Surface modification and characterization of phenanthroline nanofilms on carbon substrate

Modification of glassy carbon (GC) surfaces with phenanthroline derivatives (PDs) such as 5‐amino‐1,10‐phenanthroline (5AP) and 5,6‐diamino‐1,10‐phenanthroline (56DAP) is described in this study. Surface modification experiments were performed by cyclic voltammetry (CV) scanning from + 1.2 to + 2.7 V at scan rate of 100 mV/s applying 30 potential scans in acetonitrile (CH₃CN) containing 1 mM PDs and 100 mM tetrabutylammoniumtetrafluoroborate (TBATFB). The presence of PDs on GC electrode was confirmed using CV, electrochemical impedance spectroscopy (EIS), contact angle measurements and ellipsometry and comparing with the results of bare GC electrode. A mechanism was proposed for the electrochemical modification of the GC electrode surface with PDs. The structure of the 5AP and 56DAP films was also discussed in the light of electrochemical and spectroscopic data. The complex‐forming ability of the modified surfaces against metal cations was investigated by square‐wave voltammetry (SWV). It was shown that surfaces having 1,10‐phenanthroline ligands with different functional groups were quite useful for the determination of transition metal ions. Copyright © 2010 John Wiley & Sons, Ltd.     

The effects of low dose leukotriene receptor antagonist therapy on airway remodeling and cysteinyl leukotriene expression in a mouse asthma model

Airway structural changes that occur in patients with asthma in response to persistent inflammation are termed airway remodeling. The cysteinyl leukotrienes (LTC(4), D(4) and E(4)) are known to play important roles in the pathobiology of asthma. To evaluate the effect of low dose montelukast (MK) on the development of airway remodeling using a chronic murine model of allergic airway inflammation with subepithelial fibrosis, BALB/c mice, after intraperitoneal ovalbumin (OVA) sensitization on days 0 and 14, received intranasal OVA periodically on days 14-75. MK treated mice received montelukast sodium intraperitoneally on days 26-75. The OVA sensitized/challenged mice developed an extensive eosinophil cell inflammatory response, goblet cell hyperplasia, mucus occlusion, and smooth muscle hypertrophy of the airways. In addition, in OVA sensitized/challenged mice, dense collagen deposition/fibrosis was seen throughout the lung interstitium surrounding the airways, blood vessels, and alveolar septae. The cysteinyl leukotriene 1 (CysLT1) receptor antagonist, MK significantly reduced the airway eosinophil infiltration, goblet cell hyperplasia, mucus occlusion, and lung fibrosis except airway smooth muscle hypertrophy in the OVA sensitized/challenged mice. The OVA sensitized/challenged mice had significantly increased epithelial desquamation compared with control mice. MK markedly reduced epithelial desquamation of airways in OVA/MK treated animals compared with OVA sensitized/challenged mice. MK treatment did not affect the levels of CysLT in lung tissue. Our results show that the important role of cysteinyl leukotrienes in the pathogenesis of asthma. Lower dose of CysLT1 receptor antagonism has a significant anti-inflammatory effect on allergen-induced lung inflammation and fibrosis but not airway smooth muscle hypertrophy in an animal model of asthma.     

On some constacyclic codes over $$\mathbb {Z}_{4}\left[ u\right] /\left\langle u^{2}-1\right\rangle $$, their $$\mathbb {Z}_4$$Z4 images,and new codes

In this paper, we study \(\lambda \)-constacyclic codes over the ring \(R=\mathbb {Z}_4+u\mathbb {Z}_4\) where \(u^{2}=1\), for \(\lambda =3+2u\) and \(2+3u\). Two new Gray maps from R to \(\mathbb {Z}_4^{3}\) are defined with the goal of obtaining new linear codes over \(\mathbb {Z}_4\). The Gray images of \(\lambda \)-constacyclic codes over R are determined. We then conducted a computer search and obtained many \(\lambda \)-constacyclic codes over R whose \(\mathbb {Z}_4\)-images have better parameters than currently best-known linear codes over \(\mathbb {Z}_4\).     

Light-Mediated Formal Radical Deoxyfluorination of Tertiary Alcohols through Selective Single-Electron Oxidation with TEDA2+.

The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of C−F bonds from (hetero)benzylic, propargylic, and non-activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single-electron oxidation of cesium oxalates—which are readily available from the corresponding tertiary alcohols—with in situ generated TEDA^2+. (TEDA: N-(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor®.     

Analysis of high molecular mass proteins larger than 150 kDa using cyanogen bromide cleavage and conventional 2-DE

Proteomic approaches including high-resolution 2-DE are providing the tools needed to discover disease-associated biomarkers in complex biological samples. Although 2-DE is an extremely powerful approach to analyze the proteome, the separation of proteins with extreme molecular masses still remains an issue requiring improvement. Because high molecular mass (HMM) proteins larger than 150 kDa have already been observed to be differentially expressed in several pathologies such as cancer, we developed an original strategy to analyze this part of the proteome that is not easily separated by 2-DE in polyacrylamide gels. This strategy is based on the 2-DE separation of cyanogen bromide (CNBr) fragments of purified HMM protein fractions, and combines techniques including SEC fractionation, TCA precipitation, CNBr cleavage, 2-DE and MS analysis. The method was first tested on a model protein, the BSA. Preliminary results obtained using colonic tissues led to the identification of six HMM proteins with M(r) comprised between 163 and 533 kDa in their reduced state. These results demonstrated that our CNBr/2-DE approach should provide a powerful tool for identification of new biomarkers larger than 150 kDa.     

Swelling studies of copolymeric acrylamide/crotonic acid hydrogels as carriers for agricultural uses

In this study, highly swollen acrylamide/crotonic acid hydrogels (in a rod form) containing some inorganic salts such as ammonium nitrate, potassium nitrate and ammonium sulphate used as fertilizer, an agricultural drug such as Dalapon (sodium 2,2‐dichloropropionate) and two crosslinkers such as ethylene glycol dimethacrylate and 1,4‐butandiol dimethacrylate were prepared by copolymerization of acrylamide and crotonic acid with γ‐radiation. As a result of swelling tests, the influence of γ‐ray dose and relative content of crotonic acid on the swelling properties, the diffusional behavior of water, diffusion coefficients and network properties of the hydrogel systems were examined. Acrylamide/crotonic acid hydrogels containing these salts and agricultural drug were swollen in the range 2045–400% in water, while polyacrylamide hydrogels swelled in the range 660–700%. Water intake of hydrogels followed a nonFickian‐type diffusion. Copyright © 2000 John Wiley & Sons, Ltd.     

Crystalline structure and morphological properties of undoped and Sn doped ZnO thin films

Undoped and tin (Sn) doped ZnO thin films have been prepared by spray pyrolysis method. Effect of Sn dopant on the crystalline structure and morphological properties of ZnO thin films has been investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) method. XRD patterns confirm that the films have polycrystalline nature. While undoped ZnO film has (101) as the preferred orientation, Sn doped ZnO thin films have (002) as the preferred orientation. Grain sizes, lattice parameters and texture coefficient values of the films were determined. Microstructure was analyzed by SEM and the influence of the doping concentration in the microstructure of the films is investigated.     

Effect of ultrasound on the kinetics of cation exchange in NaX zeolite

In this study, we focused on the effect of ultrasound on ion exchange kinetics to obtain the Li-, Ca- and Ce-rich NaX zeolite. The results were compared to those obtained from the traditional batch exchange method under similar conditions. Contact time and initial cation concentration (fold equivalent excess) were studied. Ultrasound enhanced the replacement of Na⁺ ion with Li⁺, Ca²⁺ and Ce³⁺ ions in the extra-framework of zeolite up to 76%, 72% and 66%, respectively. The intraparticle diffusion is the rate limiting step in the ion exchange for both exchange methods. As compared to the traditional exchange method, the ultrasonic method applied in this study was found to be very effective on the exchange amount at equilibrium.     

Successive heterolytic cleavages of H2 achieve N2 splitting on silica-supported tantalum hydrides: a DFT proposed mechanism

DFT(B3PW91) calculations have been carried out to propose a pathway for the N(2) cleavage by H(2) in the presence of silica-supported tantalum hydride complexes [(≡SiO)(2)TaH(x)] that forms [(≡SiO)(2)Ta(NH)(NH(2))] (Science 2007, 317, 1056). The calculations, performed on the cluster models {μ-O[(HO)(2)SiO](2)}TaH(1) and {μ-O[(HO)(2)SiO](2)}TaH(3), labelled as (≡SiO)(2)TaH(x) (x = 1, 3), show that the direct hydride transfers to coordinated N-based ligands in (≡SiO)(2)TaH(η(2)-N(2)) and (≡SiO)(2)TaH(η(2)-HNNH) have high energy barrier barriers. These high energy barriers are due in part to a lack of energetically accessible empty orbitals in the negatively charged N-based ligands. It is shown that a succession of proton transfers and reduction steps (hydride transfer or 2 electron reduction by way of dihydride reductive coupling) to the nitrogen-based ligands leads to more energetically accessible pathways. These proton transfers, which occur by way of heterolytic activation of H(2), increase the electrophilicity of the resulting ligand (diazenido, N(2)H(-), and hydrazido, NHNH(2)(-), respectively) that can thus accept a hydride with a moderate energy barrier. In the case of (≡SiO)(2)TaH(η(2)-HNNH), the H(2) molecule that is adding across the Ta-N bond is released after the hydride transfer step by heterolytic elimination from (≡SiO)(2)TaH(NH(2))(2), suggesting that dihydrogen has a key role in assisting the final steps of the reaction without itself being consumed in the process. This partly accounts for the experimental observation that the addition of H(2) is needed to convert an intermediate, identified as a diazenido complex [(≡SiO)(2)TaH(η(2)-HNNH)] from its ν(N-H) stretching frequency of 3400 cm(-1), to the final product. Throughout the proposed mechanism, the tantalum remains in its preferred high oxidation state and avoids redox-type reactions, which are more energetically demanding.