scholarly journals Low-temperature studies on mixed-valence cytochrome oxidase by using magnetic circular dichroism

1976 ◽  
Vol 159 (3) ◽  
pp. 811-813 ◽  
Author(s):  
T Brittain ◽  
J Springall ◽  
C Greenwood ◽  
A J Thomson

The spin states of the haem components of mixed-valence cytochrome oxidase were studied at room temperature and at temperature down to 20K by using magnetic circular dichroism. The room-temperature studies show the presence of a low-spin ferrous haem together with a low-spin ferric haem, which we attribute to heams a3 and a respectively. At temperatures below 100K it appears that the CO of the mixed-valence CO complex may be irreversibly photolysed, and that in this case haems a and a3 assume their high-spin states. Thus in this enzyme haem-haem interactions appear possible at temperatures below 100K.




2006 ◽  
Vol 71 (11-12) ◽  
pp. 1627-1641 ◽  
Author(s):  
Marek Stupák ◽  
Jaroslava Bágeľová ◽  
Diana Fedunová ◽  
Marián Antalík

Conformational transitions of horse heart ferricytochrome c (ferricyt c) have been investigated in the presence of strong inorganic acids and their salts by optical absorption spectroscopy, magnetic circular dichroism and circular dichroism. In the presence of acids (HClO4 or H2SO4, pH 2) or their salts (1 M NaClO4 or Na2SO4, pH 2, 25 °C), the three ligation states of ferricyt c heme were identified. One is the high-spin state: His18-Fe-H2O (40-50%), and two are the low-spin states: His18-Fe-Met80 (30-25%) and His18-Fe-His (30-25%). Under these conditions low temperatures facilitate native heme coordination of ferricyt c. Transition from low-spin to high-spin heme coordination of ferricyt c is complete in 1 M HClO4 or 3 M H2SO4. At the concentration of HClO4 and H2SO4 above 3 M, different behavior in spectral transitions of ferricyt c near the heme is observed. High-spin pentacoordinated ferricyt c with the heme ligand of His18-Fe is formed in 8 M H2SO4. This state is unstable at higher concentration of H2SO4 and porphyrin ferricyt c is formed. At HClO4 concentration higher than 3 M, the new, until this time not observed heme coordination structure of ferricyt c originates.





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