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Voltammetric Determination of Selected Nitrated Heterocyclic Compounds Using Various Amalgam-Based Electrodes
Fischerová, Dana ; Barek, Jiří (advisor) ; Vytřas, Karel (referee) ; Navrátil, Tomáš (referee)
Development and testing of new non-toxic electrode materials, their preparation and the development of analytical methods applicable for determination of selected substituted nitrobenzimidazoles is the main aim of this Ph.D. Thesis. New working electrodes based on the modification of surface of polished silver solid amalgam electrode (p-AgSAE) by other electrodes materials which contain mainly mercury (mercury meniscus modified silver solid amalgam electrode (m-AgSAE), mercury film modified silver solid amalgam electrode (MF-AgSAE)), bismuth (bismuth film on silver solid amalgam electrode (BiF-AgSAE)) or carbon (electrode modified by microcrystalline natural graphite-polystyrene composite transducer (CFE)) were developed. The optimum deposition time for preparation of film electrodes were discover and verified. Their electrochemical behavior (stable and reproducible responses during measurement) were investigated and further used in voltammetric determination of mutagenic or carcinogenic environmental pollutants 2-amino-6-nitrobenzimidazole (ANBT) and 5-nitro- benzimidazole (5-NBIA). These analytes could be determined by direct current voltammetry (DCV) or differential pulse voltammetry (DPV). The attempt at increasing the sensitivity using adsorptive striping DCV or DPV at all tested electrodes...
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Electrochemical Determination of Fomesafen
Maška, Jan ; Barek, Jiří (advisor) ; Fischer, Jan (referee)
The submitted work deals with the application of voltammetric determination of Fomesafen using non-traditional mercury meniscus modified silver solid amalgam electrode on model samples of Fomesafen in real aqueous matrices of drinking and river water. This method of measurement has been developed and optimized in my bachelor thesis, which the diploma thesis is related to. Fomesafen belongs to a group of herbicides used on a mass scale in the late 20th century in the USA and in many countries around the world still used even today. Among its side effects according to the EPA include, among others, potential carcinogenicity to humans and confirmed carcinogenicity to some mammals (such as rats) which led to a legislative regulation on its use in many countries around the world including the USA, the European Union and many others. Silver solid amalgam electrode has been developed with the intention to limit the use of mercury in accordance with new legislation of the European Union and the concept of green analytical chemistry. Despite the low levels of mercury mainly bound in the form of virtually harmless silver amalgam electrode retains very similar electrochemical properties with proven mercury electrodes. As part of the thesis, direct determination of a number of partial extraction of Fomesafen...
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Silver Amalgam Electrodes in Electroanalysis of Selected Agrochemicals
Daňhel, Aleš ; Barek, Jiří (advisor) ; Vytřas, Karel (referee) ; Ludvík, Jiří (referee)
4 ABSTRACT Development and testing of novel non-toxic electrode materials, detection arrangements and analytical methods applicable in determination of selected agrochemicals is the main aim of this Ph.D. Thesis. New working electrodes based on silver solid amalgam paste (AgSA-PE) with organic pasting liquid and other based on crystallic silver amalgam (CAgAE) were developed, their electrochemical behaviour investigated and further used in voltammetric determination of widespread and toxic environmental pollutant 4-nitrophenol (4-NP). This analyte could be determined by DPV at AgSA-PE with limit of detection (LD) 1×10í6 mol lí1 and using CAgAE with LD 4×10í7 mol lí1 , both in 0.2 mol lí1 acetate buffer pH 4.8. Attempts to decrease LDs by utilization of adsorptive stripping voltammetry were not successful in either case. Crystallic silver amalgam was also successfully used for construction of microcylindric flow-through cell and tested for amperometric determination of nitrophenol mixture in HPLC-ED system. Both novel electrodes were found to be suitable alternatives to toxic mercury electrodes and the CAgAE seems to be promising working electrode for flowing systems. Method for sample preparation and voltammetric determination of broad-spectrum herbicide Glyphosate in contaminated soil samples was also...
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Voltametric Determination of 4-Nitrophenol at a Bismuth Film Electrode
Hausner, Jiří ; Barek, Jiří (advisor) ; Dejmková, Hana (referee)
This Bachelor Thesis is focussed on the study of electrochemical behaviour of 4-nitrophenol (4-NP) and the search for optimal conditions for its voltammetric determination at a bismuth film-modified gold electrode (BiF-AuE). Voltammetric behaviour of 4-NP (c = 1×10-4 mol L-1 ) was investigated using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) in dependence on the pH of the medium used (Britton-Robinson buffers). For both techniques, Britton-Robinson buffer of pH 7.0 was chosen as the optimum medium. Repeatability of the determination of 4-NP (c = 1×10-4 mol L-1 ) was 0.6 % and 0.9 % for DCV and DPV, respectively. Calibration dependences of 4-NP were measured in the concentration range from 1×10-6 to 1×10-4 mol L-1 under the optimum conditions. Attained limits of quantification (LQs) were 7.6×10-7 mol L-1 and 1.5×10-6 mol L-1 for DCV and DPV, respectively. The applicability of the newly developed voltammetric methods for the determination of 4-NP was verified on model samples of drinking water with LQ 7.5×10-6 mol L-1 for DCV at the BiF-AuE and 1.4×10-6 mol L-1 for DPV at the BiF-AuE.
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Polarographic and Voltammetric Determination of Fomesafen
Maška, Jan ; Barek, Jiří (advisor) ; Fischer, Jan (referee)
The work is related to the polarographic and voltammetric determination of Fomesafen on the basis of its cathodic reduction using classical dropping mercury electrode (DME), hanging mercury drop electrode (HMDE) and non-traditional mercury meniscus modified silver solid amalgam electrode (m-AgSAE). Silver solid electrode (AgSAE) was developed as an alternative to mercury electrodes regarding legislative complications limitating usage of mercury because of its supposed toxicity. Properties of this electrode are very similar to the ones of mercury electrodes, mainly outstandingly broad cathodic potential region but excelent sensitivity either. As an electrode material, silver amalgam was used which non-toxicity is obvious given for example even by its long-term usage in stomatology as a main item for production of tooth-fillings. For model determination, Fomesafen was chosen because of its previous and sometimes also present usage as a major component of herbicid agents in agriculture. Its factual toxicity was actually proven and it was also classified as a potential carcinogen for humans. Historically, its usage was relatively deliberately massive, significant was e.g. in USA, but presently it was already forbidden in many countries. The intention of the work was to compare the analytical qualities...
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Voltammetric Determination of Dinitronaphthalenes Using Single Crystal Silver Amalgam Electrode
Tvrdíková, Jana ; Barek, Jiří (advisor) ; Dejmková, Hana (referee)
Voltammetric methods for determination of 1,3-dinitronaphthalene (1,3-DNN), 1,5-dinitronaphthalene (1,5-DNN) and 1,8-dinitronaphthalene (1,8-DNN) using DC voltammetry (DCV) and differential pulse voltammetry (DPV) at novel single crystal silver amalgam electrode (CAgAE) were developed in this work. Developed methods may be used for determination of 1,3-DNN within a concentration range 2 - 10 μmol.L-1 with LoQ 2 μmol.L-1 using DCV and 1 - 100 μmol.L-1 with LoQ 1 μmol.L-1 by DPV; 1,5-DNN wihin a concentration range 2 - 10 μmol.L-1 with LoQ 2 μmol.L-1 using DCV and 1 - 10 μmol.L-1 with LoQ 1 μmol.L-1 by DPV and 1,8-DNN within a concentration range 2 - 10 μmol.L-1 with LoQ 2 μmol.L-1 using DCV and 0,3 - 1 μmol.L-1 with LoQ 0,3 μmol.L-1 by DPV. An attepmt to decrease LoQ by adsorptive stripping differential pulse voltammetry was not successful. Process of electrochemical reduction of selected dinitronaphthalenes on the working electrode was also studied by cyclic voltammetry. This work verified the use of CAgAE as alternative electrode material to mercury electrodes for determination of electrochemically reducible organic compounds in aqueous-methanolic media. Small dimensions of the CAgAE are the main advantages which predetermine its use in voltammetric microvolume batch analysis and amperometric detection in...
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Voltammetric and amperometric determination of 5-nitroquinoline in drinking and river water using carbon film electrode
Rumlová, Tereza ; Barek, Jiří (advisor) ; Dejmková, Hana (referee)
This work focuses on optimization and application of voltammetric methods for determination of 5-nitroquinoline in model samples of drinking and river water using carbon film electrode (CFE). The advantages of carbon film electrode are primarily its wide potential window in both cathodic and anodic regions and also low environmental stress compared to mercury electrodes. In this contribution, CV and AdSV were used to observe electrochemical processes. For determination of 5-nitroquinoline DPV and FIA were used. Solid phase extraction was investigated as a method for preliminary separation and preconcentration for DPV. Determination of 5-nitroquinoline at CFE is based on cathodic reduction of nitrogroup. This work demonstrates the application of carbon film electrode for determination of 5-nitroquinoline in submicromolar concentrations in model samples of water.
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Voltammetric and amperometric detection of genotoxic pyrene derivatives at boron-doped diamond film electrode
Yosypchuk, Oksana ; Barek, Jiří (advisor) ; Nesměrák, Karel (referee)
This thesis is concentrated on the optimization of conditions for determination of genotoxic environmental pollutants whitch belong to derivatives of polycyclic aromatic hydrocarbons − 1-nitropyrene (1-NP), 1-aminopyrene (1-AP) and 1-hydroxypyrene (1-HP). All three compounds were determined by differential pulse voltammetry (DPV) at boron-doped diamond film electrode in water-methanolic solutions. Further, 1-AP and 1-HP were determined in a model sample of urine. For this purpose, effective separative techniques such as solid phase extraction and high performance liquid chromatography with reverse phase and amperometric detection at above mentioned type of electrode were used. Limits of detection of all tested compounds in water-methanolic solutions are 9⋅10−8 −3⋅10−7 mol dm−3 using DPV and 1⋅10−8 mol dm−3 for 1-HP and 1-AP in model sample of urine determined by HPLC with amperometric detection.
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Voltammetric Determination of Anticancer Drug Flutamide and Its Metabolite 4-Nitro-3-trifluoromethylaniline
Radová, Jitka ; Barek, Jiří (advisor) ; Dejmková, Hana (referee)
The subject of this Diploma Thesis has been the study of electrochemical behavior of anticancer drug flutamide (FLD) and one of its metabolites 4-nitro-3-trifluoromethylaniline (NTMA). The aim was to find and define the optimum conditions for the determination of both compounds at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE) and at a carbon film electrode (CFE) using DC voltammetry (DCV) and differential pulse voltammetry (DPV). This Diploma Thesis follows closely the Bachelor Thesis, defended at the Department of Analytical Chemistry, Faculty of Science, Charles University in Prague. In this Bachelor Thesis, a voltammetric determination of FLD using DCV and DPV at m-AgSAE has been described, with attained limits of quantification (LQs) 5.0·10-6 mol.dm-3 (for DCV) and 3.0·10-6 mol.dm-3 (for DPV). In presented Diploma Thesis, voltammetric behavior of NTMA has been studied in dependence on the pH of the medium of Britton-Robinson (BR) buffer-methanol (9:1). The optimum conditions have been found for the determination of this substance using DCV and DPV at m-AgSAE and CFE in the cathodic area. As the optimum media, BR buffer-methanol (9:1) of resulting pHf 8.3 (for both DCV and DPV at m-AgSAE) and of pHf 5.1 (for both DCV and DPV at CFE) have been chosen. Further, the LQs have...
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New Electrochemical Methods for Determination of Nitro and Oxo Derivatives of Fluorene
Vyskočil, Vlastimil ; Barek, Jiří (advisor) ; Ludvík, Jiří (referee) ; Heyrovský, Michal (referee)
4. Conclusion This Thesis represents a contribution to the search for new analytical methods applicable on environmental and biological samples. The current state- of-art concerning the formation, occurrence, and biological activity of fluorene and its nitro and oxo derivatives was summarized in Chapter 1. Further experimental work was focused on assessment of new approaches in the detection of the studied compounds. Attention was paid mainly to nitrofluorenes, fluorenone and nitrofluorenones, namely 2-nitrofluorene, 2,7-dinitrofluorene, 9-fluorenone, 2-nitro-9-fluorenone, and 2,7-dinitro-9- fluorenone and the possibilities of their determination using polarographic and voltammetric methods. Interactions of calf thymus dsDNA with 2-nitrofluorene and 2,7-dinitrofluorene at the DNA/SPCPE were investigated and subtle DNA damage under conditions of direct DNA-analyte interaction at room temperature and damage to DNA bases under condition of electrogeneration of short-lived radicals of nitrofluorenes at human body temperature were found. The obtained results can be summarized as follows: ● Modern polarographic and voltammetric methods at mercury electrodes developed for determination of trace amounts of 9-fluorenone and 2,7-dinitro-9-fluorenone (and other NPAHs generally) in concentration ranges from 2×10-8 to...
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