Evaluation of the sputtering rate variation in SIMS ultra‐shallow depth profiling using multiple short‐period delta layers

We have developed multiple short‐period delta layers as a reference material for SIMS ultra‐shallow depth profiling. Boron nitride delta layers and silicon spacer layers were sputter‐deposited alternately, with a silicon spacer thickness of 1–5 nm. These delta‐doped layers were used to measure the sputtering rate change in the initial stage of oxygen ion bombardment. A significant variation of sputtering rate was observed in the initial 3 nm or less. The sputtering rate in the initial 3 nm was estimated to be about four times larger than the steady‐state value for 1000 eV oxygen ions. Copyright © 2003 John Wiley & Sons, Ltd.     

Thin‐Layer Cyclic Voltammetric and Scanning Electrochemical Microscopic Study of Antioxidant Activity of Ascorbic Acid at Liquid/Liquid Interface

An electron transfer reaction between ascorbic acid (H₂A) in an aqueous solution and oxidizing agent in an organic solution immiscible with water has been studied by thin‐layer cyclic voltammetry (TLCV) for charge transfer at the interface between two immiscible electrolyte solutions (ITIES). As an antioxidant, H₂A provide electrons through the aqueous/organic interface to reduce Fc⁺ and the procedure has been proved to be a one electron process again. In this work, the first combination of TLCV and scanning electrochemical microscopy (SECM) was achieved and showed a reasonable agreement between the results from the two different approaches. Otherwise, lower concentration ratios Kr of aqueous to organic reactants was adopted, which is given as evidence to the proposed procedure of Barker.     

Mass transfer to horizontal gas-generating electrodes

Mass transfer to a horizontal electrode during electrolytic evolution of oxygen and hydrogen at current densities of 100 to 10 000 A/m² is studied. The mass transfer intensity is evaluated from the diffusion layer thickness, which varies from 60 to 5 μm at such current densities. Calculations show that the decrease in the diffusion layer thickness is due to bubbles with a stationary interphase surface crossing the diffusion layer. During the hydrogen evolution, the diffusion layer thickness is nearly the same for vertical and horizontal electrodes. During the oxygen evolution, the diffusion layer is much thinner for a horizontal electrode. Additional decrease of the diffusion layer thickness during the evolution of oxygen is associated with the lesser solution density in the near-electrode layer and with its transport away by means of natural convection.     

Adsorption of the fluoride ion on the surface of various faces of a single crystal of silver: a quantum-chemical study

The fluoride ion adsorption from a gas phase on various faces of a single crystal of silver is studied by a density functional method within a cluster model for metal. The adsorption bond energy is found to increase in the series Ag(100) < Ag(111) < Ag(311) < Ag(110). A substantial structural and energetic heterogeneity of various adsorption sites is revealed. The results are utilized to simulate the electrochemical interface between individual faces of a single crystal of silver and aqueous solutions containing the fluoride ion. It is assumed that the adsorption potential may be represented as the sum of two contributions, one of which describes the metal–ion interaction and the other, the ion solvation energy. The plotted adsorption terms take into account partial degradation of the fluoride ion when adsorbed from an aqueous solution. Estimates of discreteness of the electrical double layer are presented. A conclusion on the maximum manifestation of specific adsorption of the fluoride ion for the Ag(100) face is made.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 232–238.Original Russian Text Copyright © 2005 by Nazmutdinov, Zinkicheva.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Direct electron transfer reaction of glucose oxidase at bare silver electrodes and its application in analysis

The direct electron transfer reaction of glucose oxidase (GOx) at a bare silver electrode is verified. The electron transfer number n = 2, electron transfer coefficient α = 0.45 and rate constant of the electrochemical reaction K_s = 0.1 s⁻¹ are obtained. This communication presents a multimolecular adsorption model to explain the properties of the direct electron reaction between GOx and bare silver electrodes. The residual valence force may be an important factor to ensure a direct electron transfer reaction on the bare electrode. On the basis of the experimental fact that only biologically active GOx exhibits electrochemical activity in solution, a facile analytical method for analyzing the active GOx concentration is developed. The results determined correspond very well to that of a spectrometric method.     

Characterization of peptides by liquid chromatography/electrospray ionization mass spectrometry using silver nitrate as a post-column complexant

Two model peptides, des-Arg1-bradykinin (DAB) and bradykinin (B), were cationized by Ag+ after their separation by reversed-phase liquid chromatography (RPLC) prior to mass spectrometry (MS). Silver nitrate solution was used as a post-column reagent. The RPLC and MS experimental conditions were optimized using flow injection in order to obtain sufficiently abundant silver adducts to permit MS/MS experiments. The use of water-methanol with 0.1% formic acid as mobile phase allowed a good chromatographic separation of the two peptides with a polymeric stationary phase and sufficiently abundant silver-containing adducts, [M + Ag + H]2+ and [M + 2Ag]2+. The gas-phase dissociation of [DAB + Ag + H]2+ and [DAB + 2Ag]2+ led to interpretable mass spectra during the on-line cationization experiment. Most of the ions obtained by dissociating [DAB + Ag + H]2+ and [DAB + 2Ag]2+ species are silver-containing ions but the ions produced depend on the parent. The ions coming from the dissociation of the doubly charged silver adducts [DAB + Ag + H]2+ or [DAB + 2Ag]2+ are of interest compared with those coming from the singly charged silver species or doubly charged protonated species. The fragmentation of the doubly charged silver adducts provides ions over the entire mass range. Although the presence of several prolines in des-Arg1-bradykinin prevents the formation of some expected ions, the observation of triplets [an-H + Ag]+, [bn-H + Ag]+ and [bn + OH + Ag]+ produced by the dissociation of on-line Ag(+)-cationized peptides could contribute to greater success of automatic sequencing of peptides.     

Quantification of Valerenic Acid in Valeriana jatamansi and Valeriana officinalis by HPTLC

A simple, rapid, cost-effective and accurate high performance thin layer chromatographic method has been developed for quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis which is one of the stable compounds of Valeriana officinalis and designated as a key marker compound. Valerenic acid makes substantial contribution to the sedative and spasmolytic activity of the essential oil and extract of Valeriana officinalis. Separation and quantification was achieved by HPTLC using ternary mobile phase of hexane: ethyl acetate: acetic acid (80:20:0.5 v/v) on precoated silica gel 60F₂₅₄ aluminium plates and densitometric determination was carried out after derivatization with anisaldehyde-sulphuric acid reagent at 700 nm, in absorption-reflectance mode. The calibration curves were linear in the range of (500 ng–2.5 μg). This is the first HPTLC report for the identification and quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis.     

Reactivity and Structural Properties of a Mechanochemically Treated Ag2O-V2O5 System in Relation to AgVO3 Polymorphs

Formation and chemical properties of amorphous AgVO₃, which was prepared by mechanochemical treatment of an Ag₂O-V₂O₅ mixture, and crystalline AgVO₃ were studied in relation to AgVO₃ polymorphs. A ball-milled sample of the mixture was assigned as a highly deformed β-AgVO₃ rather than the low density phase α-AgVO₃. Crystalline α-AgVO₃ and β-AgVO₃ were converted into deformed β-AgVO₃ by ball milling, which produced a clear change. δ-AgVO₃ is resistant to mechanical treatment and its structure was not markedly affected. The dissolved chemical species from the ball-milled sample precipitates to form α-AgVO₃ without a seeding crystal, but other polymorphs deposit if they are present; i.e., β-AgVO₃ and δ-AgVO₃ grow on the seeding crystal.     

Effect of Inorganic Ions on Oleate Adsorption at a Nigerian Hematite–Water Interface

Using “pure” natural hematite selected from a high silica Nigerian hematitic ore, oleate adsorption densities at the hematite–water interface were determined in the presence of various inorganic ions (anions and cations) of different charges and at varying concentrations. Adsorption density was determined using electrical conductivity measurements. The specific surface area of the hematite particles was determined using the method of adsorption of paranitrophenol in aqueous solution. Inorganic ions in solution depressed oleate adsorption at the aqueous hematite surface. The charge of the ion proved to be the dominant factor determining the depression of oleate adsorption. Ionic strength also was an influence, up to a limiting value at which monolayer oleate coverage of the hematite surface occurred. The inorganic ions in solution are considered to function through nonspecific adsorption in the diffuse region of the electric double layer.     

壳聚糖作用下一步法合成具有高电活性的AgCl@聚苯胺核壳结构

在壳聚糖的作用下，采用简单的一步法合成了具有星状结构的氯化银/聚苯胺核壳型复合材料。当壳聚糖的浓度为1%时，所制备的氯化银/聚苯胺复合材料具有高度的分散性，壳层厚度为30～80 nm、核的直径在25～60 nm范围内。通过透射电镜、红外光谱和X-射线衍射对样品的形态和组成进行了表征。循环伏安实验结果表明这种复合材料在中性条件下具有很好的电化学活性。