Abstract
Microperoxidase-11 (MP11) is an undecapeptide derived from horse heart cytochrome c (cytc). MP11 is characterized by a covalently linked solvent-exposed heme group, the heme-Fe atom being axially coordinated by a histidyl residue. Here, the reactions of ferrous and ferric MP11 (MP11-Fe(II) and MP11-Fe(III), respectively) with cyanide have been investigated from the kinetic and thermodynamic viewpoints, at pH 7.0 and 20.0 °C. Values of the second-order rate constant for cyanide binding to MP11-Fe(II) and MP11-Fe(III) are 4.5 M−1 s−1 and 8.9 × 103 M−1 s−1, respectively. Values of the first-order rate constant for cyanide dissociation from ligated MP11-Fe(II) and MP11-Fe(III) are 1.8 × 10−1 s−1 and 1.5 × 10−3 s−1, respectively. Values of the dissociation equilibrium constant for cyanide binding to MP11-Fe(II) and MP11-Fe(III) are 3.7 × 10−2 and 1.7 × 10−7 M, respectively, matching very well with those calculated from kinetic parameters so that no intermediate species seem to be involved in the ligand-binding process. The pH-dependence of cyanide binding to MP11-Fe(III) indicates that CN− is the only binding species. Present results have been analyzed in parallel with those of several heme-proteins, suggesting that (1) the ligand accessibility to the metal center and cyanide ionization may modulate the formation of heme-Fe-cyanide complexes, and (2) the general polarity of the heme pocket and/or hydrogen bonding of the heme-bound ligand may affect cyanide exit from the protein matrix.
Graphical Abstract
Microperoxidase-11 (MP11) is an undecapeptide derived from horse heart cytochrome c. Penta-coordinated MP11 displays a very high reactivity towards cyanide, whereas the reactivity of hexa-coordinated horse heart cytochrome c is very low.
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Abbreviations
- cytc :
-
Cytochrome c
- CM-cytc :
-
Carboxymethylated cytc
- CL-cytc :
-
Cardiolipin-bound cytc
- CL-CM-cytc :
-
Cardiolipin-bound CM-cytc
- Hb:
-
Hemoglobin
- legHb:
-
Leghemoglobin
- Mb:
-
Myoglobin
- Mb-Fe(II):
-
Ferrous Mb
- Mb-Fe(III):
-
Ferric Mb
- MP:
-
Microperoxidase
- MP8:
-
Microperoxidase-8
- MP11:
-
Microperoxidase-11
- MP11-Fe(II):
-
Ferrous MP11
- MP11-Fe(III):
-
Ferric MP11
- Ngb:
-
Neuroglobin
- Pgb:
-
Protoglobin
- trHb:
-
Truncated Hb
- trHbN:
-
trHb type N
- trHbO:
-
trHb type O
- trHbP:
-
trHb type P
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This study was partly supported from a Grant of the Roma Tre University (CAL 2015 to PA).
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Ascenzi, P., Sbardella, D., Santucci, R. et al. Cyanide binding to ferrous and ferric microperoxidase-11. J Biol Inorg Chem 21, 511–522 (2016). https://doi.org/10.1007/s00775-016-1361-z
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DOI: https://doi.org/10.1007/s00775-016-1361-z