You are on page 1of 36

!

 " # $


%

|  
 

  


  

 
|  


  
 &
Aox + Bred ÆÆ Ared + Box
Aox 
 ' (  $ A ) ' *
Bred 
   " $  B )   " *
+
"     
,  $  
  
  
&
Aox + n e- ÆÆ Ared e.g., Fe+++ + e- ÆÆ Fe++
Box + n e- ÆÆ Bred
Aox + n e- ÆÆ Ared
Box + n e- ÆÆ Bred
+    &
| = |   nF (ln [reduced][oxidized])
,   
  &
| = |   nF (ln [Ared][Aox])
|-  ,.-

,+-+  ,-/ 6
0  [Ared] = [Aox], | = | .
|  
 mid-point potential,
    '
 ,     [oxidant] = [reductant]
   
+   
&
ô|  = | (oxidant)  | (reductant) = | (acceptor)  | (donor)
ôGo =  nFô| 
)|12
 $  *

  
 
pontaneou ) 
ôd* |     
$  |    
,,  
 poitive ô| 

  
  
 $34'&
© O2 + 2H+ + 2e- Æ H2O
|  = +0.815 V
{AD+ + 2H+ + 2e- Æ {ADH + H+
|  = 60.315 V
3"   $ &
© O2 + {ADH + H+ Æ H2O + {AD+
ô| = +1.13 V
ôG = 6 nFô|o =  2(96494)(1.13) =  218 kJmol
|  

{AD+{ADH  FADFADH2  " 


  
FM{ )F M{"  *
 
 
" 
$ 

%

$ 
""+)+  
"  *," 5  "  
0  
 ",+!3) 5+*  
2 e- + 2 H+  $FM{H2
O O O
H H H H H
C N C C N C C N C
H3 C C C C NH H 3C C C C NH H3 C C C C NH

H3 C C C C C O H 3C C C C C O H3 C C C C C O
C N N C N N C N N
H H H H
CH 2 6 CH2 6
CH2
     
HC OH HC OH HC OH

HC OH HC OH HC OH

HC OH O HC OH O HC OH O

H 2C O P O- H2C O P O- H2C O P O-

O- O- O-
 ë 


FM{, "    
 
$($
, 
1 e6  $   " emiquinone radical
 
$6"    6  +!34
3  7  1 or 2 e6,+!3
 $ 
role $  6  
 
  
6
),34*8 
    6 ),+999*

À
 À 
 
 
 

 À    
 
À 

($:

oenzyme Q ) :,:,"6"*
hydrophobic
% 

 
      $$ 
 
""  : " 
  
   , 
$"  "
   
5 $    
  $" 
!
 -
 
   : 
         
 ,"$      $$ 


O
CH3O CH3

CH3
CH3O CH2 CH C CH2 H
O ($ 
6  

OH
CH3O CH3
 quinone  
CH3
($: 
CH3O CH2 CH C CH2 H
 "  quinol
OH ($
 6  & 

Q + 2 e6 + 2 H+ ÆÆ QH2
 À O6
 À  CH3O CH3
6
 CH3
 À     CH3O CH2 CH C CH2 H
À O
($: ($:;6
6949
À
À 


À    
À ($:4

0 " 
 


 $ '
,
oQ   1 e6  $ emiquinone radical (Q·6*
 "
 :, 5+!3, $   6 8 6

7 

oenzyme Q "

 $ 6   
 $   $$ 
%
  
$$  H+ tranport "  
6  
)Q ycle*  
"

  


    


{
 
{  {
6 

ÀÀ     
{


 



ÀÀ6 4$

Heme 
 
 " cytochrome
4$ 
  $  

$
 Fe 
  { $
   


    


{
 
{  {
6 

ÀÀ     
{


 



ÀÀ6 4$

4$
 <


  $)a,b,c*  
  

"
"
  

$$$  "

 
  
= heme c 
   5 
    
cyteine 
 "

 CH3

CH2 CH2 CH C CH2 3 H

CH3 HC OH

O
N
HC CH3
N Fe N
6
OOC CH2 CH2 CH CH2
N

CH2 CH3

CH2

COO6 ’$ 

Heme a 
"6"    
 
  
  " 
<
 "

>#  ? @

% .
!  
  
$  , 
 

$


  
 8
5
,
  Fe 
 
  


     4$ $

  $ "  1 e6  



   "

 
&Fe+++ + e6 ÆÆ Fe++
X
  
  
  $Fe 
"
"    { {
2 axial ligand, 8
Fe
   $ )A,@*
4 {    { {

>#  ? @ Y

4

'   
$ 3 {
$
  $  
  

'   
 !3
) *  4
{ ) "*
!  $ 
= $  
)$* '    
4$ $ 


 $

ytochrome 
  $
 "

  
     
  


  
"' 7 "  
$  

 $  '
 
   $
3$ $
    integral membrane
complexe,  

 
   
  
 " $"    

ytochrome c 

  
$ , 
 " 
  
  $"
 $ ># 
? @

$ $ '%D

 
 

 
 
B
< B
C

½oitively charged lyine 
 "
)$  *
"" 
  $ 
"  cytochrome c
 
$    
 "
$$ 
$ '
  
, 
  6
  
Cys S  C
S Fe
Cys
S Fe S
S Fe S
Cys Cys
S Fe
S

Cys S S S Cys
Fe Fe  
" "
   '
Cys S S S Cys
     F
%E" " 
  $ 8 
E 

þron-ulfur center )Fe-3* 
 "
 
164 iron atom $ '  $ 8
3 $

|  

$  $"  +3

4-Fe 
     
"", Fe 83 $

 

  "
s 
 
s
  
  
s s
%
" "
 
  

 one electron, 
s    s
  $
 
 $
, "
  
 
'$   s    s
$
 %E" " 


|, +$   '
 
&
Fe+++3, Fe++1 )' ( * + 1 e6 ÆÆ Fe+++2, Fe++2 ) " *


$ '



  $$ 

 

epiratory  "


$$ à $   $$ 
hain:
!

"
  
   
$   inner mitochondrial membrane
) 
$$$     *
 $   $$ 
  

  critae  
 $$   
! '     
 4993439949499G=4=

6 
% : %%% %D

à

%$$ 3 
|  
 ${ADH O2  
$" 
""
$$  complexe þ, þþþ & þV, "
oQ 8 cyt c
0   $ ', 



6"  " 


   

oQ 
        $$  

 

  : $ '

ytochrome c 
 
 $$ 
 %
  
$ '%%%%D "6  

$
 .
   $ '

{o. of ½rothetic
omplex {ame ½rotein Group

omplex þ {ADH 46 FM{,


Dehydrogenae 7 Fe-3 cntr.

omplex þþ 3uccinate-oQ 5 FAD, cyt b560,


eductae 3 Fe-3 cntr.

omplex þþþ oQ-cyt c 11 cyt bH, cyt bL,


eductae cyt c1, Fe-3ieke

omplex þV ytochrome 13 cyt a, cyt a3,


Oxidae uA, uB
 '     
 ’   ’   ’ ’    ’ 


6
% %%% %

à

%$$ E 

Mid-point potential  


"6  
 


  6  


pontaneou
.
   
 " &
otenone )  
* 5
$ '%
Antimycin A  5
  
$ '%%%
{6 8O  $ '%D
%     


  56  
 $
34=

39
34
omplex þ
  (
 $ '
'  
$   
34,  $$  $ '%
 " 
($:&
{ADH + H+ + Q 2 {AD+ + QH2
 
$$ 49 "'

    
 


"

  
'  
  
$ '%
L-haped  
 "
 

""
      
 $ ' 
$ $$
 " 
  
H


3 
 
34

 "|!

""  $ '
$ '%

$   

    $$  $ '%

  
3d 

  $  34 
" 

 $   $ '
($:
  $$  $ 
+3
  34  $ 8 
 $  
 $$ 
$
    

 &
{ADH + H+ + FM{ Æ {AD+ + FM{H2
FM{H2 + (Fe-3)ox Æ FM{H· + (Fe-3)red + H+
 +3
' (  
   
 '
" "    &
FM{H· + (Fe-3)ox Æ FM{ + (Fe-3)red + H+
| 


 "  

 
" "

$ '%," ($:
($: 
 6  5
" 49  
  "  " QH2
  6
 6
Q QH2
    
3uccinate
Dehydrogenae of    via FAD  
  K
Cy  i
 6
 6

a
o a  complex þþ
ina fu$aa
o 3uinaCoQ 3uina D  na

. ua
 ) $  %%*

+
   
+
 " FADH2 "'  
" 
 "$  
+4 
 ' (  
  

 "  

  
" "
 ($
:, QH2
$ '%%

= +
A 
   
 

 |  +3
$ '%%  
 
linear  $  :

  
  $
$$ 
$ '%%,

  $ 
   
6" 
  

& >#3|K

FAD 2 Fe3center 1 2 Fe3center 2 2 Fe3center 3 2 oQ


% 

 
""'   )=*
" 
  
" 
 '     
 ’   ’   ’ ’    ’ 


6
% %%% %

à

%$$ E 

omplex þþþ 


 
 $($ QH2  

    
$ '
%8%%
 
""   
 $ '%%%  
"

 
 

'  
  
 $, 
 " $ '%%%,
 "
cytochrome c,  
   
$ '%D
! '     
4993439949499G=4=


6
% : %%% %D

à

%$$ 3 

ytochrome oxidae )complex þV*  


" 
 
  &
O2 + 4 H+ + 4 e6 Æ 2 H2O
  "  
  
    $ ' 
 $ $  $ 
$$ 

 $'
 $) f  *

% $$  $ 
  $'

)$ '%D*

$   tranmembrane
|-helice
$ '%D
"  

$ < "#

>#= 


Metal center   $'
)$ '%D*&
$ 8 $ <,
") I  " $
*8 "#
=  
  binuclear center 

 $ <
 "#
f  

!   

$ '%D&
Heme axial ligand 4
3
$

4$ 
   
 
$$ 
|  

 ' 4

 

  f4$ 
  $ '


"  
Heme a3,  

 I  4
  

"#,
  '    
u ligand 

 4
3,8
 
  "
 
3, $ <
!3,8 d " 5= "#
| 
 
  $
$ '%D " uA #= 
8heme a

  

 binuclear center   


 $   5
 
O2 bind   '    
 heme a3,
I uB
"  
O2 + 4 H+ + 4 e6 Æ 2 H2O ’
  


 
   
6"

    
$ <
yr-Hi $ ' I  
"  

"   " 
  == 
 
 = 


  '    
  $ < $ 5


"
   {6,O,   
 
$ " J{O
 inhibit  $'
 
."  
 J3=

"