Detection of menadione sodium bisulfite (vitamin K-3) by reversed-phase high performance liquid chromatography with series dual-electrode amperometric detector

A reversed-phase high-performance liquid chromatography with series dual glassy carbon electrodes for the amperometric detection of water-soluble menadione is described. The complex post-column derivatization reaction and the high background currents were avoided. The menadione sodium bisulfite was reduced at -0.3 V vs. SCE at the upstream (generator) electrode and oxidized at +0.2V vs. SCE at the downstream (collector) electrode. The mobile phase was 0.2moll(-1) HAc-NaAc aqueous buffer (pH 5.50) and 40% (v/v) methanol. The linear response was in the range of 35 ng to 15 mu g, with a detection Limit of 15 ng (S/N=3). The correlation coefficient was 0.9997 (n=6). The electrochemical detection with series dual electrodes has a higher selectivity for menadione (vitamin K-3) compound than with UV detection.

AMPEROMETRIC DETECTION OF CATECHOLAMINES WITH LIQUID-CHROMATOGRAPHY AT A NOVELLY CONSTRUCTED PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

A novel technique for NACE coupled with simultaneous electrochemiluminescence and electrochemical detection for fast analysis of tertiary amines

A simultaneous electrochemiluminescence (ECL) and electrochemical (EC) detection scheme for NACE was presented for fast analysis of tertiary amines. Both ECL and EC signals were generated at the same Pt electrode. Triethylamine (TEA), tripropylamine (TPrA), chlorpromazine, promethazine, and dioxopromethazine (DPZ) were selected to validate NACE-ECL/EC dual detection strategy. The linear ranges for TEA and TPrA were 0.01-500 and 0.01-10 mu M with the detection limits of 8.0 and 5.0 nM (S/N=3), respectively. The RSDs (n = 6) of the migration time and the ECL intensity for 1 mu M TEA and 0.5 mu M TPrA were 0.1 and 2.8%, and 0.2 and 1.8% with theoretical plate numbers of 180 000 and 700 000 per meter, respectively. These two analytes could be separated within 92 s and the Pt electrode did not need reactivation during the experiments.

Progress in amperometric detection for capillary electrophoresis

As a high efficiency separation technique, capillary electrophoresis(CE) has been widely used in various fields of analytical science. Amperometry is one of the most sensitive electrochemical detection methods in CE. The capillary/electrode decoupling mechanism, applications,of new electrode systems in CE, detection cell technique are discussed in detail. Amperometric detection is compatible with microfabricated CE chips and will make the concept of lab-on-a-chip become a reality. Because of these progresses, amperometry is becoming a widely acceptable detection method,for more chemical and biological analytes.

Monitoring microbial sulfate reduction in porous media using multi-purpose electrodes

There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS-) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (s?) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes.

The Oxidation of Hydroxylamine on Gold Electrodes in Mildly Acidic Aqueous Electrolytes: Electrochemical and In Situ Differential Reflectance Studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge-discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g(-1) is obtained. When the acid-treated sample is heated at 300 A degrees C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g(-1). The rate capability study suggests that the sample provides about 150 mAh g(-1) at a specific discharge current of 1.25 A g(-1). Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.

Hierarchically porous Li1.2Mn0.6Ni0.2O2 as a high capacity and high rate capability positive electrode material

Layered composite samples of lithium-rich manganese oxide (Li1.2Mn0.6Ni0.2O2) are prepared by a reverse microemutsion route employing a soft polymer template and studied as a positive electrode material. The product samples possess dual porosity with distribution of pores at 3.5 and 60 nm. Pore volume and surface area decrease on increasing the temperature of preparation. Nevertheless, the electrochemical activity of the composite increases with an increase in temperature. The discharge capacity value of the samples prepared at 800 and 900 degrees C is about 240 mA h g(-1) at a specific current of 25 mA g(-1) with a good cycling stability. The composite sample heated at 900 degrees C possesses a high rate capability with a discharge capacity of 100 mA h g(-1) at a specific current of 500 mA g(-1). The high rate capability is attributed to porous nature of the composite sample.

Electrical/optical dual-function redox potential transistor

We demonstrate a new type of transistors, the electrical/optical "dual-function redox-potential transistors", which is solution processable and environmentally stable. This device consists of vertically staked electrodes that act as gate, emitter and collector. It can perform as a normal transistor, whilst one electrode which is sensitised by dye enables to generate photocurrent when illuminated. Solution processable oxide-nanoparticles were used to form various functional layers, which allow an electrolyte to penetrate through and, consequently, the current between emitter and collector can be controlled by the gate potential modulated distribution of ions. The result here shows that the device performs with high ON-current under low driving voltage (<1â€...V), while the transistor performance can readily be controlled by photo-illumination. Such device with combined optical and electrical functionalities allows single device to perform the tasks that are usually done by a circuit/system with multiple optical and electrical components, and it is promising for various applications.

Transient photocurrent investigation of photo-processes of lattice-matched MQW GaAs/AlxGa1-xAs electrode

Transient photocurrents induced by short light pulses at lattice-matched GaAs/AlxGa1-xAs multiple quantum well (MQW) electrodes were studied as a function of electrode potential. Dual exponential photocurrent decay transients were observed at various potentials. By analysis of the dual exponential decay transients, information on steady state photocurrents (I-s), surface collection of photoexcited minority carriers (G(0)) and lifetimes of surface states (T-s) was obtained. The kinetic behaviors of photoprocesses at illuminated MQW/electrolyte interface were discussed.