Synthesis and electrochemistry of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis (3,5-dichloro-2,6-dimethoxyphenyl)porphyrin (H2tdcdmpp), [CoII(tdcdmpp)] and [M(tdcdmpp)Cl](M = FeIII or MnIII)

Autret, Marie; Ou, Zhongping; Antonini, Alessandra; Boschi, T.; Tagliatesta, Pietro; Kadish, Karl M.

doi:10.1039/dt9960002793

Cited by 56 publications

(56 citation statements)

References 23 publications

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“…Metallation in methanol was accomplished under refluxing conditions, whereas in water it was achieved at room temperature. When the pH of the water was raised to ϳ12.3 (20,25), 3 metallation was accomplished in ϳ15 min. Routinely, a 1:20 ratio of porphyrin to metal in water at room temperature was applied.…”

Section: Manganese Porphyrinsmentioning

confidence: 99%

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The Ortho Effect Makes Manganese(III)Meso-Tetrakis(N-Methylpyridinium-2-yl)Porphyrin a Powerful and Potentially Useful Superoxide Dismutase Mimic

Batinić‐Haberle¹,

Benov²,

Spasojević³

et al. 1998

Journal of Biological Chemistry

254

300

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The ortho, meta, and para isomers of manganese(III) 5,10,15,20-tetrakis(N-methylpyridyl)porphyrin, MnTM-2-PyP 5؉ , MnTM-3-PyP 5؉, and MnTM-4-PyP 5؉ , respectively, were analyzed in terms of their superoxide dismutase (SOD) activity in vitro and in vivo. The impact of their interaction with DNA and RNA on the SOD activity in vivo and in vitro has also been analyzed. Differences in their behavior are due to the combined steric and electrostatic factors. In vitro catalytic activities are closely related to their redox potentials. The half-wave potentials (E1 ⁄2 ) are ؉0.220 mV, ؉0.052 mV, and ؉0.060 V versus normal hydrogen electrode, whereas the rates of dismutation (k cat ) are 6.0 ؋ 10 7 , 4.1 ؋ 10 6 , and 3.8 ؋ 10 6 M ؊1 s ؊1 for the ortho, meta, and para isomers, respectively. However, the in vitro activity is not a sufficient predictor of in vivo efficacy. The ortho and meta isomers, although of significantly different in vitro SOD activities, have fairly close in vivo SOD efficacy due to their similarly weak interactions with DNA. In contrast, due to a higher degree of interaction with DNA, the para isomer inhibited growth of SOD-deficient Escherichia coli.Due to their high stability and chemical versatility, manganese porphyrins are a promising group of compounds for development as SOD 1 mimics. Introducing ␤-electron-withdrawing substituents and modifying meso substituents of water soluble porphyrins can have a major impact on the redox and electrostatic properties of manganese porphyrins (1-7). Such substitution allows the redox potential to approach the potential of SOD itself, E1 ⁄2 ϳ ϩ0.26 V (8). This is approximately midway between the redox potentials of the two half-reactions of the dismutation process (9, 10). While maintaining the redox potential at a value close to that of SOD, it is important to also ensure electrostatic facilitation. We have already shown that ␤-bromination (11, 12) of the manganese(III) 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (13) and of manganese(III) 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin increases their SOD-like activities (13).2 However, the large positive redox potential of the former, E1 ⁄2 ϭ ϩ0.480 mV versus NHE, (13) stabilizes manganese in its 2ϩ state and diminishes stability, and the latter compound had only modest activity, probably due to lack of electrostatic facilitation (13).It has been shown that ortho substitution on the meso phenyl ring exhibits an ortho effect that is as strong as if the same substituent were placed directly on the meso position (14). Thus, meso-tetrakis(2-methylphenyl)porphyrin behaves similar to the meso tetramethylporphyrin (14). The same was found for other porphyrins in which meso phenyl groups have different ortho substituents, as well as when meso groups are ortho pyridyls, such as 5,10,15,20-tetrakis-(N-methylpyridinium-2-yl) (H 2 TM-2-PyP 4ϩ ) and its zinc complex, ZnTMP-2-PyP 4ϩ (15)(16)(17)(18)(19). Such a profound impact on the properties of the ortho isomers, known as the ortho effect, is due to the combi...

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Section: Manganese Porphyrinsmentioning

confidence: 99%

“…Introducing ␤-electron-withdrawing substituents and modifying meso substituents of water soluble porphyrins can have a major impact on the redox and electrostatic properties of manganese porphyrins (1)(2)(3)(4)(5)(6)(7). Such substitution allows the redox potential to approach the potential of SOD itself, E1 ⁄2 ϳ ϩ0.…”

mentioning

confidence: 99%

The Ortho Effect Makes Manganese(III)Meso-Tetrakis(N-Methylpyridinium-2-yl)Porphyrin a Powerful and Potentially Useful Superoxide Dismutase Mimic

Batinić‐Haberle¹,

Benov²,

Spasojević³

et al. 1998

Journal of Biological Chemistry

254

300

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“…The ortho isomer exhibited the most efficient SOD-like activity assigned to an appropriated combination of adequate redox potential and electrostatic facilitation. (Takeuchi et al 1994;Sen and Krishnan 1997;Giraudeau et al 1979;Autret et al 1996;Tagliatesta et al 1996;Binstead et al 1991;Gali et al 1996). However, other studies consider the rate constant for the reduction of Mn , while that for the oxidation of Mn…”

Section: Introductionmentioning

confidence: 99%

Towards the mechanisms involved in the antioxidant action of MnIII [meso-tetrakis(4-N-methyl pyridinium) porphyrin] in mitochondria

Araújo-Chaves

Yokomizo

Kawai

et al. 2011

J Bioenerg Biomembr

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Aerobic organisms are afforded with an antioxidant enzymatic apparatus that more recently has been recognized to include cytochrome c, as it is able to prevent hydrogen peroxide generation by returning electrons from the superoxide ion back to the respiratory chain. The present study investigated the glutathione peroxidase (GPx), superoxide dismutase (SOD) and cytochrome c-like antioxidant activities of para Mn(III)TMPyP in isolated rat liver mitochondria (RLM) and mitoplasts. In RLM, Mn TMPyP is expected to be produced at the expense of NADPH/GSH oxidation. The present results suggest GPx-like activity to be the principal antioxidant mechanism of Mn III TMPyP, whose efficiency is dependent on the NADPH/GSH content in cells.

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“…Free base porphyrins were synthesized according to literature procedures [34][35][37][38]. The manganese and iron derivatives were synthesised as reported in the literature [39].…”

Section: Synthesismentioning

confidence: 99%

Manganese and iron tetraphenylporphyrin-catalyzed oxidation of a cardanol derivative (hydrogenated tert-butylcardanol)

Tagliatesta

Crestini

Saladino

et al. 2002

J. Porphyrins Phthalocyanines

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Synthesis and electrochemistry of 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis (3,5-dichloro-2,6-dimethoxyphenyl)porphyrin (H2tdcdmpp), [CoII(tdcdmpp)] and [M(tdcdmpp)Cl](M = FeIII or MnIII)

Abstract: dimethoxypheny1)porphyrin (H,tdcdmpp), [Co"(tdcdmpp)] and [M(tdcdmpp)CI] (M = Fe"' or Mn"')

Cited by 56 publications

References 23 publications

The Ortho Effect Makes Manganese(III)Meso-Tetrakis(N-Methylpyridinium-2-yl)Porphyrin a Powerful and Potentially Useful Superoxide Dismutase Mimic

The Ortho Effect Makes Manganese(III)Meso-Tetrakis(N-Methylpyridinium-2-yl)Porphyrin a Powerful and Potentially Useful Superoxide Dismutase Mimic

Towards the mechanisms involved in the antioxidant action of MnIII [meso-tetrakis(4-N-methyl pyridinium) porphyrin] in mitochondria

Manganese and iron tetraphenylporphyrin-catalyzed oxidation of a cardanol derivative (hydrogenated tert-butylcardanol)

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