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Electrospray mass spectrometry of isomeric tetrakis(N-alkylpyridyl)porphyrins and their manganese(III) and iron(III) complexes

INES BATINIĆ-HABERLE

Department of Biochemistry, Duke University Medical Center, Durham, NC 27710, USA

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ROBERT D. STEVENS

Department of Pediatrics, Duke University Medical Center, Durham, NC 27710, USA

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, and

IRWIN FRIDOVICH

Department of Biochemistry, Duke University Medical Center, Durham, NC 27710, USA

Corresponding author: Department of Biochemistry, Duke University Medical Centre, Durham, NC 27710, USA.

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https://doi.org/10.1002/(SICI)1099-1409(200004/05)4:3<217::AID-JPP198>3.0.CO;2-ECited by:26 (Source: Crossref)

Abstract

Manganese(III) complexes of isomeric tetrakis(N-alkylpyridyl)porphyrins (N-alkyl = N-methyl, M or N-ethyl, E), MnTM(E)-2(3,4)-PyP⁵⁺, are being developed as superoxide dismutase (SOD) mimics. Simultaneously, techniques for their purification, identification and characterization are being pursued. Electrospray mass spectrometry (ESMS) proved to be an excellent method for identification and characterization of this group of water-soluble cationic porphyrins. The multiply charged parent ion is observed for both the metal-free ligands and their corresponding manganese complexes. The other major peaks in the mass spectra result from loss of N-alkyl groups, reduction of the metal center, axial coordination of chloride or hydroxo ion in the case of the Fe porphyrin, loss of metal and deprotonation of pyrrolic nitrogens. As a result of inductive and resonance effects, which stabilize the ortho isomer, almost no loss of N-alkyl groups from the manganese complex or from its parent ligand was observed. The relative intensity of the multiply charged molecular ion Mn^IIITM-3(4)-PyP⁵⁺/5 was 100% in the case of the meta and para isomers. Although manganese porphyrins display a low preference toward axial ligation, favorable electrostatics at the metal center of the ortho isomer gives rise to 100% relative intensity of the species that has chloride axially ligated at the manganese site, Mn^IIITM(E)-2-PyPCl⁴⁺/4. When the stronger preference of iron porphyrins toward axial ligation combines with the ortho effect, the monohydroxo iron porphyrin Fe^IIITM-2-PyP(OH)⁴⁺/4 dominates the ESMS of an aqueous acetonitrile solution at pH 7.8.

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