REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

MEASUREMENT OF CATALYTIC ACTIVITY VARIATION FOR H2O2 OXIDATION AT A COBALT PORPHYRIN COATED ELECTRODE

A rapid rotation-scan method was used for the electrocatalytic oxidation of H2O2 at a cobalt protoporphyrin modified pyrolytic graphite electrode (CoPP/PG). The rate constant of H2O2 oxidation at the CoPP/PG electrode at different potentials and in different pH solutions was measured. The variation of catalytic activity with reaction charges (Q) passed through the electrode was analyzed. This provided a convenient electrochemical method to study the passivation and poisoning of catalytic sites with time.

ELECTROCHEMICAL-BEHAVIOR OF HEXACYANOFERRATE(II) ON A GOLD ELECTRODE MODIFIED WITH BIS(4-PYRIDYL)DISULFIDE

The electrochemical behaviour of hexacyanoferrate(II) has been studied by using a bis(4-pyridyl)disulfide modified gold electrode. On the protonated electrode surface, hexacyanoferrate(II) can transfer an electron reversibly but no apparent adsorption was detected. On the deprotonated electrode surface, electron transfer by hexacyanoferrate(II) was more difficult. The electrochemical reversibility varied with the pH of the solution. Relationships between the currents or the standard heterogeneous rate constants and pH were derived.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

ELECTROCATALYTIC OXIDATION AND FLOW DETECTION OF HYDRAZINE COMPOUNDS IN LIQUID-CHROMATOGRAPHY AT A VITAMIN-B-12 ADSORBED GLASSY-CARBON ELECTRODE

A vitamin B-12 chemically modified electrode (CME) was constructed by adsorption of vitamin B-12 onto a glassy carbon surface. The electrode catalyzes the electrooxidation of hydrazine compounds over a wide pH range. The electrocatalytic behavior of hydrazines is elucidated with respect to the CME preparation conditions, solution pH, operating potential, mobile phase flow rate, and other variables. When applied to liquid chromatographic detection of the analytes, the vitamin B-12 CME yielded a linear response range over 2 orders of magnitude, and detection limits at the picomole level. The vitamin B-12 CME offers acceptable catalytic stability in both batch and flow systems.

A STUDY ABOUT PH CHEMICALLY MODIFIED ELECTRODES BASED ON AMINO-DERIVATIVES OF NAPHTHALENE

The electrochemical polymerization of amino-derivatives of naphthalene has been studied on the platinum wire electrodes. The effects of acidity of the modifying media and the potential scan rate on the cyclic voltammograms are verified. As potentiometric pH sensors, the electrodes prepared from 1-naphthylamine and 2,3-diaminonaphthalene showed performance characteristics superior to some other electrodes tested. The electrode modified with 1-naphthylamine in the optimum medium showed a nearly Nernstian response of 4.20-13.70 pH and a slope of -54.8 mV/pH, while the linear range of the electrode prepared by 2,3-diaminonaphthalene was 4.00-13.60 pH, with a slope of -52.4 mV/pH.

AMPEROMETRIC FLOW-INJECTION ANALYSIS OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION AT COBALT TETRAPHENYLPORPHYRIN MODIFIED ELECTRODE WITH HEAT-TREATMENT

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750-degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH3OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4-mu-g. The method is very sensitive and selective.

LIQUID-CHROMATOGRAPHY WITH ELECTROCATALYTIC DETECTION OF CYSTEINE, N-ACETYLCYSTEINE AND GLUTATHIONE BY A PRUSSIAN BLUE FILM-MODIFIED ELECTRODE

Chemically modified electrodes prepared by adsorbing prussian blue on a glassy carbon electrode are shown to catalyse the electro-oxidation of cysteine, N-acetylcysteine and glutathione in acidic media. The catalytic response is evaluated with respect to the potential scan rate, the solution pH, the concentration dependence, and other variables. Covering the electrode with Nafion(R) film improved the stability and reproducibility in liquid chromatography with electrochemical detection to the extent that repetitive sample injections produced relative standard deviations of less than 5% over several hours of operation. The limit of detection was 4 pmol for cysteine, 33 pmol for glutathione and 61 pmol for N-acetylcysteine.

ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON MODIFIED BY MACROCYCLIC TRANSITION-METAL COMPLEXES .1. COBALT PROTOPORPHYRIN DIMETHYL ESTER MODIFIED ELECTRODE

The electrocatalytic oxidation of hydrazine (N2H4) on a glassy carbon electrode (GC) modified by monolayer and polymer films of cobalt protoporphyrin dimethyl ester (CoPP) has been studied. Both the monolayer and polymer films of CoPP are very active to the anodic oxidation of N2H4. The activity of CoPP for the anodic oxidation of N2H4 is dependent on the pH of the solution, and the thickness of polymerized CoPP film. The oxidation kinetics were examined by methods of cyclic voltammetry, rotating disc electrodes and steady-state polarization measurement.

Transformation of Platymonas (Tetraselmis) subcordiformis (Prasinophyceae, Chlorophyta) by agitation with glass beads

A transient transformation system for the unicellular marine green alga, Platymonas subcordiformis, was established in this study. We introduced the pEGFP-N1 vector into P. subcordiformis with a glass bead method. P. subcordiformis was incubated in cell wall lytic enzymes (abalone acetone powder and cellulase solutions) to degrade the cell wall. The applicable conditions for production of viable protoplasts were pH 6.5, 25 degrees C, and 3 h of enzyme treatment. The protoplast yield was 61.2% when P. subcordiformis cells were added to the enzyme solution at a concentration of 10(7) cell ml(-1). The protoplasts were immediately transformed with the pEGFP-N1 vector using glass-bead method. The transformation frequency was about 10(-5), and there was no GFP activity observed in either the negative or the blank controls. This study indicated that GFP was a sensitively transgenic reporter for P. subcordiformis, and the method of cell wall enzymolysis followed by glass bead agitation was applicable for the transformation of P. subcordiformis.

Structural Evolution and Property Changes in Nd_{60}Al_{10}Fe_{20}Co_{10} Bulk Metallic Glass During Crystallization

The structural evolution and property changes in Nd60Al10Fe20Co10 bulk metallic glass (BMG) upon crystallization are investigated by the ultrasonic method, x-ray diffraction, density measurement, and differential scanning calorimetry. The elastic constants and Debye temperature of the BMG are obtained as a function of annealing temperature. Anomalous changes in ultrasonic velocities, elastic constants, and density are observed between 600–750 K, corresponding to the formation of metastable phases as an intermediate product in the crystallization process. The changes in acoustic velocities, elastic constants, density, and Debye temperature of the BMG relative to its fully crystallized state are much smaller, compared with those of other known BMGs, the differences being attributed to the microstructural feature of the BMG.

Stiffness behaviour of injection moulded short glass fibre/impact modifier/polypropylene hybrid composites

The stiffness behaviour of injection moulded short glass fibre/impact modifier/polypropylene hybrid composites has been investigated in this work by theoretical predictions and experiments. Predictions from the self-consistent method were found to be in good agreement with test results for the impact modifier/polypropylene blends. By taking into account of the fibre orientation distributions in the skin and core layers, the values of Young's modulus for the skin and core layers were predicted by employing Eshelby's equivalent inclusion method and the average induced strain approach. The prediction of the values of Young's modulus for the whole sample was obtained by applying the simple mixture theory of laminated composites to the predicted results for the skin and core layers. Good correlation between predicted and experimental Young's modulus values were found.

Anomalous Thermal Stability of Nd-Fe-Co-Al Bulk Metallic Glass

The thermal stability of Nd60Fe20Co10Al10 bulk metallic glass (BMG) has been studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), isochronal dilatation and compression tests. The results show that the glass transition of the BMG takes place quite gradually between about 460 and 650 K at a heating rate of 0.17 K/s. Several transformation processes are observed during continuous heating with the first crystallization process beginning at about 460 K, while massive crystallization takes place near the solidus temperature of the alloy. The positive heat of mixing between the two major constituents, Nd and Fe, and, consequently, a highly inhomogeneous composition of the attained amorphous phase are responsible for the anomalous thermal stability in this system. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Microstructure and Magnetic Properties of Nd60Al10Fe20Co10 Glass-forming Alloy

The microstructural variations of the Nd60Al10Fe20CO10 melt-spun ribbons and the as-cast rod were studied by high resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD) and differential scanning calorimetry. Nano-clusters in glassy m