A study of Nafion-coated bismuth-film electrodes for the determination of trace metals by anodic stripping voltammetry

This work reports on the fabrication, characterization and applications of Nafion-coated bismuth-film electrodes (NCBFE's) for the determination of trace metals by anodic stripping voltammetry (ASV). A NCBFE was typically prepared by first applying a 5 microl drop of a 1% Nafion solution onto the surface of a glassy-carbon rotating-disk electrode. After evaporation of the solvent, the Bi film was plated on the electrode in situ(i.e. by spiking the sample with 1000 microg l(-1) of Bi(iii) and simultaneous electrolytic deposition of the metal ions and bismuth film on the electrode surface at -1.4 V) or ex-situ(i.e. by electrolytic deposition of the bismuth film in a separate solution containing 1000 microg l(-1) of Bi(iii), followed by the ASV measurement step in the sample solution). Various fabrication and operational parameters were thoroughly investigated and discussed in terms of their effect on the ASV signals. It was found that this voltammetric sensor was suitable for the determination of metals at trace levels by square-wave ASV (SWASV) due to its multi-element detection potential, improved analytical sensitivity, high resistance to surfactants, low cost, ease of fabrication, robustness, speed of analysis and low toxicity (as compared to traditional mercury electrodes). In the presence of 4 mg l(-1) of Triton X-100, the NCBFE afforded a 10-fold peak height enhancement for the Pb peak and a 14-fold enhancement for the Cd peak over a bare BFE while the determination of Zn was feasible only on the NCBFE. The limits of detection (at a signal-to-noise ratio of 3) were 0.1 microg l(-1) for Cd and Pb and 0.4 microg l(-1) for Zn for a deposition time of 10 min. Finally, the electrode was applied to different real samples (tap-water, urine and wine) for the analysis of trace metals with satisfactory results.     

Equilibrium customer strategies in a single server Markovian queue with setup times

We consider a single server Markovian queue with setup times. Whenever this system becomes empty, the server is turned off. Whenever a customer arrives to an empty system, the server begins an exponential setup time to start service again. We assume that arriving customers decide whether to enter the system or balk based on a natural reward-cost structure, which incorporates their desire for service as well as their unwillingness to wait. We examine customer behavior under various levels of information regarding the system state. Specifically, before making the decision, a customer may or may not know the state of the server and/or the number of present customers. We derive equilibrium strategies for the customers under the various levels of information and analyze the stationary behavior of the system under these strategies. We also illustrate further effects of the information level on the equilibrium behavior via numerical experiments.      

Speech changes following reimplantation from a single-channel to a multichannel cochlear implant.

The speech of a postlingually deafened preadolescent was recorded and analyzed while a single-electrode cochlear implant (3M/House) was in operation, on two occasions after it failed (1 day and 18 days) and on three occasions after stimulation of a multichannel cochlear implant (Nucleus 22) (1 day, 6 months, and 1 year). Listeners judged 3M/House tokens to be the most normal until the subject had one year's experience with the Nucleus device. Spectrograms showed less aspiration, better formant definition and longer final frication and closure duration post-Nucleus stimulation (6 MO. NUCLEUS and 1 YEAR NUCLEUS) relative to the 3M/House and no auditory feedback conditions. Acoustic measurements after loss of auditory feedback (1 DAY FAIL and 18 DAYS FAIL) indicated a constriction of vowel space. Appropriately higher fundamental frequency for stressed than unstressed syllables, an expansion of vowel space and improvement in some aspects of production of voicing, manner and place of articulation were noted one year post-Nucleus stimulation. Loss of auditory feedback results are related to the literature on the effects of postlingual deafness on speech. Nucleus and 3M/House effects on speech are discussed in terms of speech production studies of single-electrode and multichannel patients.     

Hole mobility in GeTe single crystals

The mobility of GeTe indicates anisotropic behaviour. The data based on a band structure compatible with the experimental rhombohedral C⁵_3y class, show scattering due to antistructure defects in the Te rich region, while scattering from neutral centers in the Ge side.     

Spin polarons in nickel sulphide

Using a random formulation of the Hubbard model developed by the authors, thermodynamic and electronic properties of antiferromagnetic nickel sulphide are considered. The transition mechanism is shown to be magnetic in origin and not due to phonons in the high temperature phase as has been accepted. The metallic-like properties of the magnetic phase originate from hole-like spin polarons for non-stoichiometric samples. We obtain good quantitative agreement assuming a leV Ni(3d) bandwidth and predict stoichiometric NiS to behave as an intrinsic semiconductor at low temperatures.     

Voltammetric Determination of Trace Heavy Metals by Sequential-injection Analysis at Plastic Fluidic Chips with Integrated Carbon Fiber-based Electrodes

This work describes a sequential injection analysis (SIA) method for on-line strippping voltammetric determination of Pb(II), Cd(II) and Zn(II) using an injection-moulded electrochemical fluidic chip consisting of 3 conductive carbon fiber-loaded polymer electrodes embedded in a plastic fluidic holder. The sample containing the target metals and a solution containing Bi(III) were aspirated in the holding coil of the SIA manifold. Then, the flow was reversed and the two solutions were directed to the fluidic cell through a mixing coil which induced mixing of the two zones. Upon reaching the cell, simultaneous reduction of the target metals and Bi(III) occurred resulting in the formation of a metal-Bi alloy on the working electrode. Finally, the accumulated metals were stripped off the bismuth-film electrode via a positive potential scan and the oxidation current was recorded. The experimental variables (concentration of the bismuth plating solution, deposition potential, sample volume, stripping mode) were investigated and the potential interferences were assessed. The limits of quantification were 2.8 μg L⁻¹ for Pb(II), 3.6 μg L⁻¹ for Cd(II) and 4.2 μg L⁻¹ for Zn(II) and the the within-chip and between-chip % relative standard deviations were ≤6.3 % and ≤14 %, respectively. Finally, the sensor was applied to the determination of trace metals in a fish food sample.     

Analysis of the heterogeneous dynamics of imidazolium-based [Tf2N−] ionic liquids using molecular simulation

The complex dynamic behaviour of the imidazolium-based ionic liquids [C_nmim⁺][Tf₂N^?], n = 4, 8, 12 is examined at various temperatures and at atmospheric pressure using molecular dynamics simulation. An existing all-atom force field is further optimised in order to attain reasonable agreement with experimental data for transport properties, such as self-diffusivities and viscosities. Dynamical heterogeneity phenomena are quantified through the calculation of the non-Gaussian parameter and the deviation of the self-part of the van Hove correlation function from the expected normal distribution. From this analysis, ions that move faster or slower than expected are detected in the system. These subsets of ‘fast’ and ‘slow’ ions form individual clusters consisting of either mobile or immobile ions. Detailed analysis of the ions’ diffusion reveals preferential motion along the direction of the alkyl tail for the cation and along the vector that connects the two sulphur atoms for the anion. For the longest alkyl tails, the heterogeneity in the dynamics becomes more pronounced and is preserved for several nanoseconds, especially at low temperatures.     

Numerical calculation of the DC conductance by the Kubo-Greenwood formula,in one dimensional disordered systems

The DC omhic conductance G of the Anderson model in one dimension is numerically calculated by two methods both starting from the Kubo-Greenwood formula. Results verify that only the geometric mean G? is an appropriate average and that 〈G〉 and〈1/〉 are not statistically meaningful quantities. It is shown that the Green's functions representation of the Kubo-Greenwood formula for G, is similar to the arithmetic average 〈G〉, and it does not contain information about localization.     

Localization and averaged Green's functions

We present a counterexample to the idea that localization in a random material can be determined from the ensemble averaged Green's function.