Electrochemical Synthesis of Co-intercalation Compounds in the Graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>System

Anodic oxidation of highly oriented pyrolytic graphite in an electrolyte containing concentrated sulfuric and anhydrous phosphoric acids is studied for the first time. The synthesis was carried out under galvanostatic conditions at a current I = 0.5 mA and an elevated temperature (t = 80°C). Intercalation compounds of graphite (ICG) are shown to form at all concentration ratios of H₂SO₄ and H³PO⁴ acids. The intercalation compound of step I forms in solutions containing more than 80 wt % H₂SO₄, a mixture of compounds of intercalation steps I and II forms in 60% H²SO⁴, intercalation step II is realized in the sulfuric acid concentration range from 10 to 40%, and a mixture of compounds of intercalation steps III and II is formed in 5% H₂SO₄ solutions. The threshold concentration of H₂SO₄ intercalation is ∼2%. With the decrease in active intercalate (H₂SO₄) concentration, the charging curves are gradually smoothed, the intercalation step number increases, and the potentials of ICG formation also increase. As the sulfuric acid concentration in the electrolyte changes from 96 to 40 wt %, the filled-layer thickness d _i in ICG monotonously increases from 0.803 to 0.820 nm, which apparently is associated with the greater size of phosphoric acid molecules. With further increase in H₃PO₄ concentration in solution, d _i remains unchanged. According to the results of chemical analysis, both acids are simultaneously incorporated into the graphite interplanar spacing and their ratio in ICG is determined by the electrolyte composition.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 651–655.Original Russian Text Copyright © 2005 by Leshin, Sorokina, Avdeev.     

Template functions of particle monolayers on hydrophobic solid substrates

The template function of cationic particle monolayers bearing quaternary ammonium groups on their surfaces towards anionic colloids was investigated in this paper. Monodispersed cationic polymer particles having quaternary ammonium groups were self-organized on octadecylated glass plates through hydrophobic interaction. The morphology of the resulting particle monolayers was changed by tuning hydrophilic–hydrophobic balance of particles to fabricate aggregated type and dispersed type of particle monolayers. Gold and silver colloids were selectively deposited onto the particle monolayers through electrostatic interaction. The deposited gold and silver colloids on particle monolayers showed plasmon absorbance. Fluorescent silica colloids were also selectively deposited on particle monolayers to permit fluorescence labeling of the particle monolayers. Cationic particle monolayers fabricated on hydrophobic solid octadecylated were found to effectively work as templates for the deposition of above mentioned inorganic colloids.     

Operation of the quasi-optical gyrotron at harmonics of the gyrofrequency

This paper investigates the performance of a quasioptical gyrotron, when the electron beam interacts with the radiation fields at harmonics of the gyrofrequency. The nonlinear equations of motion are obtained in the slow-timescale. The expression for the linear gain is derived and the conditions for excitation are given (frequency threshold, optimal operating point, bean current and resonator quality thresholds). In the nonlinear regime, it is shown that maximum efficiencies comparable to those at the fundemental (50%) are possible, albeit at a prohitively high radiation field amplitude, while realistically feasible field amplitudes can give somewhat smaller, but nevertheless still high efficiencies (15%). Finally, the results are suplemented by empirical scaling laws, useful for experimental designs.     

The electrochemistry and determination of Ligustrazine hydrochloride

Ligustrazine is one of the active ingredients contained in Ligusticum chuanxiong Hort. (Umbelliferae), which is widely used in traditional Chinese medicine for the treatment of cardiovascular problems. In this work, the electrochemistry of Ligustrazine hydrochloride (LZC) and its determination are investigated. The detection limit is estimated to be 8.0×10^–8 M, with three linear ranges from 1.0×10^–6 to 1.0×10^–4 M, 1.0×10^–4 to 5.0×10^–4 M, and 6.5×10^–4 to 1.6×10^–3 M. The method has been proved to be highly sensitive, selective, and stable, and has been successfully applied to determining LZC in LZC injections.     

Estimating reaction parameters in mechanism-enabled population balance models of nanoparticle size distributions: A Bayesian inverse problem approach

In order to quantitatively predict nano- as well as other particle-size distributions, one needs to have both a mathematical model and estimates of the parameters that appear in these models. Here, we show how one can use Bayesian inversion to obtain statistical estimates for the parameters that appear in recently derived mechanism-enabled population balance models (ME-PBM) of nanoparticle growth. The Bayesian approach addresses the question of “how well do we know our parameters, along with their uncertainties?.” The results reveal that Bayesian inversion statistical analysis on an example, prototype nanoparticle formation system allows one to estimate not just the most likely rate constants and other parameter values, but also their SDs, confidence intervals, and other statistical information. Moreover, knowing the reliability of the mechanistic model's parameters in turn helps inform one about the reliability of the proposed mechanism, as well as the reliability of its predictions. The paper can also be seen as a tutorial with the additional goal of achieving a “Gold Standard” Bayesian inversion ME-PBM benchmark that others can use as a control to check their own use of this methodology for other systems of interest throughout nature. Overall, the results provide strong support for the hypothesis that there is substantial value in using a Bayesian inversion methodology for parameter estimation in particle formation systems.     

Self-organization of polymer particles on hydrophobic solid substrates in aqueous media. II. Self-organization of cationic polymer particles on polymer films and wettability control with particle monolayers

Self-organization of cationic polymer particles through hydrophobic interaction on polymer films in aqueous system and characteristic properties of the resulting particle monolayers were investigated. Cationic polymer particles bearing quaternary ammonium groups on their surfaces effectively self-organized on polymer films. With an increase of the particle surface charge density, the surface coverage and average aggregate size (N _a) decreased. The surface coverage control was accomplished by tuning the ionic strength of the media. The wettability of polymer films for water was imparted by the formation of particle monolayers on them. Annealing of the particle monolayers resulted in the increase of the adhesive strength, while the wettability for water was lost. Further improvements of both wettability and adhesive strength of particle monolayers were achieved by the immobilization of silica colloids on the particle monolayers. This method would be effective for the hydrophilization of polymer films.     

ToF‐SIMS observation of PTFE surfaces modified by α‐particle irradiation

The surface structure of polytetrafluoroethylene (PTFE) upon α‐particle irradiation has been investigated at doses in the range of 1 × 10⁷ to 1 × 10¹¹ Rad and compared with the surface structure of the unirradiated polymer. Both neat and 25% fiberglass content PTFE were studied. The samples, maintained at nominal room temperature, were irradiated in vacuum by 5.5 MeV ⁴He²⁺ ions generated in a tandem accelerator beam line. Static time‐of‐flight SIMS (ToF‐SIMS) was employed to probe chemical changes at the surface as a function of the irradiation level. In general, the data are indicative of increased cross‐linking at α‐doses less than 1 × 10⁹ Rad, followed by increased fragmentation and unsaturation at α‐doses greater than 1 × 10⁹ Rad. Throughout the irradiation regime, scission is a constant factor promoting cross‐linking, branching, and unsaturation. However, at α‐doses greater than 1 × 10¹⁰ Rad, extreme structural degradation of the polymer becomes evident and is accompanied by conversion to oxygen‐functionalized and aliphatic compounds. Thus, for PTFE in an α‐particle field, an upper exposure limit of ～10¹⁰ Rad is essential for nominal retention of molecular structure. Finally, a quantitative relationship between α‐dose and characteristic fragment ion intensity is developed. Copyright © 2005 John Wiley & Sons, Ltd.     

Characterisation of River Po particles by sedimentation field-flow fractionation coupled to GFAAS and ICP-MS

A procedure for elemental composition determination of water-borne river particles (Po River) on both size-fractionated and unfractionated submicron particles (0.1–1 μm) by graphite furnace atomic absorption spectroscopy (GFAAS) and inductively coupled plasma-mass spectrometry (ICP-MS) is reported. Sample fractionation was performed using sedimentation field-flow fractionation (SdFFF). The distribution of relative mass vs. particle size was determined using UV detection. Fractions were collected over a narrow size range for scanning electron microscopy. With this combination of techniques the mass, elemental composition, and shape distributions can be obtained across the size spectrum of the sample.

The size distributions of the major elements (Al, Fe) were determined by coupling both GFAAS and ICP-MS techniques to the SdFFF. The procedure was validated using a reference clay sample. Satisfactory agreement was found between both the GFAAS and ICP-MS aluminium signal and the UV detector signal. Some discrepancies were observed in the Fe/Al ratios when comparing GFAAS and ICP-MS. Thus further investigation is in order to fully assess the role of SdFFF-ICP-MS and SdFFF-GFAAS techniques for elemental characterisation of aquatic colloids. Both GFAAS and ICP-MS signals unambiguously indicate a significantly higher Fe content in the lower size range, which is consistent with previous investigations.

Trace element levels in unfractionated Po River particles, determined by both GFAAS and ICP-MS, show good agreement. The high levels of Cu, Pb, Cr and Cd found associated with the colloidal particles underlines the significance of the environmental role played by the suspended matter in rivers in both highly industrialised and intensively cultivated areas.     

Sensitive Flow-Injection Electrochemical Determination of Hydrogen Peroxide at a Palladium Nanoparticle-Modified Pencil Graphite Electrode

A novel flow-injection amperometric method was proposed for the sensitive and enzymeless determination of hydrogen peroxide based on its electrocatalytic reduction at a palladium nanoparticle-modified pretreated pencil graphite electrode in a laboratory-constructed electrochemical flow cell. Cyclic voltammograms of the unmodified and modified electrodes were recorded in pH 7.0 phosphate buffer containing 0.10 M KCl at a scan rate of 50?mV s^?1 for the investigation of electrocatalytic reduction of hydrogen peroxide at the palladium nanoparticle-modified pretreated pencil graphite electrode. Cyclic voltammograms of the pretreated pencil graphite electrode revealed an irreversible oxidation peak and a weak reduction peak of hydrogen peroxide at +1100?mV and –450?mV vs. an Ag/AgCl/KCl saturated reference electrode. However, the reduction of hydrogen peroxide was observed at –100?mV with an increase in current in the cyclic voltammograms of the palladium nanoparticle-modified pretreated pencil graphite electrode compared to the unmodified electrode. These results indicate that the palladium nanoparticle-modified pretreated pencil graphite electrode exhibits efficient electrocatalytic activity for the reduction of hydrogen peroxide. A linear concentration range was obtained between .01 and 10.0?mM hydrogen peroxide with a detection limit of 3.0 µM from flow injection amperometric current–time curves recorded in pH 7.0 phosphate buffer at –100?mV and a 2.0?mL min^?1 flow rate. The novelty of this work relies on its use of a laboratory-constructed flow cell constructed for the pencil graphite electrode using these inexpensive, disposable, and electrochemically reactive modified electrodes for the amperometric determination of hydrogen peroxide in a flow injection analysis system.     

Study of the Electrochemical Behavior of Disperse Blue 1‐Modified Graphite Electrodes. Application to the Flow Determination of NADH

The preparation and the electrochemical study of Disperse Blue 1‐chemically modified electrodes (DB1‐CME), as well as their efficiency for the electrocatalytic oxidation of NADH is described. The proposed mediator was immobilized by physical adsorption onto graphite electrodes. The electrochemical behavior of DB1‐CME was studied with cyclic voltammetry. The electrochemical redox reaction of DB1 was found to be reversible, revealing two well‐shaped pair of peaks with formal potentials 152 and ?42 mV, respectively, (vs. Ag/AgCl/3M KCl) at pH 6.5. The current I_p has a linear relationship with the scan rate up to 800 mV s^?1, which is indicative for a fast electron transfer kinetics. The dissociation constants of the immobilized DB1 redox couple were calculated pK₁=4 and pK₂=5. The electrochemical rate constants of the immobilized DB1 were calculated k₁°=18 s^?1 and k₂°=23 s^?1 (Γ=2.36 nmol cm^?2). The modified electrodes were mounted in a flow injection manifold, poised at +150 mV (vs. Ag/AgCl/3M KCl) and a catalytic current due to the oxidation of NADH was measured. The reproducibility was 1.4% RSD (n=11 for 30 μM NADH) The behavior of the sensor towards different reducing compounds was investigated. The sensor exhibited good operational and storage stability.