Poly(ethylene oxide)s hydrophobically modified. Adsorption and spreading at the air-water interface

A comparative study of spread and adsorbed monolayer of poly(ethylene oxide)s of different molecular weight hydrophobically modified with alkyl isocyanates of different length chain is reported. The modification of the polymer was carried out according to reported procedures. The polymers obtained were studied at the air-water interface by Langmuir isotherms for spread monolayers and by Gibbs isotherms for the adsorption process. Isotherms obtained are interpreted in terms of the hydrophobic and hydrophilic balance of the polymers. Limiting area per repeating unit (A(0)) and collapse pressure (pi(c)) from spread monolayers were obtained. Spread monolayers of the hydrophobically modified polymers show larger collapse pressure values than unmodified polymer monolayers. In the adsorption process the excess surface concentration Gamma(infinity), area per repeat unit sigma, and efficiency of the adsorption were determined. The values of the area occupied per repeat unit in adsorbed monolayer (sigma) were larger than those of the spread monolayer. The efficiency of the adsorption of poly(ethylene oxide)s increases with the hydrophobic modification and with the alkyl chain length.     

Synthesis of pyridin-3-yl-functionalized silica as a chelating sorbent for solid-phase adsorption of Hg(II), Pb(II), Zn(II), and Cd(II) from water

Silica gel modified with 3-aminopropyltrimethoxysilane was anchored with nicotinaldehyde to prepare a new chelating surface (or matrix). It was synthesized and characterized by elemental analysis, cross-polarization magic-angle spinning ¹³C nuclear magnetic resonance (NMR) spectroscopy, diffuse reflectance infrared Fourier-transform spectroscopy, nitrogen adsorption–desorption isotherm, Brunauer–Emmett–Teller surface area, and Barrett–Joyner–Halenda pore sizes. The new surface exhibits good chemical and thermal stability as determined by thermogravimetry curves. This new organic–inorganic material was used for preconcentration of Hg(II), Pb(II), Zn(II), and Cd(II) from water prior to their determination by inductively coupled plasma atomic emission spectrometry. The optimum pH for quantitative sorption of these metal ions is in the range of 6–8, and the sorption capacity is in range of 486–1,449 μmol/g. By batch method, 95 % extraction takes ≤30 min. All the metals could be desorbed with a solution of hydrochloric acid (6 N) without loss of the expensive ligand. Solutions of the metal ions were prepared by dissolution of the nitrate solution.     

Electrochemical Study of the Interaction of the Alkylating Agent Busulfan with Double Strand DNA

Damage of salmon sperm double strand ss dsDNA in solution or immobilized on screen‐printed carbon electrode (SPCE) induced by incubation of DNA with the antineoplastic alkylating agent busulfan (BUS) at various conditions was detected for the first time by simple electrochemical methods. Chemical changes in DNA bases can be detected through the altered electroactivity of the DNA. Electrochemical voltammetric sensing of damage caused by BUS to dsDNA in solution was monitored by the appearance of peaks diagnostic of the oxidation of guanine and adenine. Moreover, crystal violet, which interacts with the DNA immobilized on SPCEs, was used as an effective electroactive indicator, in combination with cyclic voltammetry and differential pulse voltammetry techniques to monitor the cross‐links or damage to DNA. The interaction between BUS and DNA were determined by the changes in the voltammetric peak of crystal violet. The effects of various conditions upon the crystal violet signal were investigated.     

A Third‐Generation Hydrogen Peroxide Biosensor Based on Horseradish Peroxidase Covalently Immobilized on Electrografted Organic Film on Screen‐Printed Carbon Electrode

A new convenient strategy to fabricate a third‐generation hydrogen peroxide biosensor was described. The screen‐printed carbon electrode (SPCE) was first modified with a layer of 4‐nitrophenyl assembled from the 4‐nitroaniline diazonium salt synthesized in situ in acidic aqueous solution. Next, the nitro groups were converted to amines followed by crosslinking to the horseradish peroxidase (HRP) by glutaraldehyde. The redox chemistry of the active center of the HRP was observed and the HRP‐modified electrode displayed electrocatalytic activity towards the reduction of hydrogen peroxide (H₂O₂) without any mediators. H₂O₂ was determined in a linear range from 5.0 μM to 50.0 μM, with a detection limit of 1.0 μM. Furthermore, the biosensor exhibited fast amperometric response, good reproducibility and long‐term stability.     

Molecularly Imprinted Poly-o-phenylenediamine Electrochemical Sensor for Entacapone

We have developed a molecularly imprinted polymer (MIP) electrochemical sensor for entacapone (ETC) based on an electropolymerised polyphenylenediamine (Po-PD) on a glassy carbon electrode (GCE) surface. The direct electropolymerisation of the o-phenylenediamine monomer (o-PD) was carried out with ETC as a template. The steps of electropolymerization process, template removal and binding of the analyte were tested by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using [Fe(CN)₆]³⁻/[Fe(CN)₆]^{4 −} as a redox probe. The operation of the sensor has been investigated by differential pulse voltammetry (DPV). Under optimal experimental conditions, the response of the DPV was linearly proportional to the ETC concentration between 1.0×10⁻⁷ and 5.0×10⁻⁶ M ETC with a limit of detection (LOD) of 5.0×10⁻⁸ M. The developed sensor had excellent selectivity without detectable cross-reactivity for levodopa and carbidopa. The MIP sensor was successfully used to detect ETC in spiked human serum samples.     

Anodic voltammetric methods for determination of the antiparasitic drug nitazoxanide in bulk form, pharmaceutical formulation, and its metabolite tizoxanide in human serum

Abstract  

The oxidative behavior of nitazoxanide was studied on a carbon paste electrode in phosphate buffer solutions using cyclic and differential-pulse voltammetry. The oxidation process was shown to be irreversible over the pH range 3.4–11.0 and was adsorption-controlled process. An analytical method was developed for the determination of nitazoxanide in phosphate buffer solution at pH 5.6 as the supporting electrolyte. The anodic peak current varied linearly with nitazoxanide concentration in the range 4.0 × 10⁻⁷ to 1.0 × 10⁻⁵ M with a limit of detection of 7.5 × 10⁻⁸ M. Validation parameters such as sensitivity, accuracy, precision, and recovery were evaluated. The proposed method was applied to the determination of nitazoxanide in the pharmaceutical formulation. The results were compared with those obtained by a spectrophotometric method. No difference was found statistically. Based on the adsorption behavior of the metabolite tizoxanide onto the carbon paste electrode surface, a simple and sensitive differential-pulse adsorptive anodic stripping voltammetric method was developed for the determination of tizoxanide in spiked human serum without the need for extraction.     

Degenerate and two‐color resonant four‐wave mixing of C2− in a molecular beam environment

In this paper, we demonstrate that degenerate and two‐color resonant four‐wave mixing spectroscopy is applicable for the sensitive and selective characterization of negative ions in a molecular beam environment. Results are shown for C , which is produced by discharging a mixture of acetylene and argon prior to supersonic expansion. Substantial signal‐to‐noise ratios of ≈ 150 show that the method is generally applicable for high‐resolution optical double‐resonance spectroscopy of negative ions. A detection sensitivity for C of ≈ 10⁷ ions/cm³ is estimated. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of Ge islands from a Ge layer on Si substrate during post-growth annealing

We have deposited a 12 nm thick Ge layer on Si(1 0 0) held at 200 °C by thermal evaporation under high vacuum conditions. Upon subsequent thermal annealing in vacuum, self-assembled growth of nanostructural Ge islands on the Ge layer occurred. Atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS) were used to characterize such layers. GISAXS measurements evidenced the formation of cylinder shaped structures upon annealing at 700 °C, which was confirmed by AFM measurements with a very sharp tip. A Ge mass transport from the layer to the islands was inferred by X-ray reflectivity and an activation energy of 0.40 ± 0.10 eV for such a process was calculated.     

OH Concentration Measurements by Resonant Holographic Interferometry and Comparison with Direct Numerical Simulations

We apply a novel laser diagnostic technique — Resonant Holographic Interferometry (RHI) to measure the concentration of hydroxyl radical (∼2000 ppm) in a co-flow diffusion flame of diluted hydrogen and air stabilized on a Wolfhard-Parkerburner. This methodology is based upon the dispersion of light of frequency close to an electronic transition of a target molecule. The two-color setup utilized in RHI provides a two-dimensional distribution of the target species concentration and quantitative information can be obtained from the interferogram without requiring any calibration. To provide independent flame data for comparison, a two-dimensional numerical simulation was performed taking into account the effects of detailed chemical kinetics and transport phenomena. In spite of a number of simplifying assumptions made in the simulation, computational and experimental results are in good agreement with respect to the magnitude and width of the region where OH is found. We do observe a difference of approximately 1 mm in the flame position due to the simplifying assumptions made in the simulation. The comparison between the experimental and numerical results clearly demonstrated the potential of RHI in flame diagnostics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electrochemical reduction of secnidazole and its determination in tablets

The electrochemical reduction of secnidazole has been carried out in aqueous solution in the pH range of 2.0–12.0 by DC polarography, AC polarography and cyclic voltammetry. Two well-defined reduction waves appear in acidic media, whereas at higher pHs the two waves overlap. The variation of E_1/2 or E_p and I_lim or I_p with pH was studied. The diffusion-controlled nature of the waves was established and the irreversibility of the electrode process was verified by different criteria. The mechanism of reduction was discussed. A method for the detemination of secnidazole by DC polarography at pH 8.5 which allows quantitation over the 1 × 10⁻⁵ M-4 × 10⁻⁴ M range was proposed and applied to the determination of secnidazole in tablets. The mean recovery was 99.67% and the relative standard deviation was 0.89%. Excipients did not interfere in the determination.