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Influence of surface termination of boron-doped diamond electrode on the electrochemical behaviour of phenol and its derivatives
Nedvěd, Michal ; Schwarzová, Karolina (advisor) ; Gabriel, Jiří (referee)
This thesis is devoted to the study of electrochemical oxidation of meta-substituted phenolic substances on a boron-doped diamond electrode. In the first phase, it was studied the effect of pH on their electrochemical oxidation by the methods of classical "direct current" voltammetry (DCV) and differential pulse voltammetry (DPV). The study was performed on three types of boron doped diamond (BDD) surfaces: polished, anodic and cathodically activated. In the second phase, attention was paid to the Hammett correlation to study the effect of the substituent on the potential of electrochemical oxidation of selected phenolic compounds. Among the substituents studied were (-H, -CH3, -OCH3, -(CH2)2COOH, -COOH a -NO2). In general, the oxidation potentials were lower in the basic medium than in the acidic medium on all studied surfaces. An exception was the studied phenolic acids, which could not be detected in an alkaline medium on the O-terminated BDD, probably due to electrostatic repulsion between the partially negative electrode surface and the acid dianion. The highest correlation coefficient for the dependence composed of all studied phenols was obtained for the polished and H-terminated surface at pH 11, ie the dissociated form of phenolic substances. The high electron density leads to easy...
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Optimization of electrodeposition of polyaniline on platinum electrode for propanol oxidation
Dobiášová, Klára ; Schwarzová, Karolina (advisor) ; Coufal, Pavel (referee)
Optimization of electrodeposition of polyaniline on platinum electrode for propanol oxidation Dobiášová Klára 2023 Abstract Composites of polyaniline (PANI) with rare metal nanoparticles (metal/PANI) are a promising material for the oxidation of aliphatic alcohols. In this work, the deposition of a polyaniline (PANI) film on a platinum electrode (Pt-PANI electrode) was performed potentiostatically and using cyclic voltammetry (CV). For both methods, the parameters influencing the deposition were optimized. For cyclic voltammetry, electrodeposition in aniline solution is significantly influenced by the final potential Efin of the scan. The PANI film with the highest current response during the deposition itself, which correlates with the thickness of the formed film, was created in the case of Efin + 1.1 V; i.e. the peak potential of the aniline oxidation peak. However, this method proved unreliable due to the poor reproducibility of the current response corresponding to PANI formation. For the PANI film formed by the CV method, its color change related to its oxidation state was investigated, with the color change being imperceptible to the naked eye in a basic environment and the most visible colour change occurring between + 0.05 V and + 0.2 V in an acidic environment. Potentiostatic deposition of...
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Development of voltammetric methods for detection of bile acids and their conjugates
Petráňová, Karolína ; Schwarzová, Karolina (advisor) ; Nesměrák, Karel (referee)
The aim of this thesis is to study the electrochemical properties of bile acids and their conjugates. Specifically, cholic acid, chenodeoxycholic acid, taurocholic acid, taurochenodeoxycholic acid, glycocholic acid, and glycochenodeoxycholic acid were studied. The measurements were carried out on a boron-doped diamond electrode in an environment of acetonitrile and perchloric acid, with a water content of 0.55% in the solution by method of cyclic voltammetry. In order for bile acids to be electrochemically active, they must first be dehydrated, which takes place in a reaction with perchloric acid. This reaction requires a relatively long time, so it was accelerated by heating the compounds. The goal of this work was to determine the conditions under which the dehydration products of bile acids can be detected. The water content that can be added to the solution after dehydration to keep the voltammetric signal stable was determined. Furthermore, it was found that the voltammetric determination can be carried out even at a pH that is not extremely acidic in which is the the dehydration carried out. Finally, calibration dependencies were compiled.
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Conjugate Addition Coupled with Enolate Oxidation in the Total Synthesis of Natural Polyphenols
Mašek, Tomáš ; Jahn, Ullrich (advisor) ; Pospíšil, Jiří (referee) ; Švenda, Jakub (referee)
1 ABSTRACT This thesis describes the development of the concept of C-C bond forming conjugate addition/oxidative cyclisation reactions and their application in the total synthesis of natural polyphenols. The first part deals with the development of methodology for conjugate addition of main- group organometallic reagents to unsaturated carbonyl compounds coupled with in situ single electron transfer oxidation. The resulting radical undergoes stereoselective cyclisation, that can be followed by a second SET oxidation, leading to further cationic cyclisation. This methodology is ideally suited for the synthesis of furoindane stilbenolignans (FIS), a neglected and structurally distinct class of natural polyphenols. Using this process, racemic synthesis of a derivative of kompasinol A was achieved, confirming the relative configuration of FISs. In an effort to develop asymmetric route to FISs, an unprecedented direct conjugate addition of aryllithiums to ylidenemalonates mediated by diethers and diamines was discovered, leading to asymmetric synthesis of gnetifolin F and 11- deoxykompasinol A. Based on X-ray evidence, a related annulation methodology consisting of direct conjugate addition/epoxide opening was shown to result in bridged lactones, instead of isomeric FISs. This finding led to an approach for the...
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Electrochemical oxidation of ibuprofen
Bolíková, Markéta ; Křížek, Tomáš (advisor) ; Kozlík, Petr (referee)
- 4 - Abstract This diploma thesis deals with the electrochemical oxidation of the active pharmaceutical ingredient ibuprofen as one of the parts of the stability studies of pharmaceutical products. The task is to ensure optimal conditions for the course of electrochemical oxidation, which produces the largest percentage of degradation products, to compare the flow and static experimental setup and its effect on the result of electrochemical oxidation and to identify the resulting degradation products. The examined conditions include the pH of the buffer used to dissolve ibuprofen, the potential applied to the working electrode and the duration of oxidation. Ultra-high performance liquid chromatography coupled with mass detection was used to separate and determine degradation products. Acquity UPLC BEH C18 (2.1 × 100 mm; 1.7 µm) was chosen as the separation column. The mobile phase consisted of an aqueous component (10mM ammonium formate with pH 3.0) and an organic component (acetonitrile). Detection was performed using a photodiode array detector at a wavelength of 222 nm and a quadrupole mass detector in the scan range m/z 50-400. The electrochemical oxidation was performed in a radial electrochemical flow cell and the conditions under which the largest percentage of degradation products formed were as...
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Voltammetric behaviour of cholesterol and lanosterol on boron doped diamond electrode
Kubešová, Jana ; Schwarzová, Karolina (advisor) ; Nesměrák, Karel (referee)
The aim of this thesis is to investigate procedures leading to regeneration of boron- doped-diamond's (BDD electrode) surface and study of voltammetric behaviour of cholesterol and lanosterol on BDD electrode. Three options of regeneration of electrode's surface were were studied: the stirring, the mechanical polishing using alumina and the anodic oxidation. The anodic oxidation was studied using electrolytes: 0,1 mol l−1 perchloric acid in acetonitrile, 0,1 mol l−1 sodium perchlorate in acetonitrile and tetrahexylammonium hexafluorofosphate in acetonitrile. Each electrolyte was studied with 0 or 0,43 % and 20 % volume of water. Further, voltammetric behaviour of cholesterol on BDD electrode in the presence of 0,1 mol l−1 perchloric acid in acetonitrile was investigate. The second part of the thesis was the study of voltammetric behaviour of lanosterol on BDD electrode in the presence of 0,1 mol l−1 perchloric acid in acetonitrile and 0,1 mol l−1 sodium perchlorate in acetonitrile. The study was performed using cyclic voltammery. Lanosterol provides two anodic signals in the presence of both electrolytes, the first one at the potential of +1200 mV, the second one at the potential of +1500 mV. The stability of lanosterol in the presence of perchloric acid and sodium perchlorate was studied by...
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The study of the electrochemical and chemical oxidative degradation of salicylic and acetylsalicylic acid
Tonnerová, Barbora ; Kubíčková, Anna (advisor) ; Křížek, Tomáš (referee)
The aim of this Thesis was to study the degradation of salicylic acid by the electrochemical oxidation. The electrochemical oxidation of salicylic acid was compared to the electrochemical oxidation of acetylsalicylic acid. Two electrochemical cells were tested - batch cell and thin- layer flow-cell. The newly developed and validated method of ultra-high performance liquid chromatography has been used to analyse the degradation products, salicylic acid and acetylsalicylic acid. The optimal analysis was made by the Kinetex column C18 (2,1 x 100 mm; 1,7 µm) and mobile phase with two components - acetonitrile and water with addition of 0,1% formic acid. These two components of the mobile phase were mixed by the gradient program from 10 % to 60 % (v/v) acetonitrile. The mobile phase flow was set to 0,3 ml min-1 and the volume of injection was 2 µl. The detection was performed by photodiode array detector at the wavelength 240 nm. Total time of the analysis was 11 minutes. The electrochemical degradation has been studied by an anodic oxidation in a flow cell with a boron-doped diamond (BDD) anode and a stainless-steel cathode. The samples of salicylic acid and acetylsalicylic acid was dissolved in the ammonium acetate, concentration 200 mmol dm-3 at pH=4,0. The 20 % oxidation rate of salicylic acid was...
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Oxidation of a psychoactive substance fluoromethoxyacetyl fentanyl
Krejčí, Michaela ; Kubíček, Vladimír (advisor) ; Nováková, Veronika (referee)
7 2. ABSTRACT Fluoromethoxyacetyl fentanyl (FMAcF) is a new psychoactive substance that belongs to the group of newly illegally synthesized fentanyl derivatives that have been entering the European drug market since 2009. The aim was to define the electrochemical behavior of FMAcF and to suggest possible oxidation mechanisms. In this research, the electrochemical methods and in situ UV-Vis spectroelectrochemistry were used to study drug oxidation and reduction mechanism. Electrochemical techniques were combined with high performance liquid chromatography with diode array detector. FMAcF in the aqueous medium provided a single oxidation peak whose potential depended on pH. The substance was not reduced under the studied conditions. UV-Vis spectroelectrochemistry showed the formation of a reaction intermediate. The substance was electrolyzed and the UV-Vis absorption spectra of the products were determined. The oxidation mechanism of the substance has been proposed. In future the incubation with liver microsomes will be performed to detect metabolic pathways. Key words: Cyclic voltammetry, Oxidation, Bioactive substance, Fentanyls, Fluoromethoxyacetyl fentanyl
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Bulk materials from oxidized powder feedstock
Luptáková, Diana ; Molliková, Eva (referee) ; Jan, Vít (advisor)
In this thesis, methods of effective aluminium powder oxidation are evaluated, such as oxidation at higher temperatures in atmosphere, anodic oxidation and oxidation during high-energy ball milling. It describes following treatment and methods creating volume sammples in such way, where ductile properties are preserved, but the process of hardening by aluminium oxide occurs.
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The biochemical parameters of wine and their changes during ageing
Vacková, Tereza ; Hudeček, Jiří (advisor) ; Hodek, Petr (referee)
3. Abstract Wines marketed under the same brandname and designation may differ in color and other characteristic, as they may come from different batches. These differences may reflect different concentrations of individual components in wine, reflecting, for example, different compositions of individual cupages. We used the reagent set "Malá vinařská laboratoř" (supplied by the BS Vinařské závody, Velké Bílovice, ČR) to determine principal parameters of two samples of a white wine with the same brandname, differing in color. For comparison, one sample of red wine was studied with the same methods. After opening the wine, we followed the changes of selected parameters during ageing, for 14 days (keeping the wine in a cold place), and also in a short-term experiment under elevated temperature. Our laboratory data were complemented by a more detailed analysis of phenolics and other antioxidants, performed in a specialised laboratory (Mendel Agricultural University, Brno, ČR).
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