Electrocatalytic oxidation of methanol at the titanium oxide electrode modified with Pt microparticles

The electrocatalytic oxidation of methanol at the Titanium oxide (TiOx, x<2) film modified with Pt microparticles has been studied. The results show that the modified electrodes exhibit a significant electrocatalytic activity and good stability for the oxidation of methanol. Under the optimal conditions, the peak current density at 0.58 V for the oxidation of methanol in the positive-going sweep is about 526 mA/cm(2) at the scan rate of 5 mV/s in 0.5 mol/L CH3OH and 0.5 mol/L H2SO4 solution and the over potential of the methanol oxidation at the modified electrode increases about 30 similar to 40 mV after 70 minutes at the current density of 100 mA/cm(2) and 50 mA/cm(2). The enhanced electrocatalytic activity and good stability are ascribed to the high dispersion of Pt microparticles in and on the TiOx film and the synergistic effect between Pt microparticles and TiOx.

Permselectivity of 4-aminophenol, paracetanol and phenacetin on the self-assembled n-alkanethiol monolayer modified gold electrode

The gold electrodes coated by n-alkanethiol with various chain lengths were used to study the permeability of uric acid, ascorbic acid, 4-aminophenol, paracetanol and phenacetin by means of linear sweep voltammetry. The results show that the optimum chain length is n=10. The improvements in the selectivity and the stability of the amperometric detection of these compounds in a flow stream were obtained by n-alkanethiol self assembled monolayers modified electrodes based on their differences in the hydrophobicity and the permeability.

INFLUENCE ON THE THIN-LAYER SPECTROELECTROCHEMISTRY - DIFFUSION WITHIN A THIN-LAYER CELL

The potential step and cyclic voltammetric experiments in the thin layer cell were studied by the digital simulation method in this work. A relationship between the time needed for exhaustive electrolysis of the electroactive species and the thickness of the thin layer cell was obtained. On the basis of this formula, the lower time limit for a kinetic plot of the following chemical reaction can be estimated. For the cyclic voltammetry, a semiempirical formula was derived for the peak-peak potential difference (Delta Ep) in terms of the sweep rate (v), thickness of the cell (d), diffusion coefficient (D) and electron transfer number (n) 59 - n Delta Ep/n Delta Ep = 0.328(RT D/nF vd(2))(1.20).

ELECTROCATALYTIC OXIDATION OF REDUCED NICOTINAMIDE COENZYMES AT ORGANIC DYE-MODIFIED ELECTRODES

Chemically modified electrodes (CMEs) were prepared by adsorbing different dyes, including methylene blue (MB), toluidine blue (TB) and brilliant cresyl blue (BCB), onto glassy carbon electrodes (GCE) with anodic pretreatment. The electrochemical reactions of adsorbed dyes are fairly reversible at low coverages. The CMEs are more stable in acid solutions than in alkaline ones, which is mainly due to decomposition of the dyes in the latter media. They exhibit an excellent catalytic ability for the oxidation of nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between the coenzyme and the adsorbed mediator has been demonstrated using a rotating disk electrode. The charge transfer complex decomposition is a slow step in the overall electrode reaction process. Some kinetic parameters are estimated. Dependence of the electrocatalytic activity of the CMEs on the solution pH is discussed.

POLYANILINE-DISPERSED MERCURY-ELECTRODE FOR THE DETECTION OF MONOCHLORAMINE AND DICHLORAMINE

A novel type of electrochemical detector based on a polyaniline-dispersed mercury-coated glassy carbon chemically modified electrode was investigated for the detection of monochloramine and dichloramine. A polyaniline dispersed-mercury modified electrode, which was prepared by coating polyaniline on a thin mercury film electrode using fast-sweep voltammetry, was developed. The selectivity could be altered using various counter ions incorporated into the polymer. The results indicated that the use of a conducting polymer-based electrochemical sensor for the selective determination of chloramine is a feasible approach.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATES AND HETEROPOLY-OXOMETALLATES FILM MODIFIED MICROELECTRODES .3. FURTHER STUDY OF ELECTRODE PROCESS OF ISOPOLYMOLYBDIC ANION DOPED IN POLYANILINE FILM

The isopolymolybdic anion-polyaniline film modified carbon fiber (CF) microelectrode with high stability and electroactivity in aqueous acid solution has been successfully prepared by cycling the potential between -0.15 V and +0.85 V vs. sce at 100 mV s-1 or applying constant potential (+0.85 V) for electropolymerization in a 0.5 M H2SO4 solution containing 5.0 x 10(-2) M aniline and 5.0 x 10(-3) M H4Mo8O26. The electrochemical behaviour of the isopolymolybdic anion entrapped in the polyaniline film is strongly influenced by the sweep-potential range besides the acidity of electrolyte solution. In some acidic electrolyte solution (eg 0.5 M H2SO4), the change of the sweep-potential range causes the structure alternation of the isopolymolybdic anion and resulting in a new electrode process. The cyclic voltammogram of Mo8O264- in 0.5 M H2SO4 solution exhibits three two-electron reversible waves between +0.70 and -0.20 V. However, when the potential sweeps to the lower-limit of -0.3 V, where the fourth four-electron cathodic wave appears, the redoxidation process of the reduction product of Mo8O264- becomes relatively complicated. The 10-electron reduction product seems to change into other isopolyanion (this unknown structure isopolyanions are simply called [Mo-O]), which can be reoxidized to Mo8O264- by five successive two-electron oxidation steps from -0.30 to +0.70 V. However, when the lower-limit of the cycling potential is maintained at -0.30 V and the upper-limit reduces to +0.40 V from +0.70 V, the [Mo-O] in the film exhibits four two-electron reversible waves. We have presented a novel explanation about its electrode reaction mechanism on the basis of our experimental results.

CATALYTIC REDUCTION OF HEMOGLOBIN AT THIONINE CHEMICALLY MODIFIED ELECTRODE AND FIA APPLICATIONS

Thionine-containing chemically modified electrode (cme) was constructed with glassy carbon substrate by potential sweep oxidation, electrodeposition and adsorption procedures, and electrocatalytic reduction of hemoglobin was carried out and characterized at the cme under batch and flow conditions. Comparison of the catalytic response toward hemoglobir obtained at the cme was made mainly in terms of the potential dependence, the detectability and long-term stability. When used in flow injection analysis (FIA) experiments with the detector monitored at a constant potential applied at -0.35 V vs sce, detection limit of 0.15-1.5 pmol level of hemoglobin injected was achieved at the cme, with linear response range over 2 orders of magnitude. All the cme s retained more than 70% of their initial hemoglobin response level over 8 h of continuous service in the flow-through system.

DIRECT ELECTRON-TRANSFER REACTION OF HEMEPROTEINS PROMOTED BY METHYLENE-BLUE MODIFIED ELECTRODE

The heterogeneous electron transfer reaction of hemeproteins including hemoglobin, myoglobin and cytochrome C at Pt mesh electrode adsorbed methylene blue has been investigated. Thin-layer spectroelectrochemical technique was used for observing the electron transfer processes of three kinds of proteins, and the corresponding electrode rate constants were measured.

The Bifurcation Interpreter: A Step Towards the Automatic Analysis of Dynamical Systems

The Bifurcation Interpreter is a computer program that autonomously explores the steady-state orbits of one-parameter families of periodically- driven oscillators. To report its findings, the Interpreter generates schematic diagrams and English text descriptions similar to those appearing in the science and engineering research literature. Given a system of equations as input, the Interpreter uses symbolic algebra to automatically generate numerical procedures that simulate the system. The Interpreter incorporates knowledge about dynamical systems theory, which it uses to guide the simulations, to interpret the results, and to minimize the effects of numerical error.

Multistep Methods for Integrating the Solar System

High order multistep methods, run at constant stepsize, are very effective for integrating the Newtonian solar system for extended periods of time. I have studied the stability and error growth of these methods when applied to harmonic oscillators and two-body systems like the Sun-Jupiter pair. I have also tried to design better multistep integrators than the traditional Stormer and Cowell methods, and I have found a few interesting ones.

Theory of Handwriting

Handwriting production is viewed as a constrained modulation of an underlying oscillatory process. Coupled oscillations in horizontal and vertical directions produce letter forms, and when superimposed on a rightward constant velocity horizontal sweep result in spatially separated letters. Modulation of the vertical oscillation is responsible for control of letter height, either through altering the frequency or altering the acceleration amplitude. Modulation of the horizontal oscillation is responsible for control of corner shape through altering phase or amplitude. The vertical velocity zero crossing in the velocity space diagram is important from the standpoint of control. Changing the horizontal velocity value at this zero crossing controls corner shape, and such changes can be effected through modifying the horizontal oscillation amplitude and phase. Changing the slope at this zero crossing controls writing slant; this slope depends on the horizontal and vertical velocity zero amplitudes and on the relative phase difference. Letter height modulation is also best applied at the vertical velocity zero crossing to preserve an even baseline. The corner shape and slant constraints completely determine the amplitude and phase relations between the two oscillations. Under these constraints interletter separation is not an independent parameter. This theory applies generally to a number of acceleration oscillation patterns such as sinusoidal, rectangular and trapezoidal oscillations. The oscillation theory also provides an explanation for how handwriting might degenerate with speed. An implementation of the theory in the context of the spring muscle model is developed. Here sinusoidal oscillations arise from a purely mechanical sources; orthogonal antagonistic spring pairs generate particular cycloids depending on the initial conditions. Modulating between cycloids can be achieved by changing the spring zero settings at the appropriate times. Frequency can be modulated either by shifting between coactivation and alternating activation of the antagonistic springs or by presuming variable spring constant springs. An acceleration and position measuring apparatus was developed for measurements of human handwriting. Measurements of human writing are consistent with the oscillation theory. It is shown that the minimum energy movement for the spring muscle is bang-coast-bang. For certain parameter values a singular arc solution can be shown to be minimizing. Experimental measurements however indicate that handwriting is not a minimum energy movement.

Sparsely Faceted Arrays: A Mechanism Supporting Parallel Allocation, Communication, and Garbage Collection

Conventional parallel computer architectures do not provide support for non-uniformly distributed objects. In this thesis, I introduce sparsely faceted arrays (SFAs), a new low-level mechanism for naming regions of memory, or facets, on different processors in a distributed, shared memory parallel processing system. Sparsely faceted arrays address the disconnect between the global distributed arrays provided by conventional architectures (e.g. the Cray T3 series), and the requirements of high-level parallel programming methods that wish to use objects that are distributed over only a subset of processing elements. A sparsely faceted array names a virtual globally-distributed array, but actual facets are lazily allocated. By providing simple semantics and making efficient use of memory, SFAs enable efficient implementation of a variety of non-uniformly distributed data structures and related algorithms. I present example applications which use SFAs, and describe and evaluate simple hardware mechanisms for implementing SFAs. Keeping track of which nodes have allocated facets for a particular SFA is an important task that suggests the need for automatic memory management, including garbage collection. To address this need, I first argue that conventional tracing techniques such as mark/sweep and copying GC are inherently unscalable in parallel systems. I then present a parallel memory-management strategy, based on reference-counting, that is capable of garbage collecting sparsely faceted arrays. I also discuss opportunities for hardware support of this garbage collection strategy. I have implemented a high-level hardware/OS simulator featuring hardware support for sparsely faceted arrays and automatic garbage collection. I describe the simulator and outline a few of the numerous details associated with a "real" implementation of SFAs and SFA-aware garbage collection. Simulation results are used throughout this thesis in the evaluation of hardware support mechanisms.

Calculation of the multimode Franck-Condon factors based on the coherent state method

The equivalence of two ways for the calculation of overlap integrals, i.e. the Sharp Rosenstock generating function method and the Doktorov coherent state method, has been proved. On the basis of the generating function of the overlap integrals, a new closed form expression for the Franck - Condon integrals for overlap multidimensional harmonic oscillators has been exactly derived. In addition, some useful analytical expressions for the calculations of the multimode Franck - Condon factors have been given.

Synchronized Oscillations During Cooperative Feature Linking in a Cortical Model of Visual Perception

A neural network model of synchronized oscillator activity in visual cortex is presented in order to account for recent neurophysiological findings that such synchronization may reflect global properties of the stimulus. In these recent experiments, it was reported that synchronization of oscillatory firing responses to moving bar stimuli occurred not only for nearby neurons, but also occurred between neurons separated by several cortical columns (several mm of cortex) when these neurons shared some receptive field preferences specific to the stimuli. These results were obtained not only for single bar stimuli but also across two disconnected, but colinear, bars moving in the same direction. Our model and computer simulations obtain these synchrony results across both single and double bar stimuli. For the double bar case, synchronous oscillations are induced in the region between the bars, but no oscillations are induced in the regions beyond the stimuli. These results were achieved with cellular units that exhibit limit cycle oscillations for a robust range of input values, but which approach an equilibrium state when undriven. Single and double bar synchronization of these oscillators was achieved by different, but formally related, models of preattentive visual boundary segmentation and attentive visual object recognition, as well as nearest-neighbor and randomly coupled models. In preattentive visual segmentation, synchronous oscillations may reflect the binding of local feature detectors into a globally coherent grouping. In object recognition, synchronous oscillations may occur during an attentive resonant state that triggers new learning. These modelling results support earlier theoretical predictions of synchronous visual cortical oscillations and demonstrate the robustness of the mechanisms capable of generating synchrony.

Creation of a complex butterfly attractor using a novel Lorenz-type system

A novel Lorenz-type system of nonlinear differential equations is proposed. Unlike the original Lorenz system, where the chaotic dynamics remain confined to the positive half-space with respect to the Z state variable due to a limiting threshold effect, the proposed system enables bipolar swing of this state variable. In addition, the classical set of parameters (a, b, c) controlling the behavior of the Lorenz system are reduced to a single parameter, namely a. Two possible modes of operation are admitted by the system; switching between these two modes results in the creation of a complex butterfly chaotic attractor. Numerical simulations and results from an experimental setup are presented