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Optimization of anodic and cathodic pre-treatments of boron doped diamond electrode surfaces for electroanalysis
Baudisová, Kateřina ; Fischer, Jan (advisor) ; Dejmková, Hana (referee)
This bachelor thesis deals with the optimization of anodic and cathodic pretreatment of BDD electrodes and subsequent comprehensive characterization and comparison of electrochemical parameters of unmodified, O-terminated and H-terminated BDD electrodes. The study was carried out using cyclic voltammetry of two model inner sphere redox systems [Fe(CN)6]4−/3− and dopamine/dopamine-o-quinone. Boron concentrations in the BDD films ranged from 500 ppm to 8000 ppm. O-termination of the electrode surface was most effectively achieved when an activation potential of Eakt = +3.0 V was inserted for 10 min into 0.5 mol l−1 H2SO4. For the dopamine/dopamine-o-quinone system, the O-terminated BDD electrodes caused deceleration of electron transfer compared to the unmodified BDD electrodes, which was accompanied by an increase in the potential difference with the highest ΔEp at 500 ppm BBD electrode (ΔEp = 711 mV). To achieve the H-terminal surface, single and cumulative reduction was tested by inserting Eakt = −3.0 V. A sufficient single reduction time for the [Fe(CN)6]4−/3− system was determined to be 60 s, whereas in the case of dopamine, the electrochemical parameters did not stabilize at the selected reduction times, but the cathodic and anodic peak signal at the H-terminated 1000 ppm BDD electrode was up...
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Determination of cholesterol, 7-dehydrocholesterol and cholecalciferol by HPLC with spectrophotometric and electrochemical detection
Dostálková, Lucie ; Schwarzová, Karolina (advisor) ; Vyskočil, Vlastimil (referee)
The aim of this thesis is to verify the possibility of simultaneous determination of three structurally related biologically active substances (cholesterol, 7-dehydrocholesterol and cholecalciferol) after previous separation by high-performance liquid chromatography followed by electrochemical (on a boron-doped diamond electrode) and spectrophotometric detection, which were compared in this work. The influence of the water content in the mobile phase (in the range of 0-10 %) on the retention factor of the analytes and their response for both types of detectors was investigated. Using all mentioted water contents, the analytes baseline-separated. As the water content increased, the retention factor of the analytes increased as well as the background current for higher positive detection potentials. Based on the recorded hydrodynamic voltammograms, the optimum detection potential + 1.8 V was chosen. The optimum wavelength for spectrophotometric detection was 200 nm. The concentration dependence was measured in an of 50 mmol l−1 sodium perchlorate in acetonitrile mixed with water (95:5, v/v). The spectrophotometric detector provided lower detection limits compared with the electrochemical detector, which had detection limits of 2.3 μmol l−1 for cholesterol, 1.4 μmol l−1 for 7-dehydrocholesterol and...
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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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Study of degradation behavior of abacavir using a diamond film electrode
Pražáková, Lucie ; Kubíčková, Anna (advisor) ; Kozlík, Petr (referee)
In this work the electrochemical degradation behavior of the drug abacavir is studied with the use of boron-doped diamond electrode. Oxidative degradation of the active substance abacavir, used to treat patients with HIV disease, was studied in a batch of three-electrode and two-electrode settings. In this work, the characteristics of five working boron-doped diamond electrodes, differing in a boron/carbon doping ratio of 500 ppm, 1000 ppm, 2000 ppm, 4000 ppm and 8000 ppm, were studied. The degradation in the three-electrode arrangement took place under potenciostatic electrolysis at potentials from 0,6 V to 2,0 V. The degradation in the two-electrode arrangement took place under conditions of potenciostatic electrolysis at higher potentials from 2,0 to 4,5 V. Optimal degradation, to the required values up to 25 %, was achieved at a potential of 3,5 V for an oxidation time of 10 minutes on a boron-doped diamond electrode with a boron/carbon doping ratio of 500 ppm and 1000 ppm. Separation and determination of abacavir and its degradation products were performed by ultra-high performance liquid chromatography with a mass detector. The degradation of abacavir produced two known degradation products, DP1 with relative retention times of 0,40 and DP2 with relative retention times of 0,45. The...
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Novel Approaches in Electrochemical Determination of Xenobiotic Compounds and in Study of Their Interaction with DNA
Hájková, Andrea ; Vyskočil, Vlastimil (advisor) ; Trnková, Libuše (referee) ; Labuda, Ján (referee)
Presented Ph.D. Thesis is focused on the development of analytical methods applicable for determination of selected xenobiotic compounds and for monitoring DNA damage they can induce. The main attention has been paid to the development and testing of non-toxic electrode materials for preparation of miniaturized electrochemical devices and novel electrochemical DNA biosensors. 2-Aminofluoren-9-one (2-AFN) was selected as a model environmental pollutant, which belongs to the group of hazardous genotoxic substances. Its carcinogenic and mutagenic effects may represent a risk to living and working environment. 2-AFN has one oxo group, where the cathodic reduction occurs, and one amino group, where the anodic oxidation occurs. The voltammetric behavior of 2-AFN in the negative potential region was investigated at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE) representing a non-toxic and more mechanically robust alternative to mercury electrodes. This working electrode was subsequently used for the development of a newly designed miniaturized electrode system (MES), which has many benefits as the possibility of simple field measurements, easy portability, and the measurement in sample volume 100 µL. Moreover, a glassy carbon electrode (GCE) was used for further investigation of...
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Factors influencing electrochemical oxidation of m-cresol at boron-doped diamond electrode
Procházková, Kateřina ; Schwarzová, Karolina (advisor) ; Vyskočil, Vlastimil (referee)
This study investigates electrochemical oxidation of m-cresol on boron-doped diamond electrode using direct current voltammetry (DCV), differential pulse voltametry (DPV) and cyclic voltammetry (CV). In aqueous media in pH range 2.0 - 12.0 m-cresol provides one oxidation peak. The electrode reaction is diffusion-controled. Because of electrode passivation two types of pretreatment were applied for reactivation of electrode surface., i.e. alumina polishing and anodic activation using potential of +2400 mV. Peak heights and potentials are strongly dipending on the type of pretreatment for DCV and DPV - the difference in peak potentials can reach 430 mV. Using optimal conditions for alumina polishing in 0.01 μmol·L-1 NaOH the linear dynamic range is 1.0 - 75 μmol·L-1 for DCV and 0.75 - 75 μmol·L-1 for DPV. And for anodic activation in BR buffer pH 2.0 the linear dynamic range is 0.75 - 75 μmol·L-1 for DCV and DPV. The influence of boron-doping level was investigated using a semiconductive and mettalic-type BDD film. For the latter the sensitivity in DP voltammetry is two times higer and for both types the linear dynamic range is ca 1 - 25 μmol·L-1 . The voltammetric response of m-cresol was further investigated in the presence of cationic surfactants. In the presence of CTAB and CPB the peak current...
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Voltammetric detection of stigmasterol at boron-doped diamond electrode in mixed media
Benešová, Lenka ; Schwarzová, Karolina (advisor) ; Nesměrák, Karel (referee)
V o l t a m m e t r i c d e t e c t i o n o f s t i g m a s t e r o l a t b o r o n d o p e d d i a m o n d e l e c t r o d e i n m i x e d m e d i a L e n k a B e n e š o v á Univerzita Karlova v Praze Přírodovědecká fakulta Praha 2015 Abstract The aims of the study thesis was to suggest suitable solvent for oxidation of stigmasterol on boron doped diamond electrode. Cyclic voltammetry in mixed media of water and organic solvents was used for this purpose. First of all, the effect of organic solvent on potential window of boron doped diamond electrode was studied. Solvents used were methanole, isopropanole, N-dimethylformamide and acetonitrile; the water components was phosphate buffer (0,075 mol.l-1, pH 3,0). It was deduced from the results, that suitable solvent for detection of stigmasterol on was the acetonitrile, which provided sufficiently large potential window in anodic area. Keywords: boron doped diamond electrode, cyclic voltammetry, organic solvent, oxidation, stigmasterol
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Utilization of complexation of tebuconazole with Cu(II) ions for its voltammetric detection
Dostálková, Lucie ; Fischer, Jan (advisor) ; Křížek, Tomáš (referee)
Tebuconazole is a triazole fungicide used in agriculture that can be present in the environment and have a negative effect on various organisms. Therefore, the electrochemical properties of tebuconazole and its complexation with Cu(II) ions on a boron doped diamond electrode were studied for its possible indirect detection in the presence of these ions. For the determination of Cu(II) ions, conditions in the concentration range 0.1-10 mol l-1 were optimized by differential pulse voltammetry in a 0.01 mol l-1 HNO3 environment on anodically oxidized BDDE, the limit of quantitation was 0.087 µmol l-1 . After optimization of the conditions, the indirect determination of tebuconazole was tested. The signal of free Cu(II) ions after the addition of tebuconazole was monitored. A decrease in this signal was observed and a linear calibration dependence could be measured for a decrease in the signal of 10 µmol l-1 Cu(NO3)2 in the concentration range of 2-10 µmol l-1 tebuconazole and for 1 µmol l-1 Cu(NO3)2 in the concentration range of 2-10 µmol l-1 and 10-100 µmol l-1 tebuconazole. Complexation of tebuconazole with Cu2+ was shown to occur almost instantaneously. Tebuconazole itself gives an anodic peak at a potential of +1550 mV in aqueous medium of 0.01 mol l-1 HNO3. Using differential pulse voltammetry,...
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Development of voltammetric methods for detection of cholesterol and its prekursor lathosterol
Bláhová, Eva ; Schwarzová, Karolina (advisor) ; Fischer, Jan (referee)
Cholesterol is an irreplaceable sterol found in animal cells, lathosterol is one of its precursors. The first aim of this Thesis is to develop a method for determining cholesterol after liquid- liquid extraction from milk matrices by differential pulse voltammetry on a boron doped diamond electrode in the presence of perchloric acid in acetonitrile where cholesterol provides an irreversible anodic response at the potential between +1300 and +1600 mV depending on the water content. The second aim is a study of the voltammetric behavior of lathosterol on boron doped diamond and glassy carbon electrodes using cyclic voltammetry and differential pulse voltammetry mainly in perchloric acid but also sodium perchlorate where lathosterol provides an irreversible anodic response at the potential of about +1650 mV on the boron doped diamond electrode and at the potential of +1350 mV on a glassy carbon electrode. The effect of other acids - sulfuric, nitric and phosphoric - on the response of lathosterol was also investigated. The influence of the water content in the measured solution and the influence of the polarization rate on the response of lathosterol were studied. Furthermore, the calibration dependence of lathosterol was measured using differential pulse voltammetry after optimization of its...
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A new approach to the electroanalysis of primary bile acids and related steroids
Klouda, Jan
In this doctoral thesis, a novel method for the determination of primary bile acids cholic acid and chenodeoxycholic acid is presented. Bile acids play various vital roles in the mammalian body. Moreover, their determination is extremely helpful in liver and biliary disease diagnosis and management. These saturated organic compounds lack strong chromophores and fluorophores in their structure, and thus are usually hard to detect in spectroscopy. For this reason, either instrumentally advanced but expensive methods, such as mass spectrometry, or less reliable enzymatic methods are commonly employed in bile acids quantitation. Hence, the demand for simple and reliable methods for their determination is strong. Bile acids are also known to be virtually inert for direct electrochemical oxidation. Herein, a simple method for their chemical activation for electrochemical oxidation on bare electrode materials was developed, optimized and applied to cholic acid and chenodeoxycholic acid determination. The activation is based on a dehydration reaction of a primary bile acid with 0.1 mol L-1 HClO4 in acetonitrile (water content 0.55%) that introduces double bond(s) into the originally fully saturated steroid core. This naturally increases the electron density in the structure, and thus allows electrochemical...
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