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Electrochemical Properties of Branched Pyridinium Cations
Lachmanová, Štěpánka ; Hromadová, Magdaléna ; Pospíšil, Lubomír ; Lainé, P. P.
The electrochemical properties of branched extended pyridinium cations depend strongly on the structure of the molecule. This work is focused on the redox processes of the electron transfer of four derivatives of pyridinium. The electron transfer mechanism was studied by various electrochemical methods. Although the structures of the studied molecules seem to be quite similar, 1-N-methyl-2,4,6-triphenylpyridinium and 1',3',5'-trimethyl-2,4,6-triphenyl-1,4'-bipyridine-1,1'-diium are reduced in two separate one-electron transfer steps. On the other hand, 1'-methyl-2,4,6-triphenyl-1,4'-bipyridine-1,1'-diium and 1',3,5-trimethyl-2,4,6-triphenyl-1,4'-bipyridine-1,1'-diium accept two electrons, but in a single two-electron transfer. The heterogeneous rate constants of the electron-transfer processes were determined.
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Electrochemistry of halogenated benzenonitrils
Sokolová, Romana ; Pospíšil, Lubomír ; Hromadová, Magdaléna ; Ludvík, Jiří
Autoprotonation in reduction mechanism of 3,5-dihalogeno-4-hydroxy-benzonitriles was studied in dimethylsulfoxide by electrochemical methods. The overall one electron reduction process was found. Aryl radical formed by the cleavage of halogenide undergroes further electron transfer in EC type reaction. The anion is protonated by parent molecule resulting in total consumption of two electrons per two starting molecules. Addition of stronger proton donor increases the height of reduction wave up to two electrons per molecule. The addition of potassium hydroxide causes the decrease of the reduction wave. The reduction products were identified by GC/MS analysis in the absence and presence of strong proton donor.
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Fullerene C60 in Aqueous Medium
Kocábová, Jana ; Gál, Miroslav ; Hromadová, Magdaléna ; Kavan, Ladislav ; Pospíšil, Lubomír ; Sokolová, Romana
The aqueous solution of C60 was investigated by electrochemical and spectroscopis methods such as UV-Vis, Raman, FTIR and AFM techniques. The association constants of fullerene-gamma-cyclodextrin complex and ,ethanofullerene conjugates with beta-cyclodextrins in aqueous solution were evaluated from the shifts of the formal redox potential of complexed and uncomplexed fullerene. The most suitable techniques for electrochemical characterization of fullerene derivatives proved to be the low-frequency phase-sensitive AC polarography and the steady-state voltammetry.
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The Electrochemistry of Natural Pigments
Sokolová, Romana ; Degano, I. ; Hromadová, Magdaléna ; Pospíšil, Lubomír
The electrochemical properties of flavonoid compounds (hemotoxylin, quercetin) were studied in buffered aqueous and non-aqueous solutions. The role of the preceding protonation/deprotonation on the electron transfer was estimated. The absorption spectra of these compounds, which contain a chromophore, were recorded during their oxidation. The electrochemical techniques were combined with GC-MS analysis in order to identify the degradation products. The mechanism of the formation of degradation products will be discussed.
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