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Development of Novel Electrochemical Methods Using Various Membrane Materials for Monitoring of Selected Anticancer Drugs and Phytochelatins
Skalová, Štěpánka
Present Ph.D. Thesis is focused on the development of electrochemical methods for determination of anticancer drugs using various types of membranes for their preliminary separation. Furthermore, this Thesis reports the study of transport mechanisms of heavy metals in the presence of phytochelatins across biological membranes. Sodium anthraquinone-2-sulphonate (AQS) was used as a model compound for its similar structure with anthraquinone-based (AQ-based) anticancer drugs (doxo/daunorubicin) and also due to its better availability. All these compounds can be easily electrochemically oxidized and/or reduced. Redox behaviour of AQS was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in a cathodic region on mercury meniscus modified (m-AgSAE) and polished silver solid amalgam (p-AgSAE) electrodes, Obtained results were used for the development of a micro-volume voltammetric cell (MVVC). Its applicability for voltammetric determination of anticancer drugs was verified by using doxorubicin (DX) as a model substance. The second part of this Thesis deals with therapeutic monitoring of anticancer drugs in the blood circulation of the patients. For pilot experiments, a liquid-flow system with dialysis catheter and amperometric detection was used. The flow rate of carrier...
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Development of Novel Electrochemical Methods Using Various Membrane Materials for Monitoring of Selected Anticancer Drugs and Phytochelatins
Skalová, Štěpánka ; Barek, Jiří (advisor) ; Labuda, Ján (referee) ; Trnková, Libuše (referee)
Present Ph.D. Thesis is focused on the development of electrochemical methods for determination of anticancer drugs using various types of membranes for their preliminary separation. Furthermore, this Thesis reports the study of transport mechanisms of heavy metals in the presence of phytochelatins across biological membranes. Sodium anthraquinone-2-sulphonate (AQS) was used as a model compound for its similar structure with anthraquinone-based (AQ-based) anticancer drugs (doxo/daunorubicin) and also due to its better availability. All these compounds can be easily electrochemically oxidized and/or reduced. Redox behaviour of AQS was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in a cathodic region on mercury meniscus modified (m-AgSAE) and polished silver solid amalgam (p-AgSAE) electrodes, Obtained results were used for the development of a micro-volume voltammetric cell (MVVC). Its applicability for voltammetric determination of anticancer drugs was verified by using doxorubicin (DX) as a model substance. The second part of this Thesis deals with therapeutic monitoring of anticancer drugs in the blood circulation of the patients. For pilot experiments, a liquid-flow system with dialysis catheter and amperometric detection was used. The flow rate of carrier...
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Electrochemical Investigation of Novel Redox Indicatiors for Detection of DNA Damage
Otépka, Tomáš ; Vyskočil, Vlastimil (advisor) ; Fischer, Jan (referee)
Cílem této práce bylo zkoumání nových redoxních systémů, které by bylo možné využít pro detekci poškození DNA na rtuťovým meniskem modifikované stříbrné pevné amalgámové elektrodě (m-AgSAE). Jako slibné se nabízely komplexy 1,10-fenantrolinu (phen) a iontů přechodných kovů. Konkrétně byly provedeny pokusy s komplexy kobaltaných iontů a phen, jejichž příprava byla provedena slitím roztoků obou složek v příslušném poměru. Chování komplexů v této směsi bylo porovnáno se syntetizovaným komplexním kationtem [Co(phen)3]3+ , a to jednak s využitím voltametrické techniky, jednak spektrofotometricky pomocí UV/VIS spektrofotometrie. Analýzy na m-AgSAE probíhaly s využitím techniky diferenční pulsní voltamerie (DPV) ve vodném prostředí. Jako základní elektrolyt byl zvolen 0,1 mol.dm-3 KCl, který poskytoval nejširší potenciálové okno v katodické oblasti potenciálů. Nízkomolekulární DNA z lososího spermatu byla využita v následujícím modifikační kroku pro vytvoření modifikované elektrody. Poškození DNA bylo provedeno vystavením takto připraveného biosenzoru UV-C záření o vlnové délce 254 nm. Poškozená DNA naadsorbovaná na m-AgSAE byla testována pomocí DPV v elektrochemické cele obsahující ionty Co2+ nebo komplex Co2+ a phen, obojí o koncentraci 1.10-3 mol.dm-3 . Na získaných voltamogramech byla sledována...
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Electrochemical reduction of dehydrocholic and chenodeoxycholic acid at stationary mercury and amalgam electrodes
Patáková, Adéla ; Schwarzová, Karolina (advisor) ; Vyskočil, Vlastimil (referee)
This thesis deals with the study of electrochemical behaviour of dehydrocholic and chenodeoxycholic acid at stationary mercury-based electrodes - hanging mercury dropping electrode and silver solid amalgam electrode modified by a mercury meniscus. This is the first study of electrochemical behaviour of dehydrocholic acid which offers tree peaks with potentials around -1270 mV, -1450 mV and -1800 mV. The last one with the potential -1800 mV is probably the main peak given by reduction of carboxylic group of side chain of steroid skeleton. By cyclic voltammetry was determined that the process is quasireversible and is strongly influenced by adsorption of DHCA on the electrode surface and also by the pH which determines dissociation degree of carboxylic group. In the environment of BR buffer (pH 7.0) - methanol (9:1) was measured concentration dependence by DC, DP and "square-wave" voltammetry. By neither one of these methods have been reached satisfying limits of detection and wide linear dynamic ranges. However, the repeatable signals in wide range of pH can be used for electrochemical characterization of DHCA. CDCA offers in environment 0,04 mol·l-1 borat buffer (pH 9.1) - methanol (9:1) one signal with potential around -1350 mV. Position of this peak on the potential axe and also its height are...
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Study of electrochemical behaviour of tauroursodeoxycholic acid at mercury-based electrodes
Pišnová, Kateřina ; Schwarzová, Karolina (advisor) ; Navrátil, Tomáš (referee)
This thesis deals with electrochemical behaviour of tauroursodeoxycholic acid (TUDCA) at silver solid amalgam electrode modified by mercury meniscus (m-AgSAE), polished silver solid amalgam electrode (p-AgSAE) and hanging mercury dropping electrode (HMDE). This thesis is a part of a bigger scientific research that deals with synthesis and characterization of supramolecular systems based on natural steroid compounds and its conjugates. TUDCA offers one reduction peak at m-AgSAE in the environment of Britton - Robinson buffer in range of pH 6.0 - 13.0. The potential of this peak is around −1200 mV. Using cyclic voltammetry was determined that the process on the electrode surface is quasireversible, the reduction is controlled by diffusion and the anodic process is controlled by adsorption. Concentration dependence measured at HMDE by direct current voltammetry in 0.04 mol∙l-1 borat buffer (pH 9.1) is linear in two concentration intervals - 1∙10-3 - 2∙10-4 mol∙l-1 and 1∙10-4 - 8∙10-6 mol∙l-1 of TUDCA. There was no linear dependence between the increase of concentration of TUDCA and the height of the peak obtained on amalgam electrodes by methods DC, DP, cyclic and "square-wave" voltammetry. On HMDE was in several short concentration intervals measured by a CV method a linear dependence of cathodic and...
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The use of mercury-based electrode materials for the study of electrochemical reduction of selected bile acids
Hulová, Dagmar ; Schwarzová, Karolina (advisor) ; Navrátil, Tomáš (referee)
The electrochemic's behaviour of the bile acids (cholic, glycocholic, deoxycholic, ursodeoxycholic and lithocholic acid) was studied on the meniscus-modified silver solid amalgam electrode (m-AgSAE) by differential pulse voltammery. Bile acids provide in the solution of the Britton - Robinson buffer and methanol (9:1) in the pH range 3.0 to 12.0 a cathodal signal in the high negative potentials: cholic acid, deoxycholic acid, ursodeoxycholic acid and lithocholic acid about −1400 mV and glycocholic acid, which alone is the conjugate with glycine, about −1500 mV. Cholic acid, glycocholic acid, deoxycholic acid and ursodeoxycholic acid provide the highest peaks to pH 5.0, approximately in their pKa values. Lithocholic acid provides peaks from pH 7.0. It was demonstrated by the cyclic voltammetry that the electrochemical behavior is influenced by the adsorption of the bile acids to the electrode; presumed reaction at the working electrode - a reduction of a proton of a carboxylic group, is controlled by the diffusion and the process is quasireversible. Utilization of the electrochemical reduction of bile acids for the voltammetric determination does not seem very suitable. It has been proven that the presence of the methanol deteriorates the measuring results for glycocholic acid. In the presence of...
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Determination of Lead Using FIA Technique with Spectrophotometric and Electrochemical Detection
Hála, Petr ; Vyskočil, Vlastimil (advisor) ; Rychlovský, Petr (referee)
The aim of this thesis was the determination of lead in water samples using complexating reaction with 4-(2-pyridylazo)-resorcinol in medium of 2-amino-2- hydroxymethyl-propan-1,3-diol hydrochloride buffer (Tris·HCl). Firstly, for the determination was chosen UV/VIS molecular spectrometry in a static arrangement. Subsequently, the method was performed in flow injection arrangement. The calibration was performed under optimal experimental conditions. The limits of detection for static and flow injection arrangements were 0.097 mol dm-3 and 0.27 mol dm-3 , respectively. Secondly, the determination of lead by differential pulse voltammetry was performed. The electrochemical properties of lead complex were investigated. During these experiments it was found out that small amount of this complex was adsorbed on the surface of silver solid amalgam electrode. The calibration was performed, the limit of detection was 0.020 mol dm-3 . Keywords Lead, 4-(2-pyridylazo)-resorcinol, flow injection analysis, UV/VIS molecular spectrometry, differential pulse voltammetry, silver solid amalgam electrode.
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Voltammetric Determination of 5-Nitroindazole Using Hanging Mercury Drop Electrode Different Electrode and Polished Silver Solid Amalgam Electrode
Hrdlička, Vojtěch ; Navrátil, Tomáš (advisor) ; Zima, Jiří (referee)
The presented Bachelor Thesis deals with a study of electrochemical behavior of 5-nitroindazole (5-NI) with the search of optimal conditions for its determination using tech- niques of DC voltammetry (DCV) and differential pulse voltammetry (DPV) at hanging mer- cury drop electrode (HMDE) and polished silver solid amalgam electrode (p-AgSAE), and with the comparison of reached limits of quantification (LQ ). The optimal conditions found for determination of 5-NI in deionized water using DPV at HDME were as follows: Britton-Robinson (BR) buffer of pH 8.0 and inital potential of +100 mV. The calibration dependences were measured in the concentration range from 1·10-7 to 1·10-5 mol·dm-3 with the LQ of 1.8·10-7 mol·dm-3 . Moreover, the posibility of using adsorbtion stirring voltametry (AdSV) for determination of 5-NI in BR buffer of pH 8 was investigated. The method was ineffective due to rising base- line. The mechanism of electrochemical reduction and oxidation in BR buffer of pH 8 at HMDE was investigated. It was found that the reduction of 5-NI was controlled by diffusion and the following oxidation was controlled by adsorbtion. For determination of 5-NI in deionized water using DVP at p-AgSAE, optimal conditions seemed to be as follows: BR buffer of pH 8.0 and initial potential of +100 mV....
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Voltammetric Determination of 5-Nitroimidazole - The Structural Unit of Nitroimidazole Drugs
Šmídková, Monika ; Vyskočil, Vlastimil (advisor) ; Fischer, Jan (referee)
Presented Diploma Thesis deals with the study of electrochemical behavior of 5-nitroimidazole (5-NI), with the search for optimal conditions for its determination using techniques of DC voltammetry (DCV) and differential pulse voltammetry (DPV) at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE) and at a boron-doped diamond film electrode (BDDFE), and with the comparison of reached limits of quantification (LQs). The optimal conditions found for measuring calibration dependences of 5-NI at the m-AgSAE in deionized water were as follows: Britton-Robinson buffer of pH 7.0 and 10.0 for DCV and DPV, respectively. At both thechniques, it is advisable to use an electrochemical regeneration of the electrode surface by the application of a couple of regeneration potentials Ereg,1 = 0 mV and Ereg,2 = −800 mV. The calibration dependences were measured in the concentration range from 1·10−6 to 1·10−4 mol·l−1 , with the LQs of 1.0·10−6 mol·l−1 for DCV at the m-AgSAE and 1.5·10−6 mol·l−1 for DPV at the m-AgSAE. The concentration dependences of 5-NI at the BDDFE were measured using the DCV technique in the BR buffer of pH 3.0. For the DPV technique, the optimal medium seemed to be the BR buffer of pH 2.0, however, because of the presence of an interfering peak in the supporting electrolyte,...
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Voltammetric Determination of Genotoxic Nitrobiphenyls
Horáková, Eva ; Vyskočil, Vlastimil (advisor) ; Navrátil, Tomáš (referee)
The presented diploma thesis is devoted to study of determination of 4-nitrobiphenyl (4-NBP) in model river water by DC voltammetry (DCV) and differential pulse voltammetry (DPV) at m-AgSAE (diploma thesis relates to bachelor thesis, in it DCV and DPV methods for determination of 4-NBP in deionized water were developed). Limit of determination (LOD) is 2·10-7 mol·l-1 by DCV and 4·10-7 mol·l-1 by DPV. The adsorptive stripping DPV (AdSDPV) technique was tested to archive lower LOD the AdSDPV, optimal conditions were not found. Electrochemical behavior of 2-nitrobiphenyl (2-NBP) at m-AgSAE was studied. Optimal conditions for its determination by both techniques DCV and DPV were found in methanol-0,01 mol·l-1 LiOH (1:9) and in this medium peak current dependence in 1·10-7 mol·l-1 to 1·10-4 mol·l-1 2-NBP (LOD ≈ 2·10-7 mol·l-1 by DCV and 1·10-7 mol·l-1 by DPV) concentration range was measured. Developed methods were successfully tested for determination of 2-NBP in drinking and river water samples. For both mediums obtained LODs were 2·10-7 mol·l-1 by DCV and 1·10-7 mol·l-1 by DPV. AdSDPV technique was unsuccessfully tested to achieve lower LOD. Optimal conditions for simultaneous determination of 4-NBP and 2-NBP by DPV technique at m-AgSAE were found: methanol-0,25 mol·l-1 acetate buffer (pH = 6,0) 3:7....
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