Sulfamethoxazole is an antibiotic that is among the drugs most frequently found in waters around the world because of its habitual consumption and its high chemical stability that prevents it from being eliminated from the environment. In this study, an electroanalytical methodology based on differential pulse voltammetry is developed for the analysis of sulfamethoxazole at trace levels in water. After the optimization of the instrumental parameters a linear range from 6.59 to 96.27 μM was found with limits of detection and quantification of 1.98 and 6.59 μM, respectively, with an RSD below 6 %. Moreover, several validation studies involving different pH values, water samples and instrumentation-techniques were performed in order to ensure the robustness of the method. For this purpose, the peak area was used as quantitative variable since it is not affected by the pH of the medium even if there is any modification of this parameter during the experiments. Furthermore, the effect of other drug such as trimethoprim on the analytical signal of sulfamethoxazole was also evaluated. Once the method was developed it was tested on the quality control of Soltrim®, obtaining recoveries between 98 and 102 %. Lastly, the voltammetric method was applied for the in situ monitoring of sulfamethoxazole's removal from water samples, specifically by anodic oxidation and electro-Fenton treatments. While the former was coupled to an adsorption process, the latter was carried out with different iron sources including commercial medicines that can be found in wastewater. The problem of significant variation in pH during the treatment was solved by working with the peak area, and so obtaining valid and reliable kinetic data. Although anodic oxidation proved to be faster considering the calculated k_obs, electro-Fenton turned out to be more efficient in eliminating the drug, achieving the disappearance of its analytical signal in only 30 min of treatment.

In this study, several materials are presented as modifiers of the screen-printed carbon electrodes with the aim of developing new sensing platforms for the voltammetric analysis of drugs. Specifically, Clotiapine and Sulfamethoxazole were selected as models for antipsychotics and antibiotics, respectively. Different nanostructures were studied as modifiers, including both transition metals and carbon-based materials. Moreover, biochar and two metal-organic frameworks (MOFs) were tested as well. The NH₂-MIL-125(Ti) MOF showed an 80% improvement in the analytical signal of Sulfamethoxazole, but it partially overlapped with an additional signal associated with the loss of the MOF ligand. For this reason, several immobilization strategies were tested, but none of them met the requirements for the development of a sensor for this analyte. Conversely, carbon nanotubes and the NH₂-MIL-101(Fe) MOF were successfully applied for the analysis of Clotiapine in the medicine Etumine^®, with RSD below 2% and relative errors that did not exceed 9% in any case, which demonstrates the precision and accuracy achieved with the tested modifications. Despite these promising results, it was not possible to lower the limits of detection and quantification, so in this sense further investigation must be performed to increase the sensitivity of the developed sensors.

This study describes the development of catalytic surface immobilizing dopamine via cross-linking or tyrosinase through covalent bonds on an electrografted screen-printed carbon electrode with a 4-nitrobenzenediazonium ion. A simple electrochemical reduction approach was used to covalently graft aryldiazonium ions onto the surface of commercial electrodes. After functionalization with aminophenyl groups, dopamine, an important neurotransmitter, was immobilized by imine bond formation using glutaraldehyde as a bifunctional cross-linking molecule. The presence of immobilized dopamine was confirmed by cyclic voltammetry following the electrochemical response of the hydroquinone/quinone redox process from catechol functionalities on the surface, which are responsible for the catalytic activity. In addition, the surface was also characterized by cyclic voltammetry using the redox probe, [Fe(CN)₆]^3−/4−, obtaining a signal approximately 14 times higher than that of a bare electrode, achieving a dynamic concentration range spanning three orders of magnitude. Remarkable sensitivity was also obtained by combining the electrografting, in situ diazotation, to generate grafted aryl diazonium ions on the surface, and coupling reaction to anchor the tyrosinase enzyme to the electrode surface. The response of the TYR-biosensor towards catechol, using the redox probe as mediator, was 10 times higher than that obtained with the dopamine modified catalytic surface. These modified surfaces offer promising alternatives for the voltammetric quantification of catechol in environmental fields.

The research work presented here describes the development of catalytic surfaces immobilizing dopamine via cross-linking or tyrosinase via covalent bond on an electrografted screen-printed carbon electrode with a 4-nitrobenzenediazonium ion. A simple electrochemical reduction approach was used to graft aryldiazonium ions onto commercial electrodes, resulting in the formation of a covalently bonded aromatic layer on the electrode surface. After functionalization with aminophenyl groups, dopamine, an important neurotransmitter, was immobilized by imine bond formation using glutaraldehyde as a bifunctional cross-linking molecule. The presence of immobilized dopamine was confirmed by cyclic voltammetry following the electrochemical response of the hydroquinone/quinone redox process from catechol functionalities on the surface, which are responsible for the catalytic activity. In addition, the surface was also characterized by cyclic voltammetry using the redox probe, [Fe(CN)6]3-/4-, obtaining a signal on this catalytic DA-biosensor about 14 times higher than that of a bare electrode, achieving a dynamic concentration range spanning three orders of magnitude. Remarkable sensitivity was also obtained by combining the electrografting, in situ diazotation to generate grafted aryl diazonium ions on the surface and coupling reaction to anchor the tyrosinase enzyme to the electrode surface. The response of the TYR-biosensor towards catechol, using the redox probe as mediator, was 10 times higher than that obtained with the dopamine modified catalytic surface. These modified surfaces offer promising alternatives for the voltammetric quantification of catechol in environmental fields.