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Hoffmann, R. A wiki for the life sciences where authorship matters. Nature Genetics (2008)
 
 
 
 
 

Protonation of two adjacent tyrosine residues influences the reduction of cytochrome c by diphenylacetaldehyde: a possible mechanism to select the reducer agent of heme iron.

We have shown that diphenlacetaldehyde (DPAA) is able to promote mitochondrial DeltaPsi disruption accompanied by damage in mitochondrial DNA, lipids, and proteins [Almeida, A. M.; Bechara, E. J. H.; Vercesi, A. E.; Nantes, I. L. Free Radic. Biol. Med. 27:744-747; 1999]. In this work, DPAA was used as a model of carbonyl reagent for cytochrome c. The results suggest that DPAA is a redox cytochrome c modifier. Conversion of Fe(III) to Fe(II) cytochrome c promoted by DPAA is pH dependent. The second-order rate determined for heme iron reduction (k2) is 698 M(-1) s(-1) and this process occurs with an activation energy of 8.5 +/- 0.8 kcal/ mol. Analysis of the pH profile suggests the presence of two ionizable cytochrome c groups (pKa1 = 8.9 and pKa2 = 11.4) related to the electron transfer from DPAA to heme iron. The heats of ionization of the two prototropic groups, pKa1 (DeltaH(ion) = 6.5 kcal/ mol, DeltaS(ion) = -29.0 cal/mol.K), and pKa2 (DeltaH(ion) = 5.0 kcal/ mol, DeltaS(ion) = -24.0 cal/mol.K), suggest involvement of two tyrosine residues, probably Y67 and Y74, related to DPAA-promoted heme iron reduction. The cytochrome c chemical modification by iodination of tyrosine groups significantly decreased the reduction rate promoted by DPAA, and shifted the pH(opt) value from 10.0 to 9.25. The cytochrome c-promoted DPAA electron abstraction quickly produces the expected enol-derived radical, as indicated by 3,5-dibromo-4-nitrosobenzenesulfonate (DBNBS) spin trapping EPR measurements. This radical reacts with molecular oxygen, producing a peroxyl intermediate radical that, via a putative dioxetane intermediate, promotes formation of benzophenone as the main final product of this reaction, detected by high-performance liquid chromatography coupled with tandem mass spectrometry.[1]

References

  1. Protonation of two adjacent tyrosine residues influences the reduction of cytochrome c by diphenylacetaldehyde: a possible mechanism to select the reducer agent of heme iron. Rinaldi, T.A., Tersariol, I.L., Dyszy, F.H., Prado, F.M., Nascimento, O.R., Di Mascio, P., Nantes, I.L. Free Radic. Biol. Med. (2004) [Pubmed]
 
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