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Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps.

Publication ,  Journal Article
Alvarez, L; Suarez, SA; Bikiel, DE; Reboucas, JS; Batinić-Haberle, I; Martí, MA; Doctorovich, F
Published in: Inorg Chem
July 21, 2014

Azanone ((1)HNO, nitroxyl) is a highly reactive molecule with interesting chemical and biological properties. Like nitric oxide (NO), its main biologically related targets are oxygen, thiols, and metalloproteins, particularly heme proteins. As HNO dimerizes with a rate constant between 10(6) and 10(7) M(-1) s(-1), reactive studies are performed using donors, which are compounds that spontaneously release HNO in solution. In the present work, we studied the reaction mechanism and kinetics of two azanone donors Angelís Salt and toluene sulfohydroxamic acid (TSHA) with eight different Mn porphyrins as trapping agents. These porphyrins differ in their total peripheral charge (positively or negatively charged) and in their Mn(III)/Mn(II) reduction potential, showing for each case positive (oxidizing) and negative (reducing) values. Our results show that the reduction potential determines the azanone donor reaction mechanism. While oxidizing porphyrins accelerate decomposition of the donor, reducing porphyrins react with free HNO. Our results also shed light into the donor decomposition mechanism using ab initio methods and provide a thorough analysis of which MnP are the best candidates for azanone trapping and quantification experiments.

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Published In

Inorg Chem

DOI

EISSN

1520-510X

Publication Date

July 21, 2014

Volume

53

Issue

14

Start / End Page

7351 / 7360

Location

United States

Related Subject Headings

  • Porphyrins
  • Oxidation-Reduction
  • Nitrogen Oxides
  • Manganese
  • Kinetics
  • Iron
  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
 

Citation

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Alvarez, L., Suarez, S. A., Bikiel, D. E., Reboucas, J. S., Batinić-Haberle, I., Martí, M. A., & Doctorovich, F. (2014). Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps. Inorg Chem, 53(14), 7351–7360. https://doi.org/10.1021/ic5007082
Alvarez, Lucía, Sebastián A. Suarez, Damian E. Bikiel, Julio S. Reboucas, Ines Batinić-Haberle, Marcelo A. Martí, and Fabio Doctorovich. “Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps.Inorg Chem 53, no. 14 (July 21, 2014): 7351–60. https://doi.org/10.1021/ic5007082.
Alvarez L, Suarez SA, Bikiel DE, Reboucas JS, Batinić-Haberle I, Martí MA, et al. Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps. Inorg Chem. 2014 Jul 21;53(14):7351–60.
Alvarez, Lucía, et al. “Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps.Inorg Chem, vol. 53, no. 14, July 2014, pp. 7351–60. Pubmed, doi:10.1021/ic5007082.
Alvarez L, Suarez SA, Bikiel DE, Reboucas JS, Batinić-Haberle I, Martí MA, Doctorovich F. Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: defining the better traps. Inorg Chem. 2014 Jul 21;53(14):7351–7360.
Journal cover image

Published In

Inorg Chem

DOI

EISSN

1520-510X

Publication Date

July 21, 2014

Volume

53

Issue

14

Start / End Page

7351 / 7360

Location

United States

Related Subject Headings

  • Porphyrins
  • Oxidation-Reduction
  • Nitrogen Oxides
  • Manganese
  • Kinetics
  • Iron
  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences