A problemática envolvendo os efluentes têxteis decorre principalmente da elevada coloração que apresentam, devido à presença de corantes que além de serem quimicamente estáveis, podem ser tóxicos e/ou carcinogênicos. Logo, quando são descartados in natura no meio ambiente causam problemas estéticos e, sobretudo, ambientais mesmo em baixas concentrações, além da possibilidade de serem nocivos à saúde humana e dos animais. Neste contexto, o objetivo deste trabalho foi estudar a degradação eletroquímica de dois corantes têxteis, Reativo Azul 19 (RA-19) e o Reativo Preto 5 (RP-5) via Oxidação Anódica (OA), utilizando ânodos de Diamante Dopado com Boro (DDB) suportados em titânio ou em nióbio, via processo Eletro-Fenton (EF) e pela combinação dos processos com H2O2 eletrogerado e OA (CP), usando um eletrodo de Carbono Vítreo Reticulado (CVR) como cátodo. As degradações foram realizadas em célula eletroquímica de um compartimento e em reator de fluxo do tipo filtro-prensa com dois compartimentos. A eficiência das degradações foi monitorada pelas técnicas de espectrofotometria no UV-VIS, Cromatografia Líquida de Alta Eficiência (CLAE) e análise do teor de Carbono Orgânico Total (COT). As variáveis estudadas foram densidade de corrente (10-100 mA cm-2 em célula e 4-41 mA cm-2 em reator), dopagem do eletrodo de DDB/Ti (5.000 e 15.000 ppm B/C), concentração inicial dos íons Fe2+ (0-0,10 mmol L-1) e dos corantes (10-250 mg L-1). As degradações dos corantes apresentaram uma cinética de pseudo ordem zero; exceto quando o corante RP-5 foi degradado pelo processo EF, sendo o melhor ajuste ao modelo de pseudo primeira ordem. Além disso, em iguais condições eletroquímicas o corante RP-5 foi degradado em menor tempo em relação ao RA-19; sendo que em todos os processos estudados os corantes foram totalmente removidos. Considerando a OA em célula com os eletrodos de DDB/Ti, a degradação foi positivamente influenciada pelo aumento da densidade de corrente e dopagem do eletrodo, especialmente em relação a cinética. Além disso, os corantes RA-19 e RP-5 foram completamente removidos em 35 e 50 min de eletrólise quando 100 mA cm-2 foi aplicada ao eletrodo de DDB/Ti dopado com 15.000 ppm relação B/C. Em 2 h, 37% em mineralização foi observado para ambos os corantes e a toxicidade do RA-19 diminuiu contra as bactérias Vibrio fischeri. Ainda nessa condição total mineralização foi alcançada após 8 h de degradação. A remoção de COT foi favorecida utilizando o reator contendo os eletrodos de DDB/Nb e CVR ao invés da célula eletroquímica, chegando a percentuais de 84 e 82% em 30 e 90 min para os corantes RA-19 e RP-5 que foram removidos em 7,5 e 5 min, respectivamente, quando a densidade de 41 mA cm-2 foi aplicada ao DDB/Nb durante a degradação via exclusivamente OA. Entre os processos realizados no reator, o EF foi o energeticamente mais favorável, promovendo remoção em COT de 60 e 74% para os corantes RA-19 e RP-5 com consumo energético de 204 e 208 kWh kg-1, além disso, a completa remoção dos corantes ocorreu em 15 e 7,5 min, respectivamente, quando o eletrólito continha íons Fe2+ na concentração de 0,10 mmol L-1 e aplicando-se -0,4 V vs Ag/AgCl ao eletrodo de CVR. Na degradação os corantes via CP o RA-19 e RP-5 foram completamente removidos em 30 e 15 min com mineralização de 72 e 82% em 90 min associada a consumos energéticos de 562 e 745 kWh kg-1, respectivamente, quando 41 mA cm-2 foi aplicada ao DDB/Nb. Por fim, concluiu-se que os resultados das degradações dos corantes foram promissores, já que rápida remoção dos corantes foi observada, além da parcial mineralização. Logo os processos propostos podem ser aplicados na remoção dos corantes em água; sendo necessários realizar mais estudos, principalmente em relação ao material eletródico e configuração do sistema eletroquímico visando a aplicação industrial. / The main problem involving the textile wastewater is theirs high coloration since they present dyes, which are chemically stable and can be toxic and/or carcinogenic. Therefore, when the textile wastewater are discarded in nature in the environment, even in low concentrations, they may cause not only aesthetic and environmental problems, but also can be harmful to human and animal health. In this context, the aim of the study was to evaluate the electrochemical degradation of two textile dyes, Reactive Blue 19 (RB-19) and Black 5 (RB-5) via Anodic Oxidation (AO) using as anodes Boron Doped Diamond electrodes (BDD) supported on titanium or niobium, via Electro-Fenton (EF) process and by combination of processes with electrogenerated H2O2 and AO (CP) using a Reticulated Vitreous Carbon electrode (RVC) as cathode. The degradations assays were carried out in an electrochemical cell with one compartment and in a filter-press flow reactor with two compartments. The efficiency of degradation was monitored by UV-VIS spectrophotometry, High Performance Liquid Chromatography (HPLC) and analysis of Total Organic Carbon (TOC). The variables studied were current density (10-100 mA cm-2 for cell and 4-41 mA cm-2 for reactor), doping of the BDD/Ti electrodes (5,000 e 15,000 ppm B/C), initial concentration of the Fe2+ ions (0-0,10 mmol L-1) and dyes (10-250 mg L-1). The kinetic results showed that the removal of dyes followed the model of pseudo zero order; except when the RB-5 dye was degraded by EF process, which the best fitted was to pseudo first order model. Furthermore, for equal conditions the RB-5 was degraded in less time in comparison to the RB-19. In addition, the dyes were fully removed in all the processes studied. Regarding the AO in cell with BDD/Ti, the degradation was positively influenced by the increasing in current density and doping of the electrode, primarily the kinetics parameters. In addition, total removal of RB-19 and RB-5 was achieved in 35 and 50 min of electrolysis when 100 mA cm-2 was applied to the electrode doped with 15,000 ppm ratio B/C. In 2 h, 37% in mineralization was attained for both dyes and the toxicity effect of the RB-19 decreased against the bacteria Vibrio fischeri. In this condition, total TOC removed was also reached after 8 h. The TOC removal was enhanced using the reactor fitted with BDD/Nb and RVC instead of the electrochemical cell, achieving TOC removal of 84 and 82% in 30 and 90 min for RB-19 and RB-5 which were removed in 7.5 and 5 min, respectively, when 41 mA cm-2 was applied to the BDD/Nb in the degradation exclusively via AO. Among the processes carried out in the reactor, the EF was the energetically most favourable since TOC removal of 60 and 74% for RB-19 and RB-5 with energy consumption of 204 and 208 kWh kg-1 were noted. In addition, the RB-19 and RB-5 were completely removed in 15 and 7.5 min, respectively, when the electrolyte containing 0.10 mmol L-1 of Fe2+ ions and -0.4 V vs Ag/AgCl was applied to CVR electrode. The combination of processes with electrogenerated H2O2 and AO for degradation of the dyes removed the RB-19 and RB-5 in 30 and 15 min with mineralization of 71.6 and 81.8% in 90 min associated to energy consumptions of 562 and 745 kWh kg-1 respectively, when 41 mA cm-2 was applied to BDD/Nb. Therefore, the degradation results of the dyes were promised since quickly removal of the dyes and partial mineralization were observed hence the proposed processes could be used to remove the dyes from water. However, more studies are needed to enable an industrial application, especially regarding the electrode material and configuration of the electrochemical system.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines.

Magister Scientiae - MSc / In this work, an electrochemical method based on a cyt c biosensor has been developed, for the detection of selected arsenic and cyanide compounds. Boron Doped Diamond (BDD) electrode was used as a transducer, onto which cyt c was immobilised and used for direct determination of Prussian blue, potassium cyanide and arsenic trioxide by inhibition mechanism. The sensitivity as calculated from cyclic voltammetry (CV) and square wave voltammetry (SWV), for each analyte in phosphate buffer (pH= 7) was found to be (1.087- 4.488 ×10-9 M) and the detection limits ranging from 0.0043- 9.1 μM. These values represent a big improvement over the current Environmental Protection Agency (EPA) and World Health Organisation (WHO) guidelines. / South Africa

?rea de concentra??o: Qu?mica anal?tica. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2016-12-21T13:02:41Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) glauber_antonio_reis_andrade.pdf: 2400963 bytes, checksum: 99ec593844d6ba3a1107158d86656739 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-01-21T11:09:00Z (GMT) No. of bitstreams: 2 license_rdf: 9 bytes, checksum: 42dd12a06de379d3ffa39b67dc9c7aff (MD5) glauber_antonio_reis_andrade.pdf: 2400963 bytes, checksum: 99ec593844d6ba3a1107158d86656739 (MD5) / Made available in DSpace on 2017-01-21T11:09:00Z (GMT). No. of bitstreams: 2 license_rdf: 9 bytes, checksum: 42dd12a06de379d3ffa39b67dc9c7aff (MD5) glauber_antonio_reis_andrade.pdf: 2400963 bytes, checksum: 99ec593844d6ba3a1107158d86656739 (MD5) Previous issue date: 2016 / A Teofilina (TF), Clindamicina (CM), Varfarina (VF) e Verapamil (VP) s?o f?rmacos de baixo ?ndice terap?utico que necessitam de um controle de qualidade rigoroso na elabora??o de suas formula??es. O desenvolvimento de m?todos mais simples e r?pidos para doseamento desses medicamentos ? de grande interesse no setor farmac?utico. Neste sentido, o presente trabalho apresenta uma nova metodologia para determina??o desses f?rmacos por amperometria de m?ltiplos pulsos (MPA) acoplada ao sistema de an?lise por inje??o em batelada (BIA), utilizando o eletrodo de Diamante dopado com Boro (DDB). A an?lise em BIA foi realizada em uma c?lula eletroqu?mica do tipo Wall Jet, onde as inje??es foram realizadas por meio de uma micropipeta autom?tica ou, manualmente, por uma seringa descart?vel para TF, CM e VF, mostrando a possibilidade de diminuir custo do sistema de an?lise. O comportamento eletroqu?mico da TF, CM, VF e VP foi investigado por voltametria c?clica e os eletr?litos suportes escolhidos foram o ?cido sulf?rico 0,1 mol L-1, tamp?o fosfato 0,1 mol L-1 (pH 7,0), tamp?o fosfato 0,1 mol L-1 (pH 7,0) com 10% de ?lcool et?lico e ?cido sulf?rico 0,2 mol L-1, respectivamente. Nesses eletr?litos tr?s f?rmacos apresentaram um ?nico processo de oxida??o: a TF em +1,33V, a CM em +1,18 V e a VF em +0,90 V. J? o VP apresentou tr?s processos de oxida??o entre +1,2V e +1,5V, al?m de um processo de redu??o em +0,2V depende das oxida??es. A detec??o MPA-BIA foi baseada na aplica??o de um pulso de potencial de detec??o e outro de limpeza do DDB para tr?s f?rmacos. Neste caso, os pulsos de potencial para detec??o da TF, CM e VF foram todos aplicados por 100ms em +1,5V, +1,6V e +1,2V, respectivamente. Para determina??o do VP foram utilizados tr?s pulsos de potencial, um para oxida??o do VP (gerador) em +1,6V/50ms, um para redu??o do produto gerado (coletor) e quantifica??o do VP em -0,1V/30ms, e um terceiro em +1,1V/100ms para limpeza da superf?cie do DDB. A velocidade de inje??o da MA foi otimizada em 100?L s-1, exceto para VP que foi de 47?Ls-1, e com a SD a velocidade de inje??o foi de aproximadamente 107 ?Ls-1 pra a TF, CM e VF, proporcionando uma frequ?ncia anal?tica te?rica de pelo menos 53 determina??es por hora desses f?rmacos. Um baixo desvio padr?o relativo (10 medidas) foi obtido para todos os f?rmacos, n?o ultrapassando 3,0% tanto pela inje??o autom?tica quanto pela manual. As curvas anal?ticas foram estabelecidas e uma boa faixa linear foi obtida para todos os f?rmacos com pelo menos duas ordens de concentra??o. Os coeficientes de correla??o linear para todas as regress?es foram maiores que 0,992 em todos os estudos. Os estudos de adi??o e recupera??o mostraram valores pr?ximos a 100 % para todas as amostras farmac?uticas analisadas. O m?todo proposto usando a inje??o autom?tica e manual foi devidamente validado pelo m?todo oficial para cada um dos f?rmacos avaliados. Portanto, a detec??o MPA-BIA usando o eletrodo de DDB mostrou ser uma alternativa mais simples e r?pida para determina??o da TF, CM, VF e VP em formula??es farmac?uticas, possibilitando ainda uma diminui??o do custo do sistema BIA pela substitui??o da micropipeta autom?tica por uma seringa descart?vel. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / Theophylline (TF), Clindamycin (CM), Warfarin (VF) and Verapamil (VP) are drugs of narrow therapeutic index that require a strict quality control in the preparation of their formulations. Thus, the development of simple and rapid methods for determination of these drugs is very important in the pharmaceutical industry. In this sense, this paper presents a new methodology for determination of these drugs by multiple-pulse amperometry (MPA) coupled to batch injection analysis (BIA), using the boron-doped diamond (BDD) electrode. The analysis in BIA system was performed in an electrochemical cell (Wall Jet), where the injections were performed by automatic micropipette or manually by an disposable syringe for TF, CM and VF, showing a possibility to reduction of the analysis cost. The electrochemical behavior of the analytes was investigated by cyclic voltammetry and the support electrolytes were chosen for TF, CM, VF and VP in medium of sulfuric acid 0.1 mol L-1, phosphate buffer 0.1 mol L-1 (pH 7.0), phosphate buffer 0.1 mol L-1 (pH 7.0) with 10% ethyl alcohol and sulfuric acid 0.2 mol L-1, respectively. In these conditions, three drugs exhibited a single oxidation process: TF in +1.33V, the CM in +1.18V and the VF in +0.90V (vs Ag/AgCl). Already the VP presented three oxidation processes between +1.2V and +1.5V, besides a reduction process in +0.20 V that depends on the oxidation. The MPA-BIA detection for three drugs (TF, CM, VF) was based on the application of two potential pulses, one for detection and other for cleaning BDD electrode. In this case, the potential pulses to detection the TF, CM and VF were all applied for 100ms at +1.5V, +1.2V and +1.6 V, respectively. In determination of the VP, were used three potential pulses, one for oxidation of VP (generator potential pulse) in +1.6V/50ms, one for reducing the generated product (collector potential pulse) and performed quantification of VP in -0.1V/30ms, and a third potential pulse at +1.1V/100ms for cleaning BDD electrode. The injection speed using automatic micropipette was 100?L s-1, except for VP that was 47?Ls-1, and injection speed by insulin syringe was approximately 107?Ls-1, which provide theoretical analytical frequency of at least 53 determinations per hour of these drugs. A low standard relative deviation (10 measures) was obtained for all drugs, not extending beyond 3.0% by both injections systems. The analytical curves were established and a good linear range was obtained for all drugs with at least two orders of concentration. The linear correlation coefficients for all regressions were higher than 0.992. The addition and recovery studies show values close to 100% for all drug samples analyzed. The proposed method using automatic and manual injection was validated by official method for each analyte. Therefore, this paper presented a fast and simple method for the determination of TF, CM, VF and VP in pharmaceutical formulations using BIA-MPA detection with BBD electrode. Moreover, this work demonstrated an inexpensive method for application in routine analysis of narrow therapeutic index drugs, mainly using a manual injection in BIA system by an disposable syringe.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / In this work we investigated the potentiality of batch injection analysis with square-wave voltammetry (BIA-SWV) detection for simultaneous determination of Zn and naphazoline (NAF) and batch injection analysis with multiple pulse amperometric (BIA-MPA) detection for simultaneous determination of NAF and pheniramine (FEN) or NAF and chlorpheniramine (CLO). In both methods, boron-doped diamond (BDD) was used as working electrode. For the simultaneous determination of Zn and NAF by BIA-SWV, the following conditions have been optimized: supporting electrolyte: acetate buffer 0.05 mol L-1 (pH = 4.7), injection volume: 100 μL, deposition time (Zn): 5 s, deposition potential (Zn) -1.5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Under these conditions, the method showed linear response range between 10 and 60 μmol L-1 for Zn (r = 0.992) and between 3.0 e 21 μmol L-1 for NAF (r = 0.999), high analytical frequency (70 injections h-1) and LOD of 0.126 μmol L-1 and 0.04 μmol L-1 for Zn and NAF, respectively. In the study of repeatability (n = 20), the calculated RSD were 0.98% and 0.97% for Zn and NAF, respectively. The simultaneous determination of NAF and FEN or NAF and CLO by BIA-MPA was performed with the application of three sequential pulses in function of time to the BDD electrode using Britton-Robinson Buffer solution 0.12 mol L-1 (pH = 10.0) as supporting electrolyte. At +1.1 V/50 ms, FEN or CLO was detected (oxidation) without interference of NAF. At +1.3 V/50 ms, both compounds (FEN + NAF or CLO + NAF) were oxidized. The current of NAF can then be obtained by subtraction of the currents detected during application of both potential pulses using a correction factor. The proposed method presented good ability (RSD = 1.7 and 4.0% for FEN and NAF; 2.1% and 3.6% for CLO and NAF, respectively; n=20); high analytical frequency (110 injections h-1), linear concentration range between 16 e 100 μmol L-1 for FEN and CLO (r > 0.996) and between 2 e 15 μmol L-1 for NAF (r > 0.997). The LOD calculated were 0.367, 0.361 e 0.148 μmol L-1, for FEN, CLO and NAF, respectively. The proposed methods were used for determination of these compounds in pharmaceutical samples. The obtained results were statistically similar to that obtained by HPLC (NAF, FEN and CLO) and atomic spectroscopy (Zn). / No presente trabalho investigou-se a potencialidade do sistema de análise por injeção em batelada com detecção por voltametria de onda quadrada (BIA-SWV) para determinação simultânea de Zn e nafazolina (NAF) e do sistema análise por injeção em batelada com detecção por amperometria de múltiplos pulsos (BIA-MPA) para determinação simultânea de NAF e feniramina (FEN) ou NAF e clorfeniramina (CLO). Em ambos os métodos, diamante dopado com boro (BDD) foi usado como eletrodo de trabalho. Para determinação simultânea de Zn e NAF empregando BIA-SWV, as seguintes condições foram otimizadas: eletrólito de suporte: tampão acetato 0,05 mol L-1 (pH = 4,7), volume de injeção: 100 μL, tempo de deposição (Zn): 5 s, potencial de deposição (Zn): -1,5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Nestas condições, o método apresentou faixa linear de resposta entre 10 e 60 μmol L-1 para Zn (r = 0,992) e entre 3,0 e 21 μmol L-1 para NAF (r = 0,999), frequência analítica de 70 injeções h-1 e limites de detecção de 0,126 μmol L-1e 0,04 μmol L-1 para Zn e NAF, respectivamente. No estudo de repetibilidade (n = 20), os DPRs foram calculados 0,98% e 0,97% para Zn e NAF, respectivamente. A determinação simultânea de NAF e FEN ou NAF e CLO por BIA-MPA foi realizada através da aplicação de dois pulsos de potenciais em função do tempo ao eletrodo de BDD usando tampão BR 0,12 mol L-1 (pH = 10) como eletrólito suporte. Em +1,1 V/50 ms, FEN ou CLO foram oxidadas livre da interferência de NAF. Em +1,3 V/50ms, ambos os compostos (NAF + FEN ou NAF + CLO) foram oxidados. A corrente proveniente da oxidação da NAF foi obtida pela subtração entre as correntes detectadas em ambos os pulsos de potenciais com auxílio de um fator de correção (FC). O método proposto apresentou boa estabilidade (DPR = 1,7 e 3,95% para FEN e NAF; 2,1 e 3,6% para CLO e NAF, respectivamente; n=20), alta frequência analítica (110 injeções h-1), faixa linear de resposta entre 16 e 100 μmol L-1 para FEN e CLO (r > 0,996) e entre 2 e 15 μmol L-1 para NAF (r > 0,997). Os limites de detecção foram de 0,367, 0,361 e 0,148 μmol L-1 para FEN, CLO e NAF, respectivamente. Os métodos propostos foram usados na determinação destes compostos em formulações farmacêuticas. Os resultados obtidos com os métodos propostos foram estatisticamente similares aos obtidos por HPLC (NAF, FEN e CLO) ou absorção atômica (Zn). / Mestre em Química

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...

Presented Ph.D. Thesis is focused on the use of the boron-doped diamond (BDD) electrodes for voltammetric and amperometric determination of selected nitrophenols: 2-nitrophenol (2NP), 4-nitrophenol (4NP), and 2,4-dinitrophenol (2,4DNP). These compounds are listed as "priority pollutants" by United States Environmental Protection Agency (US EPA) due to their negative impact on living organisms and are mainly used in agriculture as plant growth stimulators. BDD electrodes are used for determination of wide range of electrochemically both reducible and oxidisable organic compounds and have become a popular electrode material thanks to its commercial availability and excellent mechanical and electrochemical properties. A differential pulse voltammetric method was developed for the determination of 2NP, 4NP and 2,4DNP at a BDD film electrode using electrochemical reduction and of 4NP and 2,4DNP using electrochemical oxidation. The method was successfully applied for the direct determination of these compounds in drinking and river water in the concentration range from 4×10-7 to 2×10-5 mol.L-1 . To improve the limit of quantification, a preconcentration by solid phase extraction from 100 mL (drinking and river water) and 1000 mL (drinking water) of water samples was used with limit of determination...

Presented dissertation thesis is focused on the development of electrochemical methods for the determination of three important tumour biomarkers, namely homovanillic acid (HVA), vanillylmandelic acid (VMA), and 5-hydroxyindole-3-acetic acid (5-HIAA). First part of the study is focused on electrochemical behaviour of these analytes in batch arrangement using differential pulse voltammetry (DPV) at screen-printed carbon electrodes (SPCEs). It has been proved that presented method is sufficiently sensitive for monitoring above mentioned analytes. Moreover, it can be used for determination of HVA and VMA in mixture. Obtained limits of detection (LODs) were 0.24 µmol·L-1 for HVA, 0.06 µmol·L-1 for VMA, and 0.12 µmol·L-1 for 5-HIAA. The requirements to speed up the analysis and at the same time to reduce its price initialized our study of the determination of tested biomarkers in flow systems. Firstly, flow injection analysis with amperometric detection was investigated for the determination of all three biomarkers at the same SPCE, and then an analogous determination of structural more similar pair, HVA and VMA, was performed at a boron doped diamond electrode (BDDE). Obtained LODs of optimized methods were as follows: at SPCE 0.07 µmol·L-1 for HVA, 0.05 µmol·L-1 for VMA, and 0.03 µmol·L-1 for 5-HIAA,...

In this work, the application of boron-doped diamond electrodes with various surface pre- treatment were tested on selected oxidizable and reducible model compounds, specifically para and ortho cresols and 2'-deoxycytidine and 7-deazaadenosine labeled by 4-nitrophenyl triazole. The aim of the study was the investigation of electrochemical and adsorptive processes with respect to the development of electroanalytical methods of detection of the selected compounds, or utilization of boron-doped diamond electrodes as detectors in liquid-flow systems. Cresols were used as the model oxidizable compound. On O-terminated and polished boron- doped diamond electrodes, cresols provide oxidation signal owing to their oxidation to methylphenoxy radical at comparable potentials as on other carbon-based electrodes used as a reference in this work, i.e., glassy carbon electrode, pyrolytic graphite electrode, and carbon paste electrode. These carbon electrode materials show relatively high propensity to adsorption of reaction products, while such adsorption is minimal on boron-doped diamond. In situ anodic activation allows for a rapid regeneration of boron-doped diamond surface prior to each scan. A differential pulse voltammetric method that was developed with a detection limit of 0.61 mol∙l-1 to 2.97 mol∙l-1...