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Cyanide binding to ferrous and ferric microperoxidase-11

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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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Acknowledgments

This study was partly supported from a Grant of the Roma Tre University (CAL 2015 to PA).

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Correspondence to Paolo Ascenzi.

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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

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