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Electron Transport and Oxidative

Phosphorylation
Chapter 15
Chapter 3 (81-85)

Electron transport = transfer of efrom one carrier to another

15.1

Oxidative phosphorylation =
process by which energy released
from electron transport
(oxidations) is conserved in form
of phosphate-bond energy of ATP

Oxidation-reduction reactions = transfer of electrons from a


donor (reducing agent) to an acceptor (oxidizing agent).
Analogous to acid-base reaction:
acid/base: proton acceptor + H+ !
redox:

electron acceptor + e- !

proton donor
electron donor

Tendency of a substance to give up electrons (to be oxidized)


is reflected in the standard reduction potential, E
Ao + e- ! Ar

EA

Bo + e- ! Br

EB

Ao + Br ! Ar + Bo
E = EA - EB = reduction potential difference
pp. 81-83

(acceptor)

(donor)

Electrochemical cell
0.77 V

Fe3+ + e- ! Fe2+

H+ + e- ! 1/2H2

E = 0.0 V (standard conditions)

p. 82

The more
negative the
potential for a
redox pair, the
reductant has
greater tendency
to lose electrons.
The more
positive, the
reductant has less
tendency to lose
electrons.

oxidant + n e- " reductant; n = # electrons transferred

E' is related to G' and Keq by:

G'= nFE'
= nF(E'acceptor E'donor )

(eqn. 15.1)

F = Faraday constant = 96494 coulomb/mol = J/voltmol


n = # mol electrons transferred
Rearrange:

G' RT
E'=
=
ln keq
nF
nF

Ao + Br " Ar + Bo
RT [A r ][Bo ]
E = E'
ln
nF [A o ][Br ]

Variable
G
pH
E

[A r ][Bo ]
G = G' + RT ln
[A o ][Br ]
(eqn. 15.2)

Standard
=
+
term
=
=
=

G
pKa
E

Logarithmic
concentration term
RT ln

[Products]
[reactants]

[A ]
log
[HA]

RT [Ar ][Bo ]
ln
nF [Ao ][Br ]

NAD-NADH pair will tend to lose


electrons to OAA-malate pair under
standard conditions:
E (V)
NAD+ + 2H+ + 2e- ! NADH + H+ -0.32

OAA + 2H+ + 2e- ! malate
 -0.17
NADH + H+ + OAA ! malate + NAD+

E= -0.166 - (-0.32) = +0.15 V

G'= nFE'
G = -2 x 96485 J/Vmol x [-0.166V - (-0.32V)]
= -28.9 kJ/mol

acceptor

donor

Electron carriers in the respiratory chain


NAD+-linked dehydrogenases

2-electron transfers only

15.3

Flavin-linked dehydrogenases

14.6

Can handle 1- or 2-electron


transfers

Iron-sulfur proteins (Fe-S) (non-heme)

Fe(III) + e- " Fe(II)


oxidized
reduced

15.4

Ubiquinone (Coenzyme Q)

p. 631

Cytochromes (heme)

Fe(III) + e- " Fe(II)


oxidized
reduced

15.6

Cytochromes (heme)

15.5

15.6

Pathway of
electron transport

I: NADH dehydrogenase

II: Succinate-Coenzyme Q
reductase
III: Coenzyme Q -cytochrome c
oxidoreductase

IV: Cytochrome c oxidase

15.2

Multiprotein complexes in the


mitochondrial respiratory chain

15.10

15.7

NADH-Ubiquinone
oxidoreductase (Complex I)

Inhibitors:
rotenone
amytal

15.11

Complex II:
Succinate - Coenzyme Q reductase
15.2

= succinate dehydrogenase of TCA cycle

Complex II (succinate dehydrogenase or succinate-CoQ reductase)

15.12

CoQ collects electrons from


multiple flavoproteins

15.1
3

Complex III: Ubiquinone-cytochrome c oxidoreductase (cytochrome bc1 complex)

15.14

Inhibitors:
antimycin A

Q cycle of Complex III

15.15

Complex IV: Cytochrome c oxidase complex


Net reaction:
4 cyt cred + 8H+in + O2 !
4 cyt cox + 4 H+out + 2 H2O

Inhibitors:
CN-
CO
15.16

Summary of electron transport

15.19

15.7

15.18

Can calculate standard-free energy change as pair of electrons are


transferred from NADH to molecular oxygen, i.e. along entire
length of respiratory chain:
NAD+ + 2H+ + 2e- --> NADH + H+

E'
- 0.32 V (donor)

1/2O2 + 2H+ + 2e- --> H2O

+ 0.82 V (acceptor)

G'= nFE'
G = -2 x 96494[0.82 - (- 0.32)] = - 221 kJ/mol
Enough energy to make 6-7 ATP. Only make 2.5-3/passage of pair electrons

+0.031 V

+0.045 V

Complex II: succinate + Q ! fumarate + QH 2


G' = 2(96485)(0.045 0.031) = 2.7 kJ/mol
15.7

Mechanism of ATP synthesis: Chemiosmotic hypothesis (Mitchell)


15.19

C2
G = RT ln + ZF (eqn. 15.4)
C1
G ~ 20 kJ/mol H+ X 10 H+
for H+:
= ~200 kJ per 2 e- ! O2
ln(C2/C1) = 2.3pH; ~ 0.15 0.2 V

Mitochondrial ATP Synthase complex (Complex V)

15.21a

Binding-change model
(Boyer)

15.23

X-ray structure of F1 complex (Walker)

15.22

15.24

15.25

Mechanism of ATP synthesis: Chemiosmotic hypothesis

Under most physiological conditions, e- transport is tightly coupled


to phosphorylation of ADP = respiratory control

15.19

15.27

15.27

Uncouplers

p. 648

Energy-generating capacity of cell is closely attuned


to its energy demands

p. 654

Energy yields from oxidative metabolism


Glycolysis:
Glucose + 2ADP + 2Pi + 2NAD+ ! 2 pyruvate + 2ATP + 2NADH + 2H2O + 2H+
Pyruvate dehydrogenase complex:
2 pyruvate + 2NAD+ + 2 CoA-SH ! 2 acetyl-CoA + 2NADH + 2CO2
Citric acid cycle (including conversion of GTP to ATP):
2 acetyl-CoA + 4H2O + 6NAD+ + 2FAD + 2ADP + 2Pi !
4CO2 + 6NADH + 2FADH2 + + 2 CoA-SH + 2ATP + + 4H+
Net:
Glucose + 10NAD+ + 2FAD + 2H2O + 4ADP + 4Pi !
6CO2 + 10NADH + 2FADH2 + 4ATP

Based on P/O ratios of 2.5 for NADH and 1.5 for FADH2:
Total ATP yield = [4 + (2.5 X 10) + (1.5 X 2)] = 32