Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2003-06-09
2009-02-03
Wilson, James O. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
07485721
ABSTRACT:
A series of ortho isomers of meso tetrakis N-alkylpyridylporphyrins (alkyl being methyl, ethyl, n-propyl, n-butyl, n-hexyl, and n-octyl) and their Mn(III) complexes were synthesized and characterized by elemental analysis, uv/vis spectroscopy, electrospray ionization mass spectrometry and electrochemistry. An increase in the number of carbon atoms in the alkyl chains from 1 to 8 is accompanied by an increase in: (a) lipophilicity measured by the chromatographic retention factor, Rf; (b) metal-entered redox potential, E1/2from +220 to +367 mV vs NHE, and (c) proton dissociation constant, pKa2from 10.9 to 13.2. A linear correlation was found between E1/2and Rfof the Mn(III) porphyrins and between the pKa2and Rfof the metal-free compounds. As the porphyrins become increasingly more lipophilic, the decrease in hydration disfavors the separation of charges, while enhancing the electron-withdrawing effect of the positively charged pyridyl nitrogen atoms. Consequently, the E1/2increases linearly with the increase in pKa2, a trend in porphyrin basicity opposite from the one we previously reported for other water-soluble Mn(III) porphyrins. All of these Mn(III) porphyrins are potent catalysts for superoxide dismutation (disproportionation). Despite the favorable increase of E1/2with the increase in chain length, the catalytic rate constant decreases from methyl (log kcat=7.79) to n-butyl, and then increases such that the n-octyl is as potent an SOD mimic as are the methyl and ethyl compounds. The observed behavior originates from an interplay of hydration and steric effects that modulate electronic effects.
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Batinic-Haberle Ines
Fridovich Irwin
Spasojevic Ivan
Duke University
Townsend and Townsend and Crew
Ward Paul V.
Wilson James O.
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