Roberta Antigo Medeiros

In this study, a novel electrochemical assay for determining 17-β-estradiol (E2) was proposed. The approach involves modifying a glassy carbon electrode (GCE) with a nanocomposite consisting of α-Fe₂O₃ nanoparticles supported on carbon nanotubes (CNTs)—denoted as α-Fe₂O₃-CNT/GCE. The synthesis of the α-Fe₂O₃-CNT nanocomposite was achieved through a simple and cost-effective hydrothermal process. Morphological and chemical characterization were conducted using scanning electron microscopy (SEM), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDX). The presence of the α-Fe₂O₃-CNT film on the GCE surface resulted in an enhanced electrochemical response to E2, preventing electrode surface fouling and mitigating the decrease in peak current intensity during E2 oxidation. These outcomes substantiate the rationale behind the GCE modification. After the optimization of experimental conditions, E2 was determined by the square wave voltammetry technique using 0.1 mol L⁻¹ KCl solution (pH = 7.0) with 20% ethanol as a supporting electrolyte. A linear concentration range of 5.0–100.0 nmol L⁻¹ and a low limit of detection of 4.4 nmol L⁻¹ were obtained. The electroanalytical method using α-Fe₂O₃-CNT/GCE was applied for E2 determination in pharmaceutical, lake water, and synthetic urine samples. The obtained results were attested by recovery tests and by high-performance liquid chromatography as a comparative technique at a 95% confidence level. Thus, the developed electrochemical sensor is simple and fast to obtain, presents high accuracy, and is viable for determining E2 in routine analysis.

An electrochemical sensor for simultaneous determination of Benserazide (BEZ) and levodopa (L-dopa) was successfully developed using a glassy carbon electrode (GCE) modified with multi-walled carbon nanotube and nitrogen-doped titanium dioxide nanoparticles (GCE/MWCNT/N-TiO₂). Cyclic voltammetry and square wave voltammetry were employed to investigate the electrochemical behavior of different working electrodes and analytes. In comparison with unmodified GCE, the modified electrode exhibited better electrocatalytic activity towards BEZ and L-dopa and was efficient in providing a satisfactory separation for oxidation peaks, with a potential difference of 140 mV clearly allows the simultaneous determination of these compounds. Under the optimized conditions, linear ranges of 2.0–20.0 and 2.0–70.0 μmol L⁻¹ were obtained for BEZ and L-dopa, respectively, with a limit of detection of 1.6 µmol L⁻¹ for BEZ and 2.0 µmol L⁻¹ for L-dopa. The method was applied in simultaneous determination of the analytes in pharmaceutical samples, and the accuracy was attested by comparison with HPLC-DAD as the reference method, with a relative error lower than 4.0%.

This study reports a facile approach for constructing low-cost and remarkable electroactivity iron vanadate (Fe-V-O) semiconductor material to be used as a photoelectrochemical sensor for dopamine detection. The structure and morphology of the iron vanadate obtained by the Successive Ionic Adsorption and Reaction process were critically characterized, and the photoelectrochemical characterization showed a high photoelectroactivity of the photoanode in visible light irradiation. Under best conditions, dopamine was detected by chronoamperometry at +0.35 V vs. Ag/AgCl, achieving two linear response ranges (between 1.21 and 30.32 μmol L⁻¹, and between 30.32 and 72.77 μmol L⁻¹). The limits of detection and quantification were 0.34 and 1.12 μmol L⁻¹, respectively. Besides, the accuracy of the proposed electrode was assessed by determining dopamine in artificial cerebrospinal fluid, obtaining recovery values ranging from 98.7 to 102.4%. The selectivity was also evaluated by dopamine detection against several interferent species, demonstrating good precision and promising application for the proposed method. Furthermore, DFT-based electronic structure calculations were also conducted to help the interpretation. The dominant dopamine species were determined according to the experimental conditions, and their interaction with the iron vanadate photoanode was proposed. The improved light-induced DOP detection was likewise evaluated regarding the charge transfer process.

Flow injection analysis with chronoamperometry detection using a cathodically pretreated boron-doped diamond electrode (CPT-BDDE) was employed to develop and optimize a novel method for the determination of the hormones 17-α-ethinylestradiol (EE2) and cyproterone acetate (CPA). The electrochemical properties of EE2 and CPA were evaluated by cyclic voltammetry and oxidation peaks were observed at 0.97 V and 1.60 V in 0.04 mol L⁻¹ Britton-Robinson buffer (pH 2.0). Analytical curves were linear in the concentration range from 0.070 to 10.0 µmol L⁻¹ for EE2 and 1.0 to 80.0 µmol L⁻¹ for CPA with detection limits of 0.023 and 0.23 µmol L⁻¹, respectively. The developed methods presented good precision and accuracy for EE2 and CPA quantification in commercial pharmaceutical samples. The obtained results were satisfactory and consistent compared with a reference high-performance liquid chromatography method at a confidence level of 95%. Furthermore, recovery studies carried out in synthetic urine and lake water show that these methods do not suffer any significant matrix interferences and are potentially applicable for the determination of these hormones in real samples. Thus, the developed procedure for EE2 and CPA determination are simple and fast, with an analytical frequency of ∼83 determinations per hour, and attractive for routine analysis.