Polyphenol oxidase-based electrochemical biosensors: A review.

The detection of phenolic compounds is relevant not only for their possible benefits to human health but also for their role as chemical pollutants, including as endocrine disruptors. The required monitoring of such compounds on-site or in field analysis can be performed with electrochemical biosensors made with polyphenol oxidases (PPO). In this review, we describe biosensors containing the oxidases tyrosinase and laccase, in addition to crude extracts and tissues from plants as enzyme sources. From the survey in the literature, we found that significant advances to obtain sensitive, robust biosensors arise from the synergy reached with a diversity of nanomaterials employed in the matrix. These nanomaterials are mostly metallic nanoparticles and carbon nanostructures, which offer a suitable environment to preserve the activity of the enzymes and enhance electron transport. Besides presenting a summary of contributions to electrochemical biosensors containing PPOs in the last five years, we discuss the trends and challenges to take these biosensors to the market, especially for biomedical applications.

One material, multiple functions: graphene/Ni(OH)2 thin films applied in batteries, electrochromism and sensors.

Different nanocomposites between reduced graphene oxide (rGO) and Ni(OH)2 nanoparticles were synthesized through modifications in the polyol method (starting from graphene oxide (GO) dispersion in ethylene glycol and nickel acetate), processed as thin films through the liquid-liquid interfacial route, homogeneously deposited over transparent electrodes and spectroscopically, microscopically and electrochemically characterized. The thin and transparent nanocomposite films (112 to 513 nm thickness, 62.6 to 19.9% transmittance at 550 nm) consist of α-Ni(OH)2 nanoparticles (mean diameter of 4.9 nm) homogeneously decorating the rGO sheets. As a control sample, neat Ni(OH)2 was prepared in the same way, consisting of porous nanoparticles with diameter ranging from 30 to 80 nm. The nanocomposite thin films present multifunctionality and they were applied as electrodes to alkaline batteries, as electrochromic material and as active component to electrochemical sensor to glycerol. In all the cases the nanocomposite films presented better performances when compared to the neat Ni(OH)2 nanoparticles, showing energy and power of 43.7 W h kg-1 and 4.8 kW kg-1 (8.24 A g-1) respectively, electrochromic efficiency reaching 70 cm2 C-1 and limit of detection as low as 15.4 ± 1.2 µmol L-1.

Nickel nanoparticles with hcp structure: Preparation, deposition as thin films and application as electrochemical sensor.

Hexagonal close packed (hcp) nickel nanoparticles stabilized by polyvinylpyrrolidone (PVP) were synthesized through the thermal treatment of face centered cubic (fcc) nickel nanoparticles. Controlling both the temperature of the heat treatment and the amount of PVP was possible the control of the hcp/fcc rate in the samples, where the higher Ni/PVP ratio produces only the hcp-nickel phase (average size of 8.9 nm) highly stable in air. The crystalline structure, the presence of PVP, the size of the nanoparticles and the stability of the hcp-nickel were confirmed using X-ray diffractometry, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy, scanning electron microscopy and thermogravimetric analysis. Thin films of hcp and fcc nickel nanoparticles were prepared through a biphasic system and deposited over indium-doped tin oxide (ITO) substrates, which were electrochemically characterized and applied as glycerol amperometric sensors in NaOH medium. Parameters as the number of cycles applied and the scan rate were evaluated and indicate that hcp nickel nanoparticles are more reactive to form Ni(OH)2 and lead to more electroactive Ni(OH)2 structure. The hcp nickel nanoparticles-modified electrode showed the best sensitivity (0.258 µA L µmol(-1)) and detection limit (2.4 µmol L(-1)) toward glycerol.

Potentiometric determination of pantoprazole using an ion-selective sensor based on polypyrrole doped films.

The present work reports for the first time the use of polypyrrole (PPy) doped film for development of a potentiometric disposable sensor for determination of pantoprazole (PTZ), a drug used for ulcer treatment. Selective potentiometric response has been found by using a membrane of PPy doped with PTZ anions prepared under galvanostatic conditions at graphite pencil electrode (GPEM/PPy-PTZ) surface. Potentiometric response has been influenced for conditions adopted in polymerization and measurement step. After optimization of experimental (e.g. pH and time of conditioning) and instrumental parameters (e.g. current density and electrical charge) a linear analytical curve from 1.0 × 10(-5) to 1.1 × 10(-2) mol L(-1) with a slope of calibration of the 57.6 mV dec(-1) and limit of detection (LOD) of 6.9 × 10(-6) mol L(-1) was obtained. The determination of the PTZ content in pharmaceutical samples using the proposed methodology and official method recommended by Brazilian Pharmacopeia are in agreement at the 95% confidence level and within an acceptable range of error.

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex.

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L(-1) of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s(-1). A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9×10(-5) to 1.0×10(-3) mol L(-1), with a detection limit of 6.6×10(-5) mol L(-1) using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations.

An improved flow system for chloride determination in natural waters exploiting solid-phase reactor and long pathlength spectrophotometry.

A single and sensitive spectrophotometric method for chloride ions determination based on a commuted flow system with a 100cm optical path flow cell and a solid-phase reactor containing immobilized silver chloranilate was proposed. This procedure exploited the AgCl formation in the solid-phase reactor leading the chloranilate ions, monitored spectrophotometrically at 530nm. The analytical signals were 75-fold higher and the sensitivity was 12-fold than that achieved with a 1cm flow cell, allowed a chloride determination in the 0.5-100mgl(-1) range. The R.S.D. was 1.1% (n=20) with a sample throughput of 80h(-1) and a waste generated of ca. 100ng of chloranilate ions per determination. Four samples of natural waters from São Carlos and Araraquara cities were evaluated using the proposed method. Results agreed with the obtained by a reference method at the 95% confidence level.