Laser-activated voltammetry: measurement of the diffusion coefficients of electropassivating species. Application to pyrrole and phenol in aqueous solution

Clean electrode surfaces can be achieved during the electrolysis of otherwise passivating species in aqueous and other solutions by means of surface ablation using a 10-Hz pulsed Nd:YAG 532-nm laser. This ability to remove passivating electrolytically generated layers on glassy carbon and platinum electrodes is shown first by an investigation of the stripping peaks formed from the electrogeneration of the neutral forms of methyl viologen and heptyl viologen during reduction in aqueous solution of dications. Next, laser ablation was conducted under well-defined hydrodynamic conditions using a channel flow cell to identify laser power thresholds below which transport-limited currents could be seen, which were in quantitative agreement with those expected in the absence of irradiation. Levich plots recorded in the channel flow cell for K4Fe(CN)6 at glassy carbon and platinum electrodes showed such agreement for laser intensities lower than 0.17 and 0.65 W cm(-2), respectively. Working at intensities below these thresholds, steady-state voltammetry was observed for the oxidation of both phenol and pyrrole at glassy carbon and platinum electrodes, respectively, in aqueous solution. The diffusion coefficients of these two species were then measured under hydrodynamic conditions using laser ablation voltammetry to continuously clean the surface. Diffusion coefficients were inferred using the Levich equation. The result for phenol at a pH of 12 in aqueous solution was 0.9 (+/-0.1) x 10(-5) cm2 s(-1), which is in good agreement with an independent nonelectrochemical method. The diffusion coefficient of pyrrole in aqueous solution was similarly evaluated as 1.25 (+/-0.1) x 10(-5) cm2 s(-1).     

Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes

A novel method for the detection of arsenic(III) in 1 M HCl at a gold nanoparticle-modified glassy carbon electrode has been developed. The gold nanoparticles were electrodeposited onto the glassy carbon electrode via a potential step from +1.055 to -0.045 V vs SCE for 15 s from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with both AFM and cyclic voltammetry. Anodic stripping voltammetry of arsenic(III) on the modified electrode was performed. After optimization, a LOD of 0.0096 ppb was obtained with LSV.     

Investigation of crystallization and amorphization dynamics of phase-change thin films by subnanosecond laser pulses

We report experimental results on amorphization and crystallization dynamics of reversible phase-change (PC) thin-film samples, GeSbTe and GeBiTe, for optical disk data storage. The investigation was conducted with subnanosecond laser pulses using a pump-and-probe configuration. Amorphization of the crystalline films could be achieved with a single subnanosecond laser pulse; the amorphization dynamics follow closely the temperature kinetics induced in the irradiated spot. As for crystallization of the samples initially in the amorphous state, a single subnanosecond pulse was found to be insufficient to fully crystallize the irradiated spot, but we could crystallize the PC film (in the area under the focused spot) by applying multiple short pulses. Our multipulse studies reveal that the GeSbTe crystallization is dominated by the growth of nuclei whose initial formation is slow but, once formed, their subsequent growth (under a sequence of subnanosecond pulses) happens quickly. In the case of GeBiTe samples, the crystalline nuclei appear to be present in the material initially, as they grow immediately upon illumination with laser pulses. Whereas our amorphous GeSbTe samples required approximately 200 pulses for full crystallization, for the GeBiTe samples approximately 15 pulses sufficed.     

Development of a method for total inorganic arsenic analysis using anodic stripping voltammetry and a Au-coated, diamond thin-film electrode

We demonstrate that a Au-coated, boron-doped, diamond thin-film electrode provides a sensitive, reproducible, and stable response for total inorganic arsenic (As(III) and As(V)) using differential pulse anodic stripping voltammetry (DPASV). As is preconcentrated with Au on the diamond surface during the deposition step and detected oxidatively during the stripping step. Au deposition was uniform over the electrode surface with a nominal particle size of 23 +/- 5 nm and a particle density of 109 cm-2. The electrode and method were used to measure the As(III) concentration in standard and river water samples. The detection figures of merit were compared with those obtained using conventional Au-coated glassy carbon and Au foil electrodes. The method was also used to determine the As(V) concentration in standard solutions after first being chemically reduced to As(III) with Na2SO3, followed by the normal DPASV determination of As(III). Sharp and symmetric stripping peaks were generally observed for the Au-coated diamond electrode. LODs were 0.005 ppb (S/N = 3) for As(III) and 0.08 ppb (S/N = 3) for As(V) in standard solutions. An As(III) concentration of 0.6 ppb was found in local river water. The relative standard deviation of the As stripping peak current for river water was 1.5% for 10 consecutive measurements and was less than 9.1% over a 10-h period. Excellent electrode response stability was observed even in the presence of up to 5 ppm of added humic acid. In summary, the Au-coated diamond electrode exhibited better performance for total inorganic As analysis than did Au-coated glassy carbon or Au foil electrodes. Clearly, the substrate on which the Au is supported influences the detection figures of merit.     

Electrochemical study of reversible hydrogenase reaction of Desulfovibrio vulgaris cells with methyl viologen as an electron carrier.

An electrode modified with immobilized whole cells of Desulfovibrio vulgaris (Hildenborough) produces an S-shaped voltammogram with both cathodic- and anodic-catalytic-limiting currents in a methyl viologen-containing buffer saturated with H2. Methyl viologen penetrates into the bacterial cells to serve as an electron carrier in the reversible reaction of hydrogenase in the cells and functions as an electron-transfer mediator between the bacterial cells and the electrode, thus producing the catalytic currents for the evolution and consumption of H2. An equation for the catalytic current that takes into account the reversible hydrogenase reaction explains well the shape of the voltammogram. The potential at null current on the voltammogram agrees with the potential determined by potentiometry with the same electrode, which is equal to the redox potential of the H+/H2 couple in the solution--the standard potential of a hydrogen electrode at the pH of the solution. When D. vulgaris cells are suspended in an argon-saturated buffer containing methyl viologen, the suspension produces a catalytic current at a bare glassy carbon electrode for the evolution of H2. Analysis of the current by a theory for a catalytic current for a unidirectional nonlinear enzyme catalysis allows us to determine the kinetic parameters of the reaction between methyl viologen and hydrogenase in intact D. vulgaris cells. Thus we obtain the apparent Michaelis constant for methyl viologen cation radical, K'MV.+ = 0.16 mM, and the apparent catalytic constant (that is, the turnover number per D. vulgaris cell), zkcat,H+ = 1.2 x 10(7) s-1, for the H2 evolution reaction at pH 5.5 and at 25 degrees C, z being the number of hydrogenases contained in a D. vulgaris cell. The bimolecular reaction rate constant, kcat,H+/K'MV.+, of the reaction between methyl viologen cation radical and oxidized hydrogenase in intact D. vulgaris cells is estimated as 4.2 x 10(7) M-1 s-1. Similarly, the bimolecular reaction rate constant, kcat,H2/K'MV2+, of the reaction between methyl viologen and reduced hydrogenase is estimated to be 1.2 x 10(7) M-1 s-1 at pH 9.5 and 25 degrees C. Both rate constants are large enough for the reactions to be diffusion-limited processes.     

Reaction orders of Decomposition of Anhydrous Amorphates

Solids can occur either as crystalline or as (particulate) amorphates. The chemical stability of the solid in crystalline form will differ from the same entity in amorphous form. The amorphous form, furthermore, may be above or below a glass transition temperature, T_g (glassy below and rubbery above T_g), and it is shown in the following that a simple rubbery amorphate should decompose by first order and the rate constants should adhere to an Arrhenius relationship with an activation energy which is the difference between ground state and excited state energies. Indomethacin has been used as a model compound.     

A glucose sensor made of an enzymatic clay-modified electrode and methyl viologen mediator

A novel glucose sensor has been contrived by immobilizing glucose oxidase between two nontronite clay coatings on glassy carbon electrode with methyl viologen as mediator. The sandwich configuration proved to be very effective in the determination of glucose. The response of the glucose sensor was determined by measuring cyclic voltammetric peak current values under aerobic solution conditions. The effects of the amount of enzyme immobilized, the operating pH, and the common interferences on the response of the glucose sensor were studied. The detection limit was 5 μM, with a linear range extending to about 6 mM, giving a dynamic range of over 3 orders of magnitude for 0.1 mM methyl viologen. When stored in pH 7 phosphate buffer at 4 °C, the sensor shows almost no change in performance after operating for at least 2 months. A mechanism for the operation of the glucose sensor is also proposed.     

玻碳电极上核黄素的电化学行为研究

用循环伏安法和线性扫描伏安法探讨核黄素在玻碳电极上的电化学行为。在多种缓冲液中测试,发现HAe—NaAe作为缓冲液时电化学氧化还原峰形最好,峰电流较大,电化学过程表现出良好的可逆性,电子转移数n为2,扩散系数D0为2．3×10^-5cm^2·s^-1;改变缓冲液的pH值,峰电流随pH值增大而负移,说明其在电极表面有吸附作用;光照后核黄素在-0．35V和-0．45V附近出现两个还原峰;分析实验数据可得,在1．0×10^-4mol/L数量级时还原峰峰电流与其浓度呈现良好的线性关系。     

Preconcentration and Voltammetric Determination of Mercury(II) at a Chemically Modified Glassy Carbon Electrode

In this work, the organic compound 2-mercaptobenzimidazole was covalently bound on the surface of a glassy carbon rod, via silanization, yielding a material capable of selectively complexing Hg(2+) ions. This material was applied as an electrode for voltammetric determination of mercury(II) following its nonelectrolytic preconcentration. After exchanging the medium, the voltammetric measurements were carried out by anodic stripping in the differential pulse mode (pulse amplitude, 50 mV; scan rate, 1.25 mV s(-)(1)) using 10(-)(2) mol L(-)(1) NaSCN solution as supporting electrolyte. An anodic stripping peak was obtained at 0.06 V (vs SCE) by scanning the potential from -0.3 to +0.3 V. After a 5 min preconcentration period in a pH 4.0 Hg(2+) solution, this electrode shows increasing voltammetric response in the range 0.1-2.2 μg mL(-)(1), with a relative standard deviation of 5% and a practical detection limit of 0.1 μg mL(-)(1) (5.0 × 10(-)(7) mol dm(-)(3)). Compared with the conventional stripping approach, this chemically modified glassy carbon electrode procedure presented good discrimination against interference from Cu(II) in up to 10-fold molar excess.     

X-ray diffraction studies on the relative proportion and decomposition of amorphous phase in electroless NiB deposits

Electroless nickel-boron deposits with 2.34, 3.85 and 4.32 wt.% boron were produced on mild steel substrates. The deposits had a structure consisting of a mixture of microcrystalline nickel and amorphous NiB phases in the as deposited condition. From the ratios of the integrated intensities of the X-ray diffraction profiles of amorphous and crystalline phases, the relative proportion of the two phases was estimated. The quantity of amorphous phase increased with increasing boron content. The amorphous phase decomposed in one single step as Ni+Ni₃B at around 523K. There are indications that boron might be diffusing out of the crystalline phase into the amorphous phase just prior to the decomposition of the amorphous phase.     

Reaction orders of Decomposition of Anhydrous Amorphates

Abstract

Solids can occur either as crystalline or as (particulate) amorphates. The chemical stability of the solid in crystalline form will differ from the same entity in amorphous form. The amorphous form, furthermore, may be above or below a glass transition temperature, T_g (glassy below and rubbery above T_g), and it is shown in the following that a simple rubbery amorphate should decompose by first order and the rate constants should adhere to an Arrhenius relationship with an activation energy which is the difference between ground state and excited state energies. Indomethacin has been used as a model compound.     

Amorphization reaction during mechanical alloying: influence of the milling conditions

Amorphous Ni-Zr powders have been prepared by mechanical alloying of elemental crystalline powders. The glass-forming range has been determined in detail at different milling intensities. Depending on the milling conditions, at least partial crystallization of the formerly amorphous material can occur from 66 to 75 at% Ni, due to a temperature rise during milling at high intensity. In comparison with isothermal annealing experiments at various temperatures on completely amorphous powder, a relation between milling temperature and milling time is shown. This confirms the similarity of the amorphization process during mechanical alloying with the solid-state interdiffusion reaction in alternating crystalline multilayers.     

Unique Bond Breaking in Crystalline Phase Change Materials and the Quest for Metavalent Bonding

Laser‐assisted field evaporation is studied in a large number of compounds, including amorphous and crystalline phase change materials employing atom probe tomography. This study reveals significant differences in field evaporation between amorphous and crystalline phase change materials. High probabilities for multiple events with more than a single ion detected per laser pulse are only found for crystalline phase change materials. The specifics of this unusual field evaporation are unlike any other mechanism shown previously to lead to high probabilities of multiple events. On the contrary, amorphous phase change materials as well as other covalently bonded compounds and metals possess much lower probabilities for multiple events. Hence, laser‐assisted field evaporation in amorphous and crystalline phase change materials reveals striking differences in bond rupture. This is indicative for pronounced differences in bonding. These findings imply that the bonding mechanism in crystalline phase change materials differs substantially from conventional bonding mechanisms such as metallic, ionic, and covalent bonding. Instead, the data reported here confirm a recently developed conjecture, namely that metavalent bonding is a novel bonding mechanism besides those mentioned previously.     

铋膜电极阳极溶出伏安法检测痕量Cd金属

镉氧化产生的溶出电流与样品中Cd²⁺的浓度有关。本研究通过方波阳极溶出伏安法(SWASV)在活化铋膜电极(Activated BFE)上对低浓度μg/L水平的Cd(II)进行测定。通过电化学方法对电极进行初步改性, 然后电沉积制备铋膜再次对电极进行改进, 从而增强了对痕量目标Cd²⁺的敏感性。对改性前后的玻碳电极(GCE)表面进行SEM、CV、EIS和SWV的表征。为了将这种伏安法传感器应用于含有低浓度Cd²⁺的实际样品中, 对检测Cd²⁺的实验参数进行了研究。使用选定的条件, 在10 min的预富集条件下Cd²⁺的检测限为1 μg/L。     

Mechanical properties of blends of poly(methyl methacrylate) and poly(vinylidene fluoride)

The mechanical properties of blends of the crystallizable polymer poly(vinylidene fluoride) and the amorphous material poly(methyl methacrylate) have been investigated as a function of composition both for glassy amorphous materials and for partially crystalline materials. The data obtained were interpreted in terms of the molecular and super-molecular structure of the blends and in terms of their dynamic properties.The main conclusions were that the mechanical properties are not strongly dependent on details of the distribution of the two components in the material nor on the crystal modifications present. The mechanical properties were found to depend primarily on the location of the glass transition temperature relative to the elongation temperature and on the presence or absence of crystalline regions. The degree of crystallinity was found to play an important role in determining the properties only at lower values of this quantity. The advantage of these blends is that the important parameters, namely, the degree of crystallinity and the location of the glass transition temperature, can be adjusted at will by varying the composition appropriately. This allows well-defined variations of the mechanical properties to be achieved.     

A new strategy to enhance cavitational tissue erosion using a high-intensity, Initiating sequence

Our previous studies have shown that pulsed ultrasound can physically remove soft tissue through cavitation. A new strategy to enhance the cavitation-induced erosion is proposed wherein tissue erosion is initiated by a short, high-intensity sequence of pulses and sustained by lower intensity pulses. We investigated effects of the initiating sequence on erosion and cavitation sustained by lower intensity pulses. Multiple three-cycle pulses at a pulse repetition frequency of 20 kHz delivered by a 788-kHz focused transducer were used for tissue erosion. Fixing the initiating sequence at I(SPPA) of 9000 W/cm2, 16 combinations of different numbers of pulses within the initiating sequence and different sustaining pulse intensities were tested. Results showed: the initiating sequence increases the probability of erosion occurrence and the erosion rate with only slight overall increases in propagated energy; the initiating sequence containing more pulses does not increase the sustained cavitation period; and if extinguished and reinitiated, the sustained cavitation period becomes shorter after each initiation, although the waiting time between adjacent cavitation periods is random. The high-intensity, initiating sequence enhances cavitational tissue erosion and enables erosion at intensities significantly lower than what is required to initiate erosion.     

Antimony film electrode for electrochemical stripping analysis

In this work, an antimony film electrode (SbFE) is reported for the first time as a possible alternative for electrochemical stripping analysis of trace heavy metals. The SbFE was prepared in situ on a glassy carbon substrate electrode and employed in combination with either anodic stripping voltammetry or stripping chronopotentiometry in nondeaerated solutions of 0.01 M hydrochloric acid (pH 2). Several key operational parameters influencing the electroanalytical response of SbFE were examined and optimized, such as deposition potential, deposition time, and composition of the measurement solution. The SbFE exhibited well-defined and separated stripping signals for both model metal ions, Cd(II) and Pb(II), surrounded with low background contribution and a relatively large negative potential range. The electrode revealed good linear behavior in the examined concentration range from 20 to 140 microg L-1 for both test metal ions, with a limit of detection (3sigma) of 0.7 microg L-1 for Cd(II) and 0.9 microg L-1 for Pb(II) obtained after a 120 s deposition step, and good reproducibility, with a relative standard deviation (RSD) of +/-3.6% for Cd(II) and +/-6.2% for Pb(II) (60 microg L-1, n = 12). When comparing the SbFE with the commonly used mercury film electrode and recently introduced bismuth film electrode, the newly proposed electrode offers a remarkable performance in more acidic solutions (pH < or = 2), which can be advantageous in electrochemical analysis of trace heavy metals, hence contributing to the wider applicability of electrochemical stripping techniques in connection with "mercury-free" electrodes.     

Determination of Cu2+ using poly(2-aminothiazole)/ multi-walled carbon nanotubes composite film modified glassy carbon electrodes

2-Aminothiazole was electropolymerized by cyclic voltammetry (CV) on the multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) surface. Poly(2-aminothiazole)/MWCNTs/GCE was used for determination of copper ions. The anodic peak currents of copper ions evaluated by differential pulse stripping voltammetry (DPSV) are linear with the concentrations in the range from 1.0 x 10(-7) M to 2.0 x 10(-5) M with a linear coefficiency of 0.9985. The detection limit is 2.0 x 10(-9) M calculated for a signal-to-noise ratio of 3 (S/N = 3). The proposed method was applied successfully to the determination of copper ions in drinking water, and the recovery was 96%.     

The generation of mono-energetic electron beams from ultrashort pulse laser-plasma interactions

The physics of the interaction of high-intensity laser pulses with underdense plasma depends not only on the interaction intensity but also on the laser pulse length. We show experimentally that as intensities are increased beyond 10(20) W cm(-2) the peak electron acceleration increases beyond that which can be produced from single stage plasma wave acceleration and it is likely that direct laser acceleration mechanisms begin to play an important role. If, alternatively, the pulse length is reduced such that it approaches the plasma period of a relativistic electron plasma wave, high-power interactions at much lower intensity enable the generation of quasi-mono-energetic beams of relativistic electrons.     

Determination of selenium(IV) by a photooxidized 3,3'-diaminobenzidine/perfluorinated polymer mercury film electrode

A new, and easily fabricated, chemically modified electrode for the determination of selenium(IV) was examined by cathodic square-wave stripping voltammetry. This new electrode consisted of an anion-exchange perfluorinated polymer (Tosflex) coated thin mercury film electrode containing photooxidized 3,3'-diaminobenzidine (ODAB). The coating solution of Tosflex and ODAB was spin-coated on a glassy carbon electrode followed by electroplating of a thin film of mercury. During the preconcentration, ODAB was reduced electrochemically and selenium was accumulated simultaneously onto the electrode by interacting with the reduced ODAB. After a 5-min preconcentration period, linear response was observed from 0.5 to 50 ppb selenium, and the detection limit was 0.1 ppb. The proposed method does not require a darkened room, which was required in many of the previous methods involving 3,3'-diaminobenzidine. In addition, the resistance to interference from surface-active compounds was improved by incorporating Tosflex in the film.