Chloroquine is a drug belonging to the aminoquinoline family that is widely used for treating diseases such as lupus, cancer, and malaria. In this sense, the present work describes the development of a simple method based on electrogenerated chemiluminescence (ECL) and a screen-printed carbon electrode (SPE) modified with carbon black for chloroquine determination. The carbon black modified SPE was characterized by scanning electron microscopy, Raman spectroscopy, cyclic voltammetry and linear sweep voltammetry to obtain the ECL-potential curves. The ECL method is based on the chemiluminescence resulting from the interaction between chloroquine and the tris(2’2-bipyridyl) ruthenium(II) complex. Under optimized experimental conditions, the method showed a wide linear working range between 0.5 and 500 µmol L-1. The method presented good precision and accuracy in drug samples used in the treatment of malaria and artificial urine sample, showing recovery values from 100 to 103% and 99 to 103%, respectively.

This work describes the development of a platform based on bismuth oxyiodide (BiOI), sulfur-doped graphitic carbon nitride (S-g-C3N4), and bismuth-doped sodium tantalate perovskite (Bi-NaTaO3) for zero-biased photoelectrochemical immunosensing of cardiac troponin I (cTnI) biomarker. The spectroscopic, structural, morphological, and compositional characteristics of the photoelectrochemical (PEC) materials were evaluated by Raman and Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). Electrochemical impedance (EI) measurements were performed under the incidence and absence of light to investigate the effects of photons on the charge transfer resistance of the photoelectrochemical platform. The influence of the cTnI biomarker on the photoelectrochemical response of the anti-cTnI antibody-modified photoelectrochemical platform (anti-cTnI/BiOI/S-g-C3N/Bi-NaTaO3/FTO) was evaluated by measuring the photocurrent of the system. The immunosensor presented a linear response range from 1 pg mL 1 to 50 ng mL 1, mean recovery percentage between 95.98 and 99.78% in real human serum samples, and selectivity for the cTnI biomarker.

The present work is based on the development and application of a photoelectrochemical method for the amperometric determination of 3,4,5-trihydroxybenzoic acid in different samples. The method is based on the use of a photoelectrochemical platform based on a glass slide coated with fluorine-doped tin oxide, which has been modified with cadmium sulfide and poly(D-glucosamine) and subjected to a light-emitting diode (LED) lamp. The photoelectrochemical platform was sensitive to the increase of the concentration of the antioxidant 3,4,5-trihydroxybenzoic acid in the solution. Under the optimized experimental conditions, the photoelectrochemical method presented a linear response for a 3,4,5-trihydroxybenzoic acid concentration ranging from 0.2 up to 500 µmol L-1. The method was applied to 3,4,5-trihydroxybenzoic acid determination in samples of wines and teas with recoveries between 95.88 and 101.72%. The results obtained suggest that the developed platform is a promising tool for quantifying the 3,4,5-trihydroxybenzoic acid.

This work describes the development of a photoelectrochemical sensor for glucose quantification exploiting a light assisted-batch injection analysis (BIA) cell. A light-emitting diode (LED) lamp was employed to control the incidence of light on the p-Cu2O/n-Cu2O/fluorine-doped tin oxide (FTO) photoactive platform in BIA cell. The p-Cu2O/n-Cu2O/FTO platform was constructed by electrodepositing n-Cu2O and p-Cu2O and the characteristics of electrodeposited Cu2O films were investigated by X-ray diffraction (XRD), Raman spectroscopy, and electrochemical impedance spectroscopy. The light assisted-batch injection analysis of glucose based on the illuminated p-Cu2O/n-Cu2O/FTO photoelectrode presented a linear response of 10 μmol L-1-1 mmol L-1, a limit of detection of 4.0 μmol L-1, and sensitivity of 0.768 ± 0.011 μA L μmol-1 cm-2. The system presented an average recovery value of 96% when applied to the determination of glucose in an artificial saliva sample, which indicates that the incidence of light on photoelectroactive platforms is a promising approach for the determination and quantification of glucose.

The present work presents the development of a sensitive and selective amperometric sensor for the determination of hydrazine (HZ) in pharmaceutical formulations using a glassy carbon electrode (GCE) modified with a composite based on Co(Salophen), reduced graphene oxide (rGO) and deoxyribonucleic acid (DNA). The rGO/Co(Salophen)/DNA composite was characterized by using Fourier-transform infrared spectroscopy (FTIR), cyclic voltammetry, and amperometry. The proposed platform presented a well-defined voltammetric profile with a redox couple around 0.32 V vs. Ag/AgCl which showed excellent catalytic activity towards HZ oxidation. The peak current of HZ electrochemical oxidation on the proposed electrochemical platform have changed linearly with the HZ concentration in the range from 2 to 364 µmol L-1. The proposed platform presented sensitivity, limit of detection, and limit of quantification of 0.056 µA L µmol-1, 0.54 µmol L-1, and 1.64 µmol L-1 to HZ, respectively. The relative standard deviation for eight determinations using a solution of 50 µmol L-1 HZ was 0.85%. The proposed sensor was successfully applied for the determination of HZ in pharmaceutical formulations, and the recovery tests showed a good accuracy with recovery percentage between 99 and 101%.

This work presents a simple and fast method for colchicine (CO) determination in pharmaceutical formulations and urine by multiple pulse amperometry (MPA) with flow injection analysis (FIA) system using a boron-doped diamond electrode. In optimized conditions, it was possible to quantify CO in urine samples without interference of uric acid and ascorbic acid. The working linear range for CO quantification was achieved from 1.0 × 10-7 to 0.5 × 10-3mol L-1 with a low limit of detection of 2.14 × 10-8mol L-1. Furthermore, the proposed method showed high repeatability for 10 consecutive injections of 1.0 × 10-4mol L-1 CO (relative standard deviation = 1.28%) and good analytical frequency (30 determinations per hour). The addition and recovery studies in all pharmaceutical samples were approximately 100% and the results for CO determination were compared by high performance liquid chromatography (HPLC) with UV detection.

In this study, a photoelectroanalytical sensor for determination of adrenaline based on deoxyribonucleic acid (DNA) and anatase titanium dioxide (TiO2) nanoparticles sensitized with bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) was developed, which we henceforward call BEDT-TTF/DNA/TiO2/ITO. The photoelectroanalytical sensor showed high photocurrent to adrenaline under visible light emitting diode (LED) light irradiation in comparison to each component of the composite material. Under optimized conditions, the BEDT-TTF/DNA/TiO2/ITO sensor shows a linear response range from 10 nmol L-1 up to 100 µmol L-1 with a sensitivity of 8.1 nA L µmol-1 and limit of detection of 1 nmol L-1 for the detection of adrenaline. The photoelectrochemical sensor showed high photocurrent to adrenaline in comparison to photocurrent response to ascorbic acid and uric acid. The BEDT-TTF/DNA/TiO2/ITO photoelectrochemical sensor was successfully applied to urine samples, with recovery values between 96 and 106%.

This work describes the electrochemical performance of a novel composite based on nickel tetrasulfonated phthalocyanine (NiTsPc), deoxyribonucleic acid from calf thymus (CT-DNA) and reduced graphene oxide (rGO) for the electroanalysis of reduced β-nicotinamide adenine dinucleotide (NADH), through electrocatalytic oxidation. The modified electrode was denoted as CT-DNA/NiTsPc/rGO. Fourier transform infrared and ultraviolet-visible spectroscopies were performed to characterize the composite material. The electrochemical performance of the composite for NADH oxidation was investigated by cyclic voltammetry (CV), chronoamperometry and differential pulse voltammetry (DPV). The CT-DNA/NiTsPc/rGO modified glassy carbon electrode (GCE) showed an excellent electrocatalytic activity for NADH oxidation with apparent electrocatalytic rate constant (kobs) of 7.35 × 105 L mol-1 s-1 and linear response range for NADH from 1 up to 1350 µmol L-1 for n = 12 (r = 0.999). The proposed sensor shows sensitivity, detection limit and quantification limit of 0.014 µA L mol-1, 0.3 and 1 µmol L-1, respectively. The prepared sensor was further tested for the determination of NADH in artificial human urine samples, showing promising biomedical applications.

The present work describes the development of a selective electrochemical sensor for urate based on tris(1,10-phenantroline)copper(II) bis(tetracyanoquinodimethanide) (Cu(phen)3(TCNQ)2) adsorbed on multi-walled carbon nanotubes (CNT). The composite material was characterized by infrared spectroscopy, scanning electron microscopy, and electrochemical impedance spectroscopy. The composite material showed an excellent electrocatalytic activity toward oxidation of urate. The heterogeneous charge transfer rate constant (k’) between the analyte and the sensor was determined using linear sweep voltammetry experiments. The composite material shows a linear range from 5 up to 2500 µmol L-1 with limit of detection of 1.05 µmol L-1 and limit of quantification of 3.50 µmol L-1. The high sensitivity and selectivity of the sensor for urate was sufficient for its determination in biological fluids. Finally, the proposed sensor was successfully applied in urine samples.

O presente trabalho apresenta uma metodologia simples, rápida e de baixo custo para a determinação de citrato de sildenafila (SC) em formulações farmacêuticas de referência (Viagra®) e em produtos similares, genéricos e manipulados, por amperometria de múltiplos pulsos em sistema FIA (análise por injeção em fluxo). O método consiste na aplicação de três pulsos de potencial (sequenciais) em função do tempo sobre um eletrodo de trabalho de diamante dopado com boro. SC foi detectado em 1,6 e 1,9 V por meio de dois diferentes processos irreversíveis de oxidação. Um terceiro pulso de potencial (1,0 V) foi aplicado para regeneração da superfície do eletrodo. Foram obtidos limites de detecção na ordem de 10 nmol L-1 e desvio padrão relativo menor que 0,2% (n = 10) para SC 4,5 X 10-5 mol L-1, permitindo 86 injeções por hora. Estudos de adição e recuperação nas amostras ficaram próximos de 100% e os resultados foram validados por cromatografia.

This work presents a simple, fast and low-cost method for determining sildenafil citrate (SC) in Viagra® and in similar, generic and manipulated pharmaceutical formulations using flow injection analysis (FIA) with multiple pulse amperometric detection. The method consists on the application of three sequential potential pulses as a function of time. SC is detected at 1.6 and 1.9 V by two different irreversible oxidation processes. The third potential pulse (1.0 V) is applied for the regeneration (cleaning) of the surface of the boron-doped electrode. The limit of detection on an order of 10 nmol L-1 was reached with a relative standard deviation of less than 0.2% (n = 10) for 4.5 X 10-5 mol L-1 CS. The analytical frequency was calculated in 86 injections per hour. The addition recovery studies in all the samples were approximately 100% and the results were validated by chromatographic methods.

A construção de um sensor amperométrico para compostos fenólicos usando um eletrodo de pasta de carbono modificado com ftalocianina de manganês e histidina é relatado. Sob condições otimizadas, em 0 mV vs Ag/AgCl numa solução tampão fosfato 0,1 mol dm-3 (pH 7,0) contendo H2O2 250 µmol dm-3, uma resposta linear para catecol entre 20 e 130 µmol dm-3, com sensibilidade de 0,56 (± 0,02) µA dm³ mol-1 cm-2, foi obtida. O limite de detecção foi 1,1 µmol dm-3 e o tempo de resposta foi de 2 s. O sensor apresentou resposta estável durante 40 determinações sucessivas. A repetibilidade avaliada em termos de desvio padrão relativo foi de 3,6% para n = 5 e [catecol] = 10 µmol dm-3. As respostas do sensor para outros compostos fenólicos também foram investigadas em detalhes. Finalmente, a aplicabilidade do sensor foi testada em medicamento contendo dopamina e os resultados comparados favoravelmente com os obtidos com o método oficial.

The construction of an amperometric sensor for phenolic compounds using a carbon paste electrode modified with manganese phthalocyanine and histidine is reported. Under optimized conditions, at 0 mV vs Ag/AgCl in 0.1 mol dm-3 phosphate buffer solutions (pH 7.0) containing 250 µmol dm-3 H2O2, a linear response for catechol from 20 up to 130 µmol dm-3 was obtained with a sensitivity of 0.56 (± 0.02) µA dm³ µmol-1 cm-2. The detection limit was 1.1 µmol dm-3 and the response time was 2 s. The sensor presented stable response during 40 successive determinations. The repeatability, evaluated in terms of relative standard deviation, was 3.6% for n = 5 and [catechol] = 10 µmol dm-3. The sensor responses for other phenolic compounds were also investigated in details. Finally, the applicability of the sensor was tested in a pharmaceutical containing dopamine and the results compared favorably with those obtained with the official method.