This diploma thesis deals withthe studyof electrochemical behaviorand detection of two structurally different neurotransmitters, dopamine (DA) and serotonin (5-HT), in solutions commonly used for neuron cultivation, namely Neurobasal (NB), NB with phenol red and in phosphate buffer (PB) of a pH close to the physiological value. An electrode based on boron-doped diamondwas used for the study, examiningtwo types of surfaces obtained after oxidation (O-BDD) and mechanical polishing (p-BDD). The results were obtained by two voltametric techniques,namely cyclic and differential pulse voltammetry.The studyrevealedthat DA oxidationis a quasi-reversible process,whereas 5-HT oxidizes irreversibly on O-BDD and p-BDD. Nevertheless, for both neurotransmitters their anodic oxidationonboth BDD surfaces is controlledby diffusion. Due to the passivation of the electrode surface by the oxidation products, anodic reactivation(Eact = +2400 mV, t = 30 s) was first testedto regenerate the O-BDD surface during DA and 5-HT measurements. There was no continuous decrease in DA peak currents on O-BDD and the measuredsignals were characterizedby high repeatabilityin all studiedmedia (sr (Ip) 1.1% in PB of pH 7.0, 1.7% in NB of pH 7.34, 0.9% in NB with phenol red of pH 7.48). In the case of 5-HT, the anodic reactivation was...

The aim of this thesis was the development of a voltammetric method for the determination of 7-dehydrocholesterol as a biomarker of congenital disease Smith-Lemli-Opitz syndrome. The concentration of 7-dehydrocholesterol in plasma will increase hundred-fold to hundreds to thousands µmol L-1 in patients suffering from Smith-Lemli-Opitz syndrome. The determination of 7-dehydrocholesterol was carried out in artifical serum in this work, which was prepared to mimic the conditions of postnatal diagnosis of Smith-Lemli-Opitz syndrome. 7-dehydrocholestrol provides a well developed voltammetric signal at approximately +0.8 V vs. Ag/AgNO3 in acetonitrile. Differential pulse voltammetry with optimized parameters was used for the determination of 7-dehydrocholesterol. The presence of protein in artificial serum (human serum albumin) resulted in an unacceptably high detection limit of the method (178 µmol L-1 in artificial serum). Therefore, human serum albumin was eliminated from the artificial serum samples by precipitating it with acetonitrile and subsequently centrifuging the resulting suspension. At the same time, the ratio of aqueous and organic components in the studied medium was also adjusted with acetonitrile to achieve an optimal voltammetric response of 7-dehydrocholestrol. With regard to the...

This thesis is devoted to the study of electrochemical oxidation of meta-substituted phenolic substances on a boron-doped diamond electrode. In the first phase, it was studied the effect of pH on their electrochemical oxidation by the methods of classical "direct current" voltammetry (DCV) and differential pulse voltammetry (DPV). The study was performed on three types of boron doped diamond (BDD) surfaces: polished, anodic and cathodically activated. In the second phase, attention was paid to the Hammett correlation to study the effect of the substituent on the potential of electrochemical oxidation of selected phenolic compounds. Among the substituents studied were (-H, -CH3, -OCH3, -(CH2)2COOH, -COOH a -NO2). In general, the oxidation potentials were lower in the basic medium than in the acidic medium on all studied surfaces. An exception was the studied phenolic acids, which could not be detected in an alkaline medium on the O-terminated BDD, probably due to electrostatic repulsion between the partially negative electrode surface and the acid dianion. The highest correlation coefficient for the dependence composed of all studied phenols was obtained for the polished and H-terminated surface at pH 11, ie the dissociated form of phenolic substances. The high electron density leads to easy...

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...

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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Ce travail est une contribution à la conception d'un système portatif et intégré de type µTAS (micro-Total Analysis System) pour le traitement (préconcentration et simplification) de solution aqueuses contenant des métaux lourds et leur analyse en ligne. Pour la préconcentration amont, l'étude a porté sur la réalisation d'un micro-électrodialyseur manipulant des µL de solutions. L'optimisation des paramètres opératoires a permis d'augmenter d'un facteur 100 environ les concentrations d'analytes. Pour l'étage de détection aval, un système sur puce de type polarographique a été étudié. Le traditionnel mercure est remplacé par du diamant polycristallin dopé au bore (DDB) préparé par CVD micro-ondes. La quantification des métaux lourds par redissolution anodique sur ce matériau a été validée ainsi que les techniques de gravure compatibles avec la réalisation de microréseaux d'électrodes. / This work is a contribution to the conception of an integrated μTAS (micro-Total Analysis System) for treatment (preconcentration and simplification) of aqueous solutions containing heavy metals and their on-line analysis. For upstream preconcentration, a micro-electrodialyser handling µL of solutions was developped. The optimization of operating parameters permitted to reach an analyte pre-concentration factor of about 100. For the downstream detection step, an on-chip polarographic system, where mercury was replaced by boron doped diamond (BDD), was studied. BDD films were prepared by assited microwave plasma CVD. Quantification of heavy metals by anodic stripping on BDD was validated as well as the etching technique compatible with the realization of microarray electrodes.

L'usage intensif de pesticides dans l'agriculture engendre une contamination sans précédent des eaux de surface et des nappes phréatiques. Les traitements classiques appliqués aux eaux usées contenant des produits organiques polluants sont basés sur la biodégradation ou sur des méthodes physiques de transfert de masse (décantation, filtration, adsorption des polluants sur du charbon actif) ou des procédés chimique tels que l'oxydation à l'ozone ou au chlore. Cependant, ces procédés demeurent inefficaces dans le cas de traitement des eaux contaminées par les polluants organiques persistants (POPs). Les procédés d'oxydation avancés sont mis en œuvre pour dégrader ou même minéraliser ces polluants. Ce travail a donc pour objectif de déterminer un protocole expérimental pour détruire efficacement les pesticides, produits chimiques largement utilisés dans l'agriculture au Maroc, tels que le monochloro-benzène, le 1,2-dichlorobenzène, l'acide 2,4,5-trichlorophénoxy-acétique, et l'imazalil en utilisant les procédés d'oxydation avancée électro-Fenton et oxydation anodique avec différentes anodes telles que BDD, Pt et DSA. Ainsi, nous avons trouvé que le taux de minéralisation par procédé électro-Fenton avec l'anode BDD était de 92%, 95%, 92% et 97%pour le monochloro-benzène, le 1,2-dichlorobenzène, l'acide 2,4,5-trichlorophénoxy-acétique, et l'imazalil, respectivement, après 4 h de traitement. Ces résultats confirment l'efficacité des procédés d'oxydation avancés électrochimiques dans le traitement des eaux polluées par des pesticides / The intensive use of pesticides in agriculture generates, nowadays, an unprecedented contamination of surface water and groundwater. Conventional treatments applied to waste water containing organic pollutants are based on biological treatments méthods or physical mass transfer methods (decantation, filtration, adsorption of the pollutants on activated carbon), chemical oxidation with ozone, chlorine, etc. However, these methods remain ineffective for the treatment of water polluted by persistent organic pollutants (POPs). Advanced oxidation processes are implemented to degrade and mineralize these pollutants. This PhD thesis work aims to establish an experimental protocol to degrade and mineralize pesticides, chemicals widely used in agriculture in Morocco, such as monochlorobenzene, 1,2-dichlorobenzene, 2,4,5-trichlorophenoxy-acetic acid , and imazalil using the electro-Fenton and anodic oxidation processes with DD Pt or DSA anodes. Thus, the rate of mineralization was 92%, 95%, 92% and 97% for the monochloro-benzene, the 1,2-dichlorobenzene, the 2,4,5-trichlorophenoxyacetic acid , and the imazalil, respectively, after 4 h treatment by electro-Fenton process. These results confirm the effectiveness of electrochemical advanced oxidation processes for treating water polluted by pesticides

The aim of this Thesis is development of electroanalytical methods for determination of cholesterol and 7-dehydrocholesterol on boron doped diamond electrodes based on electrochemical oxidation of products of acid-induced dehydration reaction. Two approches have been applied, relying on their detection in 0,1 mol.l-1 perchloric acid in acetonitril containing variable water content 0,43 % - 40 %. Cyclic voltammetry revealed substantial difference in oxidation peak pontecials for 7-dehydrocholesterol (+850 mV) and cholesterol (+1500 mV) in 0,1 mol.l-1 perchloric acid in acetonitrile containing 5 % of water. The limit of detection using differential pulse voltammetry were 6,19 µmol.l-1 a 19,2 µmol.l-1 for a mixture of 7-dehydrocholesterol and cholesterol, respectively. For flow injection analysis with amperometric detection (FIA-AD) the water content in run buffer, detection potencial and the distance between the capillary outlet and electrode surface in wall-jet arrangement of amerometric flow-through detection cell were optimized. Achieved detection limits are in range of 0,61 - 3,43 µmol.l-1 depending on the detection potencial and water concent in the run buffer. The developed FIA-AD method was used for determination of a model mixture solution of 7- dehydrocholesterol and cholesterol. Key words...

Os ésteres de ácido ftálico são utilizados como aditivos na manufatura de plásticos e a contaminação do meio ambiente por esses compostos pode ocorrer por diferentes mecanismos. Dado o efeito destes no sistema endócrino de animais e seres humanos, efluentes contendo esses compostos sintéticos devem ser adequadamente tratados antes de qualquer descarte. Os tratamentos convencionais são ineficientes para tratar efluentes aquosos contendo esses ésteres e a oxidação eletroquímica tem sido utilizada como uma opção viável. Assim, neste trabalho foi estudada a degradação eletroquímica de dimetil ftalato (DMFt) utilizando três tipos de ânodos: Ti/Ru0.3Ti0.7O2, F-β-PbO2 e diamante dopado com boro (DDB). Os experimentos foram conduzidos em condições galvanostáticas em células de compartimento do tipo filtro-prensa e vários parâmetros, tais como, eletrólito suporte e a densidade de corrente, foram avaliados. Durante as eletro-oxidações, alíquotas das soluções foram analisadas cromatograficamente e por determinações de carbono orgânico total (COT) e demanda química de oxigênio (DQO). Quando utilizado o ânodo de Ti/Ru0.3Ti0.7O2, foram observados níveis de combustão próximos a 100% em baixos valores de carga elétrica aplicada, indicando um possível processo de incineração direta. Com a incidência de radiação UV incidindo diretamente na superfície do eletrodo, foi obtida a completa remoção de DMFt e 98 % de mineralização em meio ácido, elevadas concentração de cloreto e temperatura. A limitação de ambos os processos foi o transporte de massa e assim, os melhores resultados foram obtidos a baixas densidades de corrente. Com o uso do ânodo de β-PbO2 a remoção de DMFt foi superior na presença de Na2SO4 e em baixas densidades de corrente, com 40 % de mineralização. Com o ânodo de DDB foram realizadas eletro-oxidações na ausência e na presença de radiação UV e ultrassônica. Foi obtida a completa remoção de DMFt, COT e DQO em todas as condições estudadas, com maior eficiência a baixas densidades de corrente, devido a menor limitação por transferência de massa. Ocorreu um efeito positivo na eletrooxidação com aplicação conjunta das duas radiações, no entanto, menor do que o obtido com a aplicação destes processos separadamente. O mecanismo de degradação proposto apresenta a oxidação de DMFt seguida da remoção de grupos metil éster e a quebra do anel aromático para formar ácidos carboxílicos, os quais são mineralizados a dióxido de carbono. Na presença de cloreto, a produção de clorofenóis e ácido tartárico e o aumento na concentração dos intermediários formados são as principais diferenças observadas. / The phthalic acid esters are used as additives in plastics manufacturing and the environmental contamination by these compounds may occur by different mechanisms. Considering its effect on the endocrine system of animals and humans beings, effluents containing these synthetic compounds must be properly treated before any disposal. Traditional methods present limited efficiency for treating wastewater containing these esters and electrochemical oxidation has been proposed as a viable option. In this work, the electrochemical degradation of dimethyl phthalate (DMFt) using three types of anodes: Ti/Ru0.3Ti0.7O2, β-PbO2,F and boron-doped diamond (BDD) was studied. The experiments were performed under galvanostatic conditions using a one compartment filter-press cell and different parameters, such as, electrolyte and current density, were analyzed. During the electro-oxidations, aliquots of the solutions extracted at diffent times were analyzed by liquid chromatography and by variations of total organic carbon (TOC) and chemical oxygen demand (COD). Using Ti/Ru0.3Ti0.7O2 anode, the combustion levels were almost 100% when low values of electrical charge were applied, indicating a possible direct incineration process. Applying UV radiation to the electrode surface, the complete removal of DMFt and 98% mineralization were obtained in acid medium with relative high chloride concentration. Both processes were limited by mass transport and therefore, the best results were obtained at low current densities. Using β-PbO2 anode, the removal of DMFt was higher with 40% of mineralization in the presence of Na2SO4 and at low current densities. Using DDB anode, the electrooxidations were performed in the absence and presence of UV and ultrasonic radiations. The complete removal of DMFT, TOC and COD was obtained for all conditions studied with greater efficiency at low current densities because the smallest mass transfer limitation. A positive effect on the electro-oxidation was observed when UV and ultrasound radiation were applied simultaneously however, lower than that obtained with the application of the processes separately. The degradation mechanism proposed presents the oxidation of DMFt followed by removal of methyl ester groups and breakage of the aromatic ring to form carboxylic acids, which are mineralized to carbon dioxide. In the presence of chloride, the production of chlorophenol and tartaric acid and the increased concentration of the intermediates formed are the majors differences observed.