCH2 ) O Coenzyme Q (oxidized form)

2 H

+ 2 e

reduction oxidation

OH CH3 O CH3 O CH3 CH3

n

(CH2 CH= CCH2 ) OH Coenzyme QH (reduced form)

2

Complex I
the overall equation for the reaction of complex I is
N AD H + H + + E- FM N E- FM NH 2 + 2 Fe - S( ox) Fe - S( re d) + CoQ + 2 H + N AD H + H + + CoQ N AD + + E- FM NH 2 E- FM N + 2 Fe - S( re d) + 2 H + Fe - S( ox) + CoQ H 2 N AD + + CoQH 2 G' = -81 kJmol
-1

this transfer of electrons is strongly exergonic and is sufficient to drive the phosphorylation of ADP

ADP + Pi

-1 ATP + H2 O G' = +30.5 kJmol

Complex II
Succinate-coenzyme Q oxidoreductase
C O OCH2 CH2 COO Succinate E-F A D H 2 + C o Q Succinate + CoQ
-

H + E-F A D
-

C O OC C + E-F A D H 2 H

OOC

Fumarate E-F A D + C o Q H 2 Fumarate + CoQH2 G' = -13.5 kJmol

-1

the overall reaction is exergonic, but not enough to drive ATP production no H+ is pumped out of the matrix during this step

Redox Forms of CoQ

O CH3 O CH3 O O Coenzyme Q CH3 R e
-

O CH3 O CH3 O CH3 R

-

e-

OCoenzyme Q

2 H+ + e 2 H+ + e OH CH3 O CH3 O OH Coenzyme QH CH3 R

2

Complex III
CoQH2-cytochrome c oxidoreductase
CoQH2 + 2 Cyt c[ Fe( III) ] CoQ + 2 Cyt c[ Fe( II) ] + 2 H+
-1 G' = -34.2 kJmol

this decrease in free energy is sufficient to drive the phosphorylation of ADP to ATP (G0 = + 30.5 kJmol-1)

Complex IV
Cytochrome oxidase:
2 C y t c [ F e( II) ] + 2 H + + 1 O 2 2 2 C y t c [ F e( III) ] + H 2 O G' = -110 kJmol
-1

complex IV contains cytochrome a, cytochrome a3, and Cu(II), which are also involved in the electron transport complex IV is the link with molecular oxygen

+ H+ + 1 O2 NADH 2

NAD + + H2 O

The heme group of the cytochromes

Electron Transport Chain

Coupling Ox and Phos

the energy-releasing oxidations give rise to proton pumping and a pH gradient across the inner mitochondrial membrane in addition, differences in the concentration of ions across the membrane generates a voltage gradient a coupling process converts the electrochemical potential to the chemical energy of ATP the coupling factor is ATP synthase, a complex protein oligomer, separate from the electron transport complexes

ATP Synthase

Coupling Ox and Phos

P/O ratio: the number of moles of Pi consumed in phosphorylation to the number of moles of oxygen atoms consumed in oxidation
Phosphorylation (P) A D P + Pi A TP + H2 O H2 O

Oxidation (O) 1 / 2 O2 + 2 H+ + 2 e-

P/O = 2.5 or 3.0 when NADH is oxidized P/O = 1.5 or 2.0 when FADH2 is oxidized

Mechanism of Ox/Phos
The mechanism by which the proton gradient leads to the production of ATP depends on ion channels through the inner mitochondrial membrane
protons flow back into the matrix through channels the flow of protons is accompanied by formation of ATP the details of how phosphorylation takes place as a result of the linkage to the proton gradient are not explicitly specified by this mechanism

The overall effect of electron transport reaction series is to move protons out of the matrix into the intermembrane space, creating a difference in pH across the membrane.

Formation of ATP accompanies the flow of protons back into the mitochondrial matrix.

End of lecture
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