The developmental impulse of the present time has caused a continuous degradation of the environment, which increases the need of monitoring the contaminant levels launched in the natural water courses and industrial effluents. In this context, it is crucial to develop new methodologies of determination and quantification of various types of pollutants, with rapidity, selectivity and sensitivity, characteristics which were found in the chemically modified electrodes (CMEs). Many industrial processes are polluting the sources of water resources, such as the petrochemical industries and paper and cellulose industries. From those, sulfide is frequently set free causing serious demages due to its high toxicity, even in low concentrations, which suggests methods of detention of sulfide of high sensitivity, reduced time and low cost. Some analytical methodologies for the detention of sulfide are based on the reaction with methylene blue, which has recognized mediating electron capacity. Accordingly, the development and characterization of CMEs, modified with silica-niobium-methylene blue possess promising characteristics and great potential of use in these analyses. Studies of the voltametric behavior of CMEs had been carried through with different concentrations of SNAM. Beyond the effect of the paste composition, also the effect of the type of electrolyte support and of the pH had been investigated. The CMEs had been studied by cyclic voltammetry, linear voltammetry and chronoamperometry technique, presenting good reply to the ion sulfide in the linear response range between 7.59 x 10¬6 and 6,34 x 10¬5 moI L¬ 1, with correlation coefficient (r) of 0, 9979, detection limit of 2,03 x 10-6mol L-1 and quantification limit of 6,77 x 10¬6 moI L¬ 1. The results gotten in this work has allowed to conclude that the carbon paste modified with SNAM presents a good analytical performance for analysis of sulfide in samples of environmental interest

This paper reports the development of a glassy carbon electrode modified with a reduced graphene oxide (r-GO/GCE) for the determination of the food dye named Ponceau 4R (PNC). The modified sensor presented excellent signal gain in relation to the GCE and GCE modified with graphene oxide besides exhibiting well defined oxidation peaks for PNC at potential of 0.61 V. Through the application of square wave voltammetry using the medium of 0.1 mol L-1 Britton-Robinson (BR) buffer (pH 5.0), analytical curves were constructed under optimized conditions, where linear regions were found within the range of 0.200 to 20.0 μmol L-1. The limits of detection and quantification were 2.84 × 10-8 and 9.46 × 10-8mol L-1, respectively. The sensor was successfully applied towards the determination of PNC in instant juice sample. A comparison made between the result obtained through the application of this sensor and via the high-performance liquid chromatography (HPLC) technique showed no significant difference between the two methods.

Graphite was incorporated to a polydimethylsiloxane (PDMS) polymer network functionalized with amino groups to obtain an electrode material and used to detect copper ions in aqueous solutions and sugarcane spirit. The polymer network was prepared with PDMS, 3-aminopropyl-trimethoxysilane (APTMS), tetraethyl orthosilicate (TEOS) with addition of graphite to obtain the electrode material. The materials were prepared with different mass concentrations of PDMS: 0, 3, 6, 12 and 18%; and characterized by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). Quasi-reversible behavior was found when studying the [Fe(CN)6]3-/4- redox probe and were electrochemically stable up to 100 consecutive cycles. Electrochemical impedance measurements showed a second time constant at high frequencies for the PDMS electrodes, indicating a second phase in the polymer network with resistive properties, probably due to an increase in the material polymerization resistance. Square wave voltammetry studies were conducted with these electrodes to detect copper(II) ions in aqueous solution. The electrode proposed was applied to determine Cu2+ in a real sample, sugarcane spirit. The PDMS electrodes prepared here presented a potential to be applied as electrochemical sensors for detecting copper ions.

In this paper a novel supramolecular strategy to improve the efficiency of a voltammetric sensor to determine two biologically relevant molecules (epinephrine (EP) and uric acid (UA)) is presented. The strategy is based on the use of a glassy carbon electrode modified with a copper(II) complex ([Cu(H2dimpy)Cl]PF6) adsorbed on multi-walled carbon nanotubes (MWCNTs). The [Cu(H2dimpy)Cl]PF6/MWCNT composite-supported electrode was characterized by electrochemical impedance spectroscopy, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The electrocatalytic oxidation of EP and UA using the sensor was investigated by cyclic voltammetry and square wave voltammetry. Under optimized conditions, voltammetric peak currents showed a linear response for the EP and UA concentrations in the ranges 0.5-159.2 and 0.2-58.5 µmol L−1, whereas the limits of detection were 0.2 and 0.05 µmol L−1, respectively. The sensor was successfully applied in the selective and simultaneous determination of EP and UA in human urine samples. Thus, our results showed that the supramolecular strategy was successful to build an efficient sensor for simultaneous detection of these molecules in biological samples.

A novel electrochemical sensing platform was fabricated with nanohybrid consisting of graphene oxide and iron hydroxide colloid. With high surface area and excellent electrical conductivity of the nanohybrid, the prepared electrochemical sensor exhibited preeminent electrocatalytic activity towards the oxidation of phloroglucinol, resulting in the increase of the oxidation peak current and decrease of the oxidation overpotential. The nanohybrid was used as an enhanced electrochemical sensing platform for sensitive determination of phloroglucinol. The oxidation mechanism of phloroglucinol at this sensing platform was investigated in detail, the determination conditions were optimized, and the kinetic parameters were also calculated. Under the optimized conditions, the oxidation peak current was proportional to phloroglucinol concentration in the range from 5.00 to 100.00 nmol L-1 with limits of detection and of quantification of 3.45 and 11.51 nmol L-1, respectively. This sensing platform displayed long-term stability, high reproducibility and super anti-interference capability. It was employed to detect phloroglucinol in environmental water samples with good recoveries. The excellent performance, operational simplicity and low expense make the graphene-based hybrid attractive in the sensor construction.

A molecularly imprinted polymer (MIP) was prepared using the anti-inflammatory diclofenac (DCF) as a template. A non-imprinted polymer (NIP) was also prepared as a control. These MIP and NIP were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET), revealing a higher porosity in the first. Then both were used in the modification of graphite-polyurethane composites electrodes (GPUE). Differential pulse anodic stripping voltammetry was used for DCF determination at GPUE MIP DCF containing 2.5% (m/m) of the modifier in perchloric acid, pH = 2.0, after previously optimized conditions such as 300 s of accumulation time, +0.2 V accumulation potential (vs. SCE (saturated calomel electrode)), 50 mV pulse amplitude and 10 mV s-1 scan rate. A linear dynamic range from 0.010 to 0.20 μmol L-1 and a limit of detection (LOD) of 0.99 nmol L-1 were found, using GPUE 2.5 MIP DCF. DCF was determined in commercial pharmaceutical formulations and in synthetic urine samples, with recoveries between 101 and 102% (n = 3) and 101% (n = 3), respectively. The results agreed with the reference high-performance liquid chromatography (HPLC) within 95% confidence level, according to Student’s t-test. Interference from meclofenamic and mefenamic acids, which are structurally similar to DCF, was also evaluated. Interferences could not be totally avoided, but MIPs presented a considerable ability in discriminating the voltammetric response for DFC, despite the close structural similarity with the interferents.

A glassy carbon electrode modified with a molecularly imprinted polymer (MIP) containing phenacetin recognition sites is introduced. The phenacetin-selective MIP was synthesised based on the electropolymerisation of pyrrole in a 1:1 (v/v) water/ethanol with HClO4 solution. The MIP-modified electrode showed higher recognition ability in comparison with a bare electrode for procaine and aminopyrine, reported to electrochemically interfere in the quantification of phenacetin in cocaine samples. In addition, the MIP was able to preconcentrate one of the intermediates of the phenacetin electrochemical oxidation, acetaminophen, indicating the possibility of monitoring phenacetin based on the acetaminophen oxidation. The acetaminophen oxidation peak is 15 times more detectable compared to the signal obtained by the non-molecularly imprinted polymer (NIP), and it occurs 450 mV below the phenacetin electrochemical oxidation signal. These achieved characteristics decrease the possibility of interference from other electrochemical reactions that may occur in the same potential range as phenacetin electrochemical process.

A chemically modified electrode was constructed based on a multi-walled carbon nanotube-modified glassy carbon electrode (MWCNTs/GCE). It was demonstrated that this sensor can be used for the simultaneous determination of the pharmaceutically important compounds paracetamol (PAR) and tramadol (TRA). The measurements were carried out by the application of differential pulse voltammetry (DPV), cyclic voltammetry (CV) and chronoamperometry (CA) methods. Application of the DPV method demonstrated that in phosphate buffer (pH 7.5) there was a linear relationship between the oxidation peak current and the concentration of PAR over the range 0.5 µmol L-1 to 210 µmol L-1. A similar linear correlation between oxidation peak current and concentration was observed for TRA over the range of 2 µmol L-1 to 300 µmol L-1. Under optimal conditions the modified electrode exhibited high sensitivity, selectivity and stability for both PAR and TRA determination, making it a suitable sensor for the simultaneous submicromolar detection of PAR and TRA in solutions. The analytical performance of this sensor has been evaluated for detection of PAR and TRA in human serum, human urine and some pharmaceutical preparations with satisfactory results.

This work presents the construction of a novel electrochemical sensor for detection of organic analytes, using a glassy carbon electrode (GCE) modified with a chitosan-supported ruthenium film. The ruthenium-chitosan film was obtained starting from the mer-[RuCl3(dppb)(H2O)] complex as a [1,4-bis(diphenylphosphine)butane] (dppb) precursor, and chitosan (QT). The structure of the chitosan-supported ruthenium film on the surface of the glassy carbon electrode was characterized by UV-Vis spectroscopy, electron paramagnetic resonance (EPR), scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and atomic absorption spectroscopy (AAS) techniques. The glassy carbon electrode was modified with a film formed from the evaporation of 5 µL of a solution composed of 5 mg chitosan-supported ruthenium (RuQT) in 10 mL of 0.1 mol L-1 acetic acid. The modified electrode was tested as a sensor for sildenafil citrate (Viagra® 50 mg) and acetaminophen (Tylenol®) detection. The technique utilized for these analyses was differential pulse voltammetry (DPV) in 0.1 mol L-1 H2SO4 (pH 1.0) and 0.1 mol L-1 CH3COOK (pH 6.5) as supporting electrolyte. All analyses were carried out during a month using the same electrode. The electrode was washed only with water in between the analyses, keeping it in the refrigerator when it was not in use. This electrode was stable during the period utilized showing no degradation and presenting a linear response over the evaluated concentration interval (1.25 × 10-5 to 4.99 × 10-4 mol L-1).

A chemically modified electrode is constructed based on multi-walled carbon nanotube modified glassy carbon electrode (MWCNTs/GCE). It was demonstrated that this sensor could be easily used for determination of acetaminophen (ACT) in aqueous buffered media. The measurements were carried out by application of differential pulse voltammetry (DPV), cyclic voltammetry (CV) and chronoamperometry (CA) methods. Application of DPV method showed two linear dynamic ranges. The first linear dynamic range was from 0.1 to 22 µmol L-1, with a calibration equation of Ip(µA) = 1.2782c (µmol L-1) + 0.2431 (R² = 0.9984) and the second linear dynamic range was between 26 to 340 µmol L-1 with a calibration equation of Ip(µA) = 0.7793c (µmol L-1) + 11.615 (R² = 0.9986). A detection limit of 0.029 µmol L-1 (S/N = 3) was obtained. The modified electrode showed electrochemical responses with high sensitivity, excellent selectivity and stability for ACT determination at optimal conditions, which makes it a suitable sensor for submicromolar detection of ACT in solutions. The analytical performance of this sensor has been evaluated for detection of ACT in human serum, human urine and a pharmaceutical preparation with satisfactory results.