Search results for "Semiquinone"
showing 5 items of 5 documents
Decreased Electron Transfer Rates of Manganese Porphyrins with Conformational Distortion of the Macrocycle
1998
Slow electron transfer to manganese(iii) porphyrins results when the macrocycle deviates from planarity. This was demonstrated by measuring the kinetics of homogeneous electron transfer from a series of semiquinone radical anions to synthetic manganese porphyrins (shown schematically; R1 =H, Cl, F; R2 =H, F). Three of the four porphyrins studied have nonplanar macrocycles. These results could have implications for the role of manganese in biological electron transfer processes.
ESR, ENDOR and TRIPLE resonance studies on radical reactions of 1,4-benzoquinone and 1,4-hydroquinone in alkaline methanol and liquid ammonia
1990
The relative signs and absolute values of the hyperfine coupling constants of different methoxy-1,4-benzoquinones were measured by ESR, ENDOR and TRIPLE resonance spectroscopy. Reactions of 1,4-benzoquinone and 1,4-hydroquinone with methanol took place in alkaline methanol, giving rise to methoxy-substituted 1,4-benzoquinones. The same substitution reaction occurred in a mixture of ammonia and methanol. The reactions depended on temperature and the alkali concentration. Coupling constants were assigned by the modified additivity relationship method. An extremely small line width of 0.014 G was measured in the ESR spectrum of deuterated 2,5-dimethoxy-1,4-benzoquinone.
Base Control of Electron-Transfer Reactions of Manganese(III) Porphyrins
2000
Homogeneous electron-transfer kinetics for the reduction of four different manganese(III) porphyrins using different reductants were examined in deaerated acetonitrile, and the resulting data were evaluated in light of the Marcus theory of electron transfer to determine electron-exchange rate constants between manganese(III) and manganese(II) porphyrins. The investigated compounds are represented as (P)MnCl, where P = the dianion of dodecaphenylporphyrin (DPPX; X = H20, Cl12H8, or F20) or tetraphenylporphyrin (TPP). The electron transfer from semiquinone radical anion derivatives to (P)MnIIICl leads to formation of the corresponding MnII complex, [(P)MnIICl]−. The electron-exchange rate con…
Experimental and theoretical study of possible correlation between the electrochemistry of canthin-6-one and the anti-proliferative activity against …
2015
Abstract This work presents an approach to study the performance of novel targets able to overcome cancer stem cell chemoresistance, based on the voltammetric data for microparticulate films of natural or synthetic alkaloids from the canthin-6-one series. A comparison of this voltammetric technique with conventional solution phase electrochemistry suggests the differences in the anti-proliferative activity of canthin-6-ones could be tentatively correlated to their different capacity to generate semiquinone radical anions. These data also match theoretical calculations.
Marine inspired antiplasmodial thiazinoquinones: synthesis, computational studies and electrochemical assays
2015
In the search for new antimalarials, we used the quinone scaffold of marine secondary metabolites as a chemical starting point to synthesize new thiazinoquinone compounds. Most of synthetic derivatives have shown a significant pharmacological activity and some structural requirements, critical for both the antiplasmodial effect and cytotoxicity, have been evidenced. The redox properties of the prepared compounds have been investigated by computational studies and electrochemical assays, which indicated that a higher antiplasmodial activity of some thiazinoquinones is related to their greater ability to form the semiquinone species and strongly interact with free Fe(III)-protoporphyrin IX.