On-line monitoring of electrochemical degradation of paracetamol through a biomimetic sensor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Molecular structures, electrochemical and spectroscopical properties of dichlorodicarbonylbis(tripenylphosphine)ruthenium(II) and dichlorodicarbonylbis(triphenylarsine)ruthenium(II)

The cct isomers [RuCl 2(CO) 2(PPh 3) 2] (1) and [RuCl 2(CO) 2(AsPh 3) 2] (2) were synthesized from [RuCl 3(PPh 3) 2DMA]DMA and [RuCl 3(AsPh 3) 2DMA]DMA, respectively. The complexes were characterized by elemental analysis, IR and UV-vis spectroscopy and their molecular structures were found to be cis-cis-trans isomers by X-ray crystallography. Cyclic voltammetry data show that the tripenylphosphine stabilizes better the ruthernium(II) complex than the tripenylarsine ligand. © 1994.

Electrochemical studies of copper, copper-aluminium and copper-aluminium-silver alloys: Impedance results in 0.5M NaCl

The electrochemical behaviour of Cu, Cu-Al and Cu-Al-Ag alloys in aqueous solutions of NaCl (0.5 M, pH = 3.00) was studied by means of voltammetric methods and electrochemical impedance spectroscopy. The surfaces were examined by SEM and EDX analysis. Cu-Al-Ag alloy shows a potentiodynamic behaviour similar to that of the pure copper electrode while the Cu-Al alloy presents some minor differences. In the active dissolution region the electrodes suffer pitting corrosion and in the other potential regions there are the formation of a passivant film with composition depending on the potential. The impedance responses of the electrodes are discussed. An electrodissolution mechanism is proposed and the effect of the alloying elements upon the impedance response and polarisation curves is explained. The main effects are due to the production of copper and silver chlorides and aluminium oxides/ hydroxides at the corroding interface. The addition of Al or (Al + Ag) increases the corrosion resistance of pure copper. © 1995.

Forensic electrochemistry: indirect electrochemical sensing of the components of the new psychoactive substance Synthacaine

Synthacaine is a New Psychoactive Substance which is, due to its inherent psychoactive properties, reported to imitate the effects of cocaine and is therefore consequently branded as legal cocaine. The only analytical approach reported to date for the sensing of Synthacaine is mass spectrometry. In this paper, we explore and evaluate a range of potential analytical techniques for its quantification and potential use in the field screening Synthacaine using Raman spectroscopy, presumptive (colour) testing, High Performance Liquid Chromatography (HPLC) and electrochemistry. HPLC analysis of street samples reveals that Synthacaine comprises a mixture of methiopropamine (MPA) and 2-aminoindane (2-AI). Raman spectroscopy and presumptive (colour) tests, the Marquis, Mandelin, Simon's and Robadope test, are evaluated towards a potential in-the-field screening approach but are found to not be able to discriminate between the two when they are both present in the same sample, as is the case in the real street samples. We report for the first time a novel indirect electrochemical protocol for the sensing of MPA and 2-AI which is independently validated in street samples with HPLC. This novel electrochemical approach based upon one-shot disposable cost effective screen-printed graphite macroelectrodes holds potential for in-the-field screening for Synthacaine.

Electrochemical investigation of the voltammetric determination of hydrochlorothiazide using a nickel hydroxide modified nickel electrode

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On the Limit of Frequency of Electrochemical Oscillators and Its Relationship to Kinetic Parameters

The class of electrochemical oscillators characterized by a partially hidden negative differential resistance in an N-shaped current potential curve encompasses a myriad of experimental examples. We present a comprehensive methodological analysis of the oscillation frequency of this class of systems and discuss its dependence on electrical and kinetic parameters. The analysis is developed from a skeleton ordinary differential equation model, and an equation for the oscillation frequency is obtained. Simulations are carried out for a model system, namely, the nickel electrodissolution, and the numerical results are confirmed by experimental data on this system. In addition, the treatment is further applied to the electro-oxidation of ethylene glycol where unusually large oscillation frequencies have been reported. Despite the distinct chemistry underlying the oscillatory dynamics of these systems, a very good agreement between experiments and theoretical predictions is observed. The application of the developed theory is suggested as an important step for primary kinetic characterization.

Quantification of terbinafine in pharmaceutical tablets using capillary electrophoresis with contactless conductivity detection and batch injection analysis with amperometric detection

Terbinafine hydrochloride (TerbHCl) is an allylamine derivative with fungicidal action, especially against dermatophytes. Different analytical methods have been reported for quantifying TerbHCl in different samples. These procedures require time-consuming sample preparation or expensive instrumentation. In this paper, electrochemical methods involving capillary electrophoresis with contactless conductivity detection, and amperometry associated with batch injection analysis, are described for the determination of TerbHCl in pharmaceutical products. In the capillary electrophoresis experiments, terbinafine was protonated and analyzed in the cationic form in less than 1 min. A linear range from 1.46 to 36.4 mu g mL(-1) in acetate buffer solution and a detection limit of 0.11 mu g mL(-1) were achieved. In the amperometric studies, terbinafine was oxidized at +0.85 V with high throughput (225 injection h(-1)) and good linear range (10-100 mu mol L-1). It was also possible to determine the antifungal agent using simultaneous conductometric and potentiometric titrations in the presence of 5% ethanol. The electrochemical methods were applied to the quantification of TerbHCl in different tablet samples; the results were comparable with values indicated by the manufacturer and those found using titrimetry according to the Pharmacopoeia. The electrochemical methods are simple, rapid and an appropriate alternative for quantifying this drug in real samples. (C) 2012 Elsevier B.V. All rights reserved.

Highly Sensitive Neurotransmitters Analysis at Platinum-Ultramicroelectrodes Arrays

An easy way to determine norepinephrine (NE) in biological fluid using a platinum ultramicroelectrode array (Pt-UMEAs) is described. Issues related to UME electrode surface treatment and characterizations are also addressed. At optimized experimental conditions the dynamic concentration range was 1.0 to 10.0 mu mol?L-1 with a detection limit of 40.5 nmol?L-1. The repeatability of current responses for injections of 5 mu mol?L-1 NE was evaluated to be 4.0?% (n=10). This approach obtained excellent sensitivity, a reliable calibration profile and stable electrochemical response for norepinephrine detection. The content of NE in urine samples without any preconcentration, purification, or pretreatment step, was successfully analyzed by the standard addition method using the Pt-UMEAs.

Electroluminescence and electric current response spectroscopy applied to the characterization of polymer light-emitting electrochemical cells

Frequency-dependent electroluminescence and electric current response spectroscopy were applied to polymeric light-emitting electrochemical cells in order to obtain information about the operation mechanism regimes of such devices. Three clearly distinct frequency regimes could be identified: a dielectric regime at high frequencies; an ionic transport regime, characterized by ionic drift and electronic diffusion; and an electrolytic regime, characterized by electronic injection from the electrodes and electrochemical doping of the conjugated polymer. From the analysis of the results, it was possible to evaluate parameters like the diffusion speed of electronic charge carriers in the active layer and the voltage drop necessary for operation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4752438]

Direct ethanol fuel cell: Electrochemical performance at 90 degrees C on Pt and PtSn/C electrocatalysts

Carbon-supported Pt-based electrocatalysts were synthesized by Pechini method for the ethanol oxidation (EOR). Physicochemical characterizations were helpful to estimate the diameters of the obtained materials ranging from 2 nm to 5 nm. Main electrochemical experiments were carried out at 90 degrees C i.e. under the working conditions of performing the single 5 cm(2) direct ethanol fuel cell (DEFC). Pt(80)Sn(20)/C was the anode catalyst which has given the highest power density of 37 mW cm(-2). Importantly, the IR spectroscopy measurements associated with the qualitative analysis done at the output of the anodic compartment of the fuel cell have shown that ethanol oxidation on Pt(80)Sn(20)/C was mainly a two-electron sustainable process. (C) 2011 Elsevier B.V. All rights reserved.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

Local electrochemical investigation of copper patina

The patination of copper is known for its complexity and heterogeneous formation. For a deeper investigation, a locally resolved surface analysis was considered. An exact determination of the accessed area and a potentiostatic control in a three-electrode configuration was reached with the use of the electrochemical microcell technique, which enables local electrochemical measurement such as local electrochemical impedance spectroscopy and cyclic voltammetry. Such a technique provides a unique way for performing the investigation of heterogeneities on electrode surfaces. The local electrochemical measurements on the artificially patinated surface have allowed distinguishing areas of different reactivity even when the analysis of the surface revealed a homogenous chemical composition of patina. Local measurements with the electrochemical microcell showed the presence of small defects on the patina layer that can be modelled by considering a hemispherical diffusion process at small active areas surrounded by larger less reactive domains.

Electrochemical sensing strategies for the detection of interactions between biological macromolecules

Electrochemical biosensors provide an attractive means to analyze the content of a biological sample due to the direct conversion of a biological event to an electronic signal, enabling the development of cheap, small, portable and simple devices, that allow multiplex and real-time detection. At the same time nanobiotechnology is drastically revolutionizing the biosensors development and different transduction strategies exploit concepts developed in these field to simplify the analysis operations for operators and end users, offering higher specificity, higher sensitivity, higher operational stability, integrated sample treatments and shorter analysis time. The aim of this PhD work has been the application of nanobiotechnological strategies to electrochemical biosensors for the detection of biological macromolecules. Specifically, one project was focused on the application of a DNA nanotechnology called hybridization chain reaction (HCR), to amplify the hybridization signal in an electrochemical DNA biosensor. Another project on which the research activity was focused concerns the development of an electrochemical biosensor based on a biological model membrane anchored to a solid surface (tBLM), for the recognition of interactions between the lipid membrane and different types of target molecules.

Development of a microgrid with renewable energy sources and electrochemical storage system integration

Beside the traditional paradigm of "centralized" power generation, a new concept of "distributed" generation is emerging, in which the same user becomes pro-sumer. During this transition, the Energy Storage Systems (ESS) can provide multiple services and features, which are necessary for a higher quality of the electrical system and for the optimization of non-programmable Renewable Energy Source (RES) power plants. A ESS prototype was designed, developed and integrated into a renewable energy production system in order to create a smart microgrid and consequently manage in an efficient and intelligent way the energy flow as a function of the power demand. The produced energy can be introduced into the grid, supplied to the load directly or stored in batteries. The microgrid is composed by a 7 kW wind turbine (WT) and a 17 kW photovoltaic (PV) plant are part of. The load is given by electrical utilities of a cheese factory. The ESS is composed by the following two subsystems, a Battery Energy Storage System (BESS) and a Power Control System (PCS). With the aim of sizing the ESS, a Remote Grid Analyzer (RGA) was designed, realized and connected to the wind turbine, photovoltaic plant and the switchboard. Afterwards, different electrochemical storage technologies were studied, and taking into account the load requirements present in the cheese factory, the most suitable solution was identified in the high temperatures salt Na-NiCl2 battery technology. The data acquisition from all electrical utilities provided a detailed load analysis, indicating the optimal storage size equal to a 30 kW battery system. Moreover a container was designed and realized to locate the BESS and PCS, meeting all the requirements and safety conditions. Furthermore, a smart control system was implemented in order to handle the different applications of the ESS, such as peak shaving or load levelling.