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Application of Quantitative Electron Paramagnetic Resonance (EPR) and Commercially Available EPR Standards for Electrochemical Study of the Subsituted Tetrathiafulvalene Oxidation.
Habániková, Shannelle Diana ; Tarábek, Ján (advisor) ; Mazúr, Milan (referee)
Tetrathiafulvalene derivatives are remarkable molecules, with various application, reported relatively recently. The radical cation of these compounds has very inter- esting optical, electronic, electrocatalytic superconducting and magnetic properties that have been intensively studied recently. Quantitative in-situ EPR voltammetric spectroelectrochemistry studies of 2-(2-hydroxyethylsulfanyl)-3-(benzylsulfanyl)-6,7- bis(octadecylsulphanyl)tetrathiafulvalene (TTF-Der3) have been carried out with the aim to confirm the oxidation sites, follow-up reactions (after the first electron transfer), and electrochemical behaviour. The diffusion process was confirmed by the depen- dence of current on the square root of the scan rate. It was claimed that the ratio of the number of generated radicals to transferred charge (electrons) for two representative TTF derivatives was determined to 5.5:500 for and 7:500 for TTF, indicating the follow- up reactions. Experiments were performed using the commercially available EPR standards, calibrated for this method (experimental setup). The latter was validated by quantitative EPR with standard 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical concentration (1·10−4 mol dm−3). For the ratios the confidence interval was reported for the first time for TTF-Der3 it was...
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Electrochemical oxidation of selected bile acids in acetonitrile
Habániková, Shannelle Diana ; Schwarzová, Karolina (advisor) ; Fischer, Jan (referee)
The concentration of bile acids is an important parameter in hepatobiliary tract diseases. This work deals with the electrochemical oxidation of the chenodeoxycholic (CDCA) and cholic acid (CA) at boron dopped diamond (BDD) electrode in comparison with the oxidation at glassy carbon (GCE) and platinum electrode (PtE), in a mixed environment of acetonitrile and water (0.26 % from 0.1 mol·l-1 HClO4, supporting electrolyte). The measurement was carried out in an electrochemical cell with salt bridge containing 0.5 mol·l-1 NaClO4 separating the working and the Pleskov's reference electrode (0.01 mol·l-1 AgNO3 and 1 mol·l-1 NaClO4 in acetonitrile). Cyclic voltammetry (CV) characterization of BDD electrode by a redox pair [Fe(CN)6]4-/3- (c = 0.1 mmol·l-1) in 1 mol·l-1 KCl was performed. Quasi-reversible behaviour was observed and the difference of the anodic and the cathodic peak potential ranged from 80 to 200 mV, depending on the scan rate. Alumina polishing (4 min) of the BDD electrode was identified as the most appropriate method of activating the surface and it was applied between consecutive voltammetric scans in the presence of CA and CDCA. Irreversible anodic peaks of CDCA and CA in acetonitrile-water (0.26 %) were observed at the relatively high potentials of about +1100 ± 100 mV, depending on...
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