Electrochemical sensor based on multi-walled carbon nanotubes for imidacloprid determination.

A simple and robust sensor (fMWCNT-Nafion®0.5%/GCE) for determination of imidacloprid (IMI), a widely used neonicotinoid, was developed using a glassy carbon electrode (GCE) modified with functionalized multi-walled carbon nanotubes (fMWCNT) and Nafion®. The obtained data suggest that IMI reduction is an irreversible process, due to the reduction of the nitro group to hydroxylamine derivatives, with the participation of two protons and four electrons, and a charge transfer coefficient of 0.141. The optimized square-wave voltammetric conditions were: McIlvaine buffer at pH 6.0, 0.5% of Nafion® in the fMWCNT suspension, -0.6 V and 180 s as accumulation potential and time, respectively. A linearity in the range of 2.00 × 10-7 to 1.77 × 10-6 mol L-1 IMI, with the values of limit of detection and limit of quantification were equal to 3.74 × 10-8 mol L-1 and 1.25 × 10-7 mol L-1, respectively. Repeatability and reproducibility displayed relative standard deviations lower than 5%. Recovery tests performed in tap water, melon, and shrimp yielded mean values of 94 ± 6%, 97 ± 10% and 93 ± 10%, respectively. Moreover, several inorganic and organic compounds did not significantly interfere (0.6 to 4.5%) on the IMI signal, proving the selectivity and applicability of the developed sensor for IMI detection in complex samples.

Understanding the dipyrone oxidation allying electrochemical and computational approaches.

Electroanalytical methodology by boron-doped diamond electrode (BDDE) associated to the square-wave voltammetry (SWV) for the determination of hydrolyzed dipyrone (DIP) in commercial formulations, raw natural waters and in human urine was developed. Through cyclic voltammetry (CV), it was shown that the oxidation of the DIP on the BDDE was irreversible with diffusional control. Computational studies suggested that the oxidation mechanism of DIP occurred with participation of two electrons and one proton. The analytical curves were obtained for concentrations of DIP ranging from 1.0 × 10-6 to 6.5 × 10-5 mol L-1 (r = 0.9994). The values of detection limit (LOD) and quantification limit (LOQ) of DIP were calculated from SWV and found to be 2.6 × 10-7 mol L-1 and 8.8 × 10-7 mol L-1. The methodology was effectively applied to real samples with the values of calculated recoveries varying between 91.0% and 117.3% and validated by iodometric titration experiments whose values were between 93.3% and 106.9%. The proposed methodology with BDDE represents an alternative tool and it has advantageous, such as very easy handling, low cost, no need for modification, low detection limit. Furthermore, it can be used for the routine analysis of DIP in different real samples.

Chitosan-magnetite nanocomposite as a sensing platform to bendiocarb determination.

A novel platform for carbamate-based pesticide quantification using a chitosan/magnetic iron oxide (Chit-Fe3O4) nanocomposite as a glassy carbon electrode (GCE) modifier is shown for an analytical methodology for determination of bendiocarb (BND). The BND oxidation signal using GCE/Chit-Fe3O4 compared with bare GCE was catalyzed, showing a 37.5% of current increase with the peak potential towards less positive values, showing method's increased sensitivity and selectivity. Using square-wave voltammetry (SWV), calibration curves for BND determination were obtained (n = 3), and calculated detection and quantification limits values were 2.09 × 10-6 mol L-1 (466.99 ppb) and 6.97 × 10-6 mol L-1 (1555.91 ppb), respectively. The proposed electroanalytical methodology was successfully applied for BND quantification in natural raw waters without any sample pretreatment, proving that the GCE/Chit-Fe3O4 modified electrode showed great potential for BND determination in complex samples. ᅟ Graphical abstract.

Dispersion of multi-walled carbon nanotubes in [BMIM]PF6 for electrochemical sensing of acetaminophen.

The influence of functionalized multi-walled carbon nanotubes (fMWCNT) in the presence of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) in different ratios was investigated on the acetaminophen (ACOP) electrochemical determination. The electrochemical behavior of the ACOP exhibited a pair of well-defined redox peaks, suggesting that the reversibility of ACOP was significantly improved in comparison to irreversible oxidation peak on bare GCE. The redox process was controlled by adsorption, involves two electrons and the value of apparent rate constant (ks) was equal to 14.7 s-1 ±â€¯3.6 s-1. The analytical curves were obtained for concentrations of ACOP ranging from 0.3 to 3.0 µmol L-1. The values of the detection limit were calculated from SWV and found to be 6.73 × 10-8 mol L-1. The proposed electrochemical sensor exhibited good stability and reproducibility and was applied for ACOP determination in tablets (Tylenol® and Tylenol®DC) with satisfactory results.

Chemical modification of a nanocrystalline TiO2 film for efficient electric connection of glucose oxidase.

A novel biosensor for glucose was prepared by adsorption of 1,1'-bis(4-carboxybenzyl)-4,4'-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 micromol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 micromol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 microA mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose.