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Development and utilization of electrochemical flow-through detectors
Baroch, Martin ; Dejmková, Hana (advisor) ; Vyskočil, Vlastimil (referee) ; Trnková, Libuše (referee)
The proposed dissertation thesis deals with the development and investigation of electrochemical flow systems using both conventional and unconventional electrode materials. In the first part of this thesis, the problem of porous flow-through large area electrodes is addressed. As a working electrode material, a free-standing porous boron-doped diamond (fs-pBDD) was used. This was used for the first time in the construction of an electrochemical cell designed for amperometric detection in flow methods. Testing of this electrode was performed using amperometric detection combined with flow injection analysis of a ruthenium complex solution. The detection limits achieved on this material were in the submicromolar range and the linear dynamic range of the concentration dependence spanned over three orders of magnitude. In addition to amperometry, fs-pBDD was also subjected to testing by cyclic voltammetry. The main reason for using this method was to determine the electrochemically active area, which contributed to the overall physicochemical characterization of this promising material. However, it was this step that brought into question the accuracy and precision of the calculation used. For this reason, the search for new ways to calculate the electrochemically active area of the working electrode...
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Development of electrochemical flow-through detectors based on carbon nanotubes
Pavlíčková, Eva ; Dejmková, Hana (advisor) ; Kubíčková, Anna (referee)
This work deals with the development of a flow through detection cell using carbon nanotubes deposited on a membrane as the working electrode. 3D printing was used to obtain prototypes of the detection cells. Uric acid and dopamine were used as analytes to verify the functionality of the cells. Three prototype cells were prepared during the work, differing in the location of the reference electrode and in the method of inserting the working electrode. Four cells with different internal dimensions are compared in this work, the best cell is the one with a length of 3 mm and a diameter of 3 mm. This membrane has to be lined with a non-woven fabric and another membrane for lower deformation of the nanotube membrane. The optimum conditions for the determination of the dopamine-urea acid mixture are: mobile phase 90 % phosphate acetate buffer pH 6 and 10 % methanol, input potential 0,5 V and flow rate 0,5 ml/min. The concentration of the nanotubes on the membrane is 0,05 mg/ml, higher concentration does not improve the degree of conversion, which is 0,6. Different types of nanotubes are also compared in this work. The short and wide nanotubes appear to be the best ones, which have the best repeatability and are closest to the theoretical charge exchange value of the measured substances.
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Electrochemical determination of DNA using flow injection analysis
Jasenovský, Marek ; Dejmková, Hana (advisor) ; Fischer, Jan (referee)
6 Abstract The aim of this work was to create a method for electrochemical detection of DNA in a flow system and subsequently evaluate its functionality and usability. Prior to actual measurement in the flow system, an evaluation of a suitable type of working electrode was performed in a batch measurement, where a basal plane pyrolytic graphite electrode (BPPGE) was selected from the evaluated types of working electrodes. For signaling the sample zone on the surface of the working electrode in the flow arrangement, the recording of the dependence of the first derivative of current response with respect to time (dI/dt) was tested. For this measurements, a flow rate of 0,4 ml·min−1 was evaluated as optimal conditions, using a 0,35 mm-thick PTFE spacer film with a volume of 1,5 µl above the working electrode and a time delay prior stopping the flow 0,5 s after exceeding the set threshold of the dependence of dI/dt with respect to time. During the repeatability check of the procedure for automatic stopping of the sample zone on BPPGE, instability of acetate buffer noise (pH 5) was found, which greatly complicated long-term use of the procedure, and an alternative method of dispensing was therefore sought. For this purpose, a new 3D printed electrochemical cell with a dispensing hole directly into the cell...
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Modification of boron doped diamond electrode by electrochemical oxidation of p-aminobenzoic acid
Švárová, Eliška ; Fischer, Jan (advisor) ; Dejmková, Hana (referee)
This bachelor's thesis deals with the modification of a boron-doped diamond electrode (BDDE) by the electrochemical oxidation of p-aminobenzoic acid. Subsequently, the stability of the modified electrode was investigated by a study of various parameters. The modification of the electrode was performed using cyclic voltammetry (CV) in LiClO4 electrolyte. The success of the modification and its subsequent stability was investigated by the CV method in electrolyte KCl in the presence of the redox system [Fe(CN)6]4-/3- . Stability was tested in terms of ultrasonic cleaning in isopropanol and anodic cleaning in 0.5 mol l-1 H2SO4. It was found that the modification of the surface cannot be completely removed by ultrasonic cleaning in isopropanol, in contrast, pulses of period 2 seconds with a high positive potential are enough to completely remove the modification. Optimal conditions for surface stability were determined. The ideal number of cycles for surface modification was set at 5 cycles. The use of different electrolytes during modification (KClO4 and LiClO4) determined that in the case of modification in the KClO4 electrolyte, it is possible to measure in the range of the potential window from -400 to +1600 mV and in the case of LiClO4 in the range of -400 to +1500 mV without breaking the modified...
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Electrochemical study of the DNA desorption from the surface of carbon electrodes
Průcha, Jakub ; Dejmková, Hana (advisor) ; Schwarzová, Karolina (referee)
This bachelor's thesis deals with the possibility of DNA desorption from the surface of carbon electrodes. Measurements were performed using linear scan voltammetry in a three- electrode configuration, with single-stranded DNA (ssDNA) of 31 nucleotides as the sample. The working electrodes were a boron-doped diamond electrode and an electrode made of highly oriented pyrolytic graphite. The efficiency of desorption was assessed by comparing the heights of oxidation signals of adsorbed nucleic bases, which were measured before and after the application of the desorption procedure. The first approach involved desorption through mixing or rinsing in solutions with different properties, specifically in organic solvents: methanol, acetone, toluene, and DMSO; in acids and bases: HCl, HNO3, NaOH; and subsequently in surfactants and detergents: Triton X-100, TWEEN 80, CTAB, and Tergazyme. Among the tested substances, a 0.1 mol·l-1 solution of NaOH and a 1 % solution of Tergazyme proved to be effective. Subsequently, the time and temperature dependence of the rinsing strength of these two solutions on ssDNA desorption were examined. From the conducted experiments, it was determined that time and temperature of the solution do not increase the efficiency of the desorption by NaOH solution. For rinsing with a...
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Testing of the electrochemical properties of flow-through diamond detector
Pecák, Jakub ; Dejmková, Hana (advisor) ; Vyskočil, Vlastimil (referee)
In the presented bachelor thesis, the functionality of a flow-through multitubular boron- doped diamond electrode (mtBDDE) was verified on two selected neurotransmitters, DA and NE, using the HPLC technique with isocratic elution. An aqueous solution of Britton-Robinson (B-R) buffer was chosen as the mobile phase and a Kinetex EVO C18 reverse column (150 x 4.6 mm) as the stationary phase. The flow rate of the mobile phase was set at 1 ml/min. For electrochemical detection, mtBDDE was used and UV detection at 280 nm was applied as an assistant to the main detector. The electrochemical response of the DA and NE solution (cΘ = 1.10-4 mol/dm3 ) was investigated in the form of hydrodynamic voltammograms over a potential range from 0.1 V to 1.3 V in different pH ranges of the mobile phase (2.5; 4.0; 6.0; 8.0 and 10.0). It was found that the potential wave shifts to lower potentials with increasing pH of the mobile phase, while the response of individual analytes does not change significantly with pH. Under optimal conditions, i.e., mobile phase B-R buffer at pH = 6 and a potential loaded on the mtBDDE of 0.6 V, the repeatability and reproducibility of the measurement results were verified. The electrode gave repeatable results (RSD < 4 %) comparable to the UV detector used (RSD ≤ 4 %) over the series of...
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Development of electroanalytical methods for detection of bile acids possessing 7α hydroxyl group
Jelšíková, Kristýna ; Schwarzová, Karolina (advisor) ; Dejmková, Hana (referee)
This master's thesis contains a study of electrochemical processes of selected bile acids possessing 7 hydroxyl group (cholic, chenodeoxycholic and −muricholic). The measurements were performed on boron−doped diamond electrode in the non-aqueous medium of acetonitrile and perchloric acid (water content 0.55 %) by cyclic voltammetry. It is known that the electrochemical activity of 7 bile acids is increased by a dehydration reaction between perchloric acid and the 7 bile acid. The subject of the study was the stability of the voltammetric response of chemically activated bile acids in the region of negative potentials. It was found that the presence of oxygen in the measured solution is an important factor for obtaining the cathodic signal of 7 bile acids. It probably performs a regenerative function; the product of the electrochemical reduction is re-oxidized in its presence, which leads to an increase in the voltammetric response. At the same time, it is important that the direction of the scan in cyclic voltammetry first proceeds to positive values. A potential of +2.0 V (vs. Ag/AgNO3 in acetonitrile) must be reached for the HO● radicals to be formed. It is these radicals that presumably lead to the formation of the product(s) of bile acids electrochemical oxidation that can be subsequently...
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Voltammetric Determination of Warfarin at a Screen-Printed Carbon Electrode
Žužičová, Victória ; Vyskočil, Vlastimil (advisor) ; Dejmková, Hana (referee)
In this Bachelor Thesis, the electrochemical behaviour of the drug warfarin sodium was studied at a screen-printed carbon electrode (SPCE) using DC voltammetry (DCV) and differential pulse voltammetry (DPV). The dependence of the voltammetric behaviour of the substance on the pH of the medium was studied in Britton-Robinson buffer (BR buffer) in the pH range of 2.0−12.0. A pH of 7.0 was chosen as the optimum pH for both voltammetric techniques. A repeatability of 3.8% for DCV and 4.3% for DPV was determined for the selected pH. Calibration dependence was monitored under the selected optimal conditions in the concentration range 2∙10−6 to 1∙10−4 mol∙dm−3 . The limit of detection (LOD) was determined to be 1.05∙10−6 mol∙dm−3 for DCV and 2.59∙10−7 mol∙dm−3 for DPV. The limit of quantification (LOQ) was 3.50∙10−6 mol∙dm−3 for DCV and 8.62∙10−7 mol∙dm−3 for DPV. These newly developed methods were used for the determination of the active ingredient in the pharmaceutical formulation Warfarin Orion 5 mg. The values measured by voltammetric methods were compared with those obtained by spectrophotometric measurements. Key words Electrochemistry, Warfarin, Anticoagulants, Direct Current Voltammetry, Differential Pulse Voltammetry, Screen-Printed Carbon Electrode
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Sulfate determination using ion selective electrode
Hrbková, Petra ; Dejmková, Hana (advisor) ; Fischer, Jan (referee)
In this bachelor thesis, literature survey was performed covering the topic of sulphate ion selective electrodes. For sulphates with their very hydrophilic nature and thus position at the end of the Hofmeister series, many ionophores have been tested to ensure sufficient selectivity for ISE. Standard methods used for sulphate determination such as gravimetry, ion chromatography or turbidimetry have certain disadvantages which are overcome by ISE. The basic properties of newly developed sulfate ion selective electrodes were tested. It was found that a sufficient stabilization time of the electrode in a sulfate anion solution of 10−4 mol dm−3 was one day. The electrode with a potential response most closely approximating the theoretical Nernst response showed linear behavior toward the sulfate anion in the concentration range of 10−6 -10−1 mol dm-3 with a slope of −9.2±2.9 mV per order of magnitude; however, the repeatability of the measurement was quite poor. Interference from nitrate, chloride and acetate anions was significant, monohydrogen phosphate and sulfite anions could be considered negligible.
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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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