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Cytochrome P450-Like Biomimetic Oxidation Catalysts Based on Mn Porphyrins as Redox Modulators

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Book cover Redox-Active Therapeutics

Abstract

In this chapter, we put forward an emerging concept on which the therapeutic action of some Mn porphyrins (MnPs) used in vivo may not be restricted to an SOD-type antioxidant catalytic role per se, but involve P450-type oxidation catalysis. ROS/RNS-type oxidants, such as hydrogen peroxide, hydroperoxides, and hypochlorite, are all classic oxygen donors in the chemistry literature of metalloporphyrin-based systems, mostly unavailable in the Pubmed database. Whereas the association of MnPs to a pro-oxidant therapeutic role is rather recent, MnPs have been explored as biomimetic oxidant catalysts for more than three decades in the fields of chemistry and catalysis. Merging the biological new discoveries and the typical oxidation chemistry findings would bring a breath of fresh air to both chemistry and biology with very positive prospects to the medicinal development of MnP-based therapeutics. The chapter includes, thus, a brief description of the general mechanism of the cytochromes P450 and related heme-containing enzymes, such as peroxidases (e.g., horseradish peroxidase) followed by the presentation of selected aspects of the 30+ years of biomimetic chemistry of MnPs as P450 models. It is not the goal of this chapter to provide a full account on the MnP-based biomimetic oxidation systems, but highlight some of the main features of P450-type MnP reactions that may become relevant on interpreting some of the biological results on the use of MnPs as redox-active therapeutics.

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Abbreviations

AH:

A generic 1-electron donor (AH → A• + H+ + 1e−)

AO:

A generic oxygen donor such as PhIO, ClO−, and H2O2 etc.

FeP:

Iron porphyrin

FeTPP+:

Fe(III) meso-tetraphenylporphyrin

HRP:

Horseradish peroxidase

LOOH:

Lipid hydroperoxide or an alkyl hydroperoxide

MnP:

Manganese porphyrin

MnTBAP3− :

Mn(III) meso-tetrakis(benzoic acid)porphyrin or Mn(III) meso-tetrakis(carboxyphenyl)porphyrin

MnTE-2-PyP5+ :

Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin

MnTM-2-PyP5+ :

Mn(III) meso-tetrakis(N-methylpyridinium-2-yl)porphyrin

MnTM-3-PyP5+ :

Mn(III) meso-tetrakis(N-methylpyridinium-3-yl)porphyrin

MnTM-4-PyP5+ :

Mn(III) meso-tetrakis(N-methylpyridinium-4-yl)porphyrin

MnTnBuOE-2-PyP5+ :

Mn(III) meso-tetrakis(N-n-butoxyethylpyridinium-2-yl)porphyrin

MnTnHex-2-PyP5+ :

Mn(III) meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin

MnTPP+:

Mn(III) meso-tetraphenylporphyrin

NADP+ :

Nicotinamide adenine dinucleotide phosphate

NADPH:

Reduced form of nicotinamide adenine dinucleotide phosphate

P450:

Cytochrome P450

PhIO:

Iodosylbenzene

RH:

A generic organic substrate usually an alkane

SOD:

Superoxide dismutase

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Acknowledgments

The authors thank Drs. Ynara M. Idemori, Brian R. James, Artak Tovmasyan, Ludmil Benov, Margaret E. Tome, Dayse C. S. Martins, Gilson DeFreitas-Silva, and Shirley Nakagaki, for many helpful scientific discussions throughout these years. Financial support by The Brazilian Research Council (CNPq, Brazil), CAPES Foundation (Ministry of Education, Brazil), Financiadora de Estudos e Projetos (FINEP, Brazil), and the National Institutes of Health (NIH, USA) are greatly acknowledged.

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Authors and Affiliations

  1. Departamento de Química, CCEN, Universidade Federal da Paraíba, Jardim Cidade Universitária, João Pessoa, PB, 58051-900, Brazil

    Victor Hugo A. Pinto, Nathália K. S. M. Falcão, Jacqueline C. Bueno-Janice & Júlio S. Rebouças

  2. Department of Radiation Oncology, Duke University Medical Center, Durham, NC, 27710, USA

    Jacqueline C. Bueno-Janice

  3. Department of Medicine and Duke Cancer Institute, Pharmaceutical Research Shared Resource, PK/PD Core Laboratory, Duke University School of Medicine, Duke Hospital South, 5317 Orange Zone, Trent Drive, Durham, NC, 27710, USA

    Ivan Spasojević

  4. Department of Radiation Oncology, Duke University School of Medicine, Research Drive, 281b/285 MSRB I, Box 3455, Durham, NC, 27710, USA

    Ines Batinić-Haberle

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  1. Duke University School of Medicine, Durham, North Carolina, USA

    Ines Batinić-Haberle

  2. Universidade Federal da Paraíba, João Pessoa, Paraíba, Brazil

    Júlio S. Rebouças

  3. Duke University School of Medicine, Durham, North Carolina, USA

    Ivan Spasojević

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Pinto, V.H.A., Falcão, N.K.S.M., Bueno-Janice, J.C., Spasojević, I., Batinić-Haberle, I., Rebouças, J.S. (2016). Cytochrome P450-Like Biomimetic Oxidation Catalysts Based on Mn Porphyrins as Redox Modulators. In: Batinić-Haberle, I., Rebouças, J., Spasojević, I. (eds) Redox-Active Therapeutics. Oxidative Stress in Applied Basic Research and Clinical Practice. Springer, Cham. https://doi.org/10.1007/978-3-319-30705-3_9

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