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作者 Moeller Quintavalla, Suzanne M
書名 Synthesis, characterization, and applications of novel water-soluble pyridyl porphyrins
國際標準書號 0496707566
book jacket
說明 291 p
附註 Source: Dissertation Abstracts International, Volume: 65-02, Section: B, page: 0744
Adviser: John T. Groves
Thesis (Ph.D.)--Princeton University, 2004
The family of tetracationic N-substituted meso -pyridyl porphyrins are unique catalysts that have found use as DNA nucleases, peroxynitrite decomposition catalysts, oxidation catalysts, and photosensitizers
The pyridyl porphyrins 4-PyP and 2-PyP were tetrasubstituted at the pyridyl nitrogen in good yield with a variety of alkylating agents, including iodides, tosylates, bromoesters, and bromoacetamides. The resulting free base or metallated complexes were characterized by UV spectroscopy, 1D and 2D 1H NMR, and electrospray and MALDI mass spectroscopy. Certain alkylations of meso-tetrakis(2-pyridyl)porphyrin resulted in nonstatistical distributions of atropisomers, which could be resolved by column chromatography or preparatory HPLC using a high-salt mobile phase
Alkylation of 2-PyP with (R)-(+)-methylbenzylacetamido groups resulted in a single atropisomer, which was identified as the alphaalphabetabeta isomer by 1D and 2D 1H NMR. When treated with oxidant at pH 8.9, Mn 2-T(MBz)PyP was shown to stabilize the oxoMn(V) intermediate for 95 s. Oxidations of styrene and styrene-like substrates were performed in water using the triple salt Oxone as the oxidant. The best results were obtained for styrene oxide at 11% yield and 2.21% ee, and the best ee was obtained for cis-beta-methylstyrene at 4.4%
A novel peroxynitrite decomposition catalyst was synthesized from 2-PyP and triethylene glycol monomethyl ether and characterized by UV, 1 H NMR, and mass spectroscopy. The iron complex of 2-T(PEG3)PyP was found to decompose peroxynitrite at a rate of 7.6 x 106 M-1 s-1 at 10 muM porphyrin. Tetraalkylated derivatives of 2-PyP were found to be inefficient DNA nucleases and bound poorly to DNA due to steric bulk above and below the porphyrin plane. In vitro and in vivo, Fe 2-T(PEG3)PyP exhibited significant cytoprotective abilities for pancreatic cells stressed with peroxynitrite and for murine models of oxidative stress-related injuries
School code: 0181
Host Item Dissertation Abstracts International 65-02B
主題 Chemistry, Organic
Chemistry, Analytical
Alt Author Princeton University
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