Synthesis,electrochemistry, and electrocatalytic activity of thiazole-substituted phthalocyanine complexes

Journal of Solid State Electrochemistry - We report the synthesis of non-peripheral metallophthalocyanines which carry four 4-(4-methoxyphenyl)-2-thiazole-2-thio units. 1H-NMR, FT-IR, UV–Vis,...     

Analysis of diversity schemes employing antenna selection in the presence of channel estimation errors and feedback delay

The main objective of this paper is to provide an extensive and complete examination on the effect of practical impairments such as channel estimation errors (CEEs) and feedback delay (FD) on the performance of diversity schemes over Nakagami‐m fading channels. Under erroneous channel estimation and outdated feedback cases, statistical expressions and several performance metrics related to the post‐processing signal‐to‐noise ratio (SNR) are derived for four different diversity schemes: transmit antenna selection (TAS)/orthogonal space–time block coding, TAS/maximal‐ratio transmission (MRT), MRT/receive antenna selection (RAS), and joint transmit and RAS. Exact analytical expressions for outage probability and average error rates of M‐ary modulations are derived in order to provide insightful perspectives on the capacity and error performance of diversity schemes that experience both CEE and FD. The asymptotic diversity order of the investigated diversity schemes are derived via a high‐SNR approximation approach. In order to assess the real‐world performance of the investigated diversity schemes and to observe their robustness or sensitivities in practical imperfections, various configurations are considered together with several performance comparisons. Also, Monte Carlo simulations are performed in order to validate the theoretical results. Copyright © 2014 John Wiley & Sons, Ltd.     

Rhenium/rhenium oxide nanoparticles production using femtosecond pulsed laser ablation in liquid

In this study, rhenium/rhenium oxide nanoparticles (Re / ReO₃ NPs) have been produced for the first time in ultrapure water by using Femtosecond Pulsed Laser Ablation in Liquid (fsPLAL) method. X-Ray Diffraction (XRD) measurements and results obtained for NPs show the existence of well-crystallized peaks and preferred phases. Re NPs have hexagonal structure while ReO₃ NPs have the perovskite-like cubic crystal structures. The Re / ReO₃ ratio is also determined to be 53 / 47 with ~ 20 nm crystallite size, while pure ReO₃ crystallite sizes were measured to be ~ 25 nm. The TEM results have shown that the produced particles have a spherical shape, and particle sizes changes between ~ 20 nm and ~ 60 nm. The crystallite size is similar due to XRD results. Obtained nanoparticles exhibit promising applications for photonic devices with broad bandgap values which have measured to be 4.71 eV for Re / ReO₃ NPs mixture and 4.36 eV for pure ReO₃ NPs.     

Synthesis,crystal structure,spectroscopy, thermal properties and carbonic anhydrase activities of new metal(II) complexes with mefenamic acid and picoline derivatives

The mononuclear six metal(II) complexes ([Co(mef)₂(3-pic)₂(CH₃OH)₂] (1), [Ni(mef)₂(3-pic)₂(CH₃OH)₂] (2), [Cu(mef)₂(3-pic)₂] (3), [Co(mef)₂(4-pic)₂] (4), [Ni(mef)₂(4-pic)₂] (5), and [Cu(mef)₂(4-pic)₂] (6) with mefenamic acid and picoline ligands were synthesized, characterized, and their carbonic anhydrase inhibitory activities were evaluated. The six complexes were characterized by elemental analysis, FT-IR spectroscopy, and thermal analyses. The crystal structures of 1, 3, and 6 were determined by X-ray crystallography. The complexes have octahedral geometry. In 1, the mefenamato ligand behaved as monodentate whereas in 3 and 6, the mefenamato ligand acted as a bidentate ligand. Complexes 3 and 6 consist of the mefenamate and 4-picoline ligands. In 1, unlike the other complexes, methanol acted as a ligand and was involved in the coordination. Carbonic anhydrase I and II isoenzymes were purified from human erythrocytes. The in vitro effects of mefenamic acid, 3-picoline, 4-picoline, and the six metal(II) complexes on these isoenzymes were evaluated.     

A new dioxime ligand and its trinuclear copper(II) complex: Synthesis, characterization and optical properties

The synthesis and characterization of a new dioxime ligand, (H₂L), (III) and its trinuclear copper(II) complex, [Cu₃L₂(H₂O)₂](ClO₄)₂, (V) is described. IR spectra show that the ligand acts in a tetradentate manner and coordinates N₄ donor groups of H₂L to copper(II) ion. The structure of the metal chelate is clarified with the help of elemental analysis, magnetic moment, conductometric and spectroscopic measurements. The optical absorption studies reveal that the transition is direct with band gap energy values are calculated. The optical constants such as refractive index and dielectric constant of the compound were determined. The refractive index dispersion curves of the films obey the single-oscillator model and oscillator parameters. Optical dispersion parameters E₀ and E_d developed by Wemple-DiDomenico were calculated.     

Fluorescence of Zn(II) 8-hydroxyquinoline complex in the presence of aqueous micellar media: The special cetyltrimethylammonium bromide effect

Mixtures of Zn(II) and 8-hydroxyquinoline (8QOH) in a 1:2 proportion, in aqueous solutions, result in fast complexation, followed by precipitation. Addition of 0.05 M sodium dodecyl sulfate (SDS), N-dodecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-12), N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-16) or Triton X-100 results in considerable retardation of precipitation. In the presence of SDS, SB3-12, SB3-16 and Triton X-100 the 8QOH chelates are only kinetically stable in solution and after 24 h, the precipitation is almost quantitative. Conversely, upon addition of the cationic surfactant hexadecyltrimethylammonium bromide (CTABr), the absorbance of the complex remains constant even after at least six months. The interaction of the ligand 8QOH (and of the (8QO)(2)Zn(II) complex) with the cationic surfactant was studied by ultraviolet and NMR spectroscopy and 8QOH has a pK(a)=9.05 in the presence of the cationic surfactant and the ligand intercalates in the micelle, being preferentially located near the headgroup of the micelle. Although the solubilization site of the (8QO)(2)Zn(II) complex is similar to that of 8QOH, the interaction of the aromatic moiety with the CTA(+) headgroup is much stronger, due to the increased electron density in the aromatic ring of the ligand. As a consequence of this interaction, sphere to rod transition and an increase in microscopic and macroscopic viscosity are observed.     

The chameleon-like nature of zwitterionic micelles. Control of anion and cation binding in sulfobetaine micelles. Effects on acid equilibria and rates

The rate of specific hydrogen ion catalyzed hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane and equilibrium protonation of 1-hydroxy-2-naphthoate ion in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3-, are increased markedly by NaClO4 which induces anionic character and uptake of H3O+ in the micelles. Other salts, for example, NaNO3, NaBr, and NaCl, have similar but much smaller effects on this uptake of H3O+.     

Specific anion binding to sulfobetaine micelles and kinetics of nucleophilic reactions

With fully micellar bound substrates reactions of OH- with benzoic anhydride, Bz(2)O, and of Br- with methyl naphthalene-2-sulfonate, MeONs, in micellized sulfobetaines are strongly inhibited by NaClO4 which displaces the nucleophilic anions from the micellar pseudophases. Micellar incorporations of ClO4- and Br- are estimated with an ion-selective electrode and by electrophoresis, and partitioning of Br- between water and micelles is related to changes in NMR spectral (79)Br- line widths. Extents of inhibition by ClO4- of these nucleophilic reactions in the micellar pseudophase are related to quantitative displacement of the reactive anions from the micelles by ClO4-. The kinetic data are correlated with physical evidence on the strong interactions between sulfobetaines and ClO4-, which turn sulfobetaine micelles anionic and effectively provoke displacement of OH- and Br-.     

Remarkable bismuth-gold alloy decorated on MWCNT for glucose electrooxidation: the effect of bismuth promotion and optimization via response surface methodology

In this study, the carbon nanotube supported gold, bismuth, and gold-bismuth(Au/MWCNT, Bi/MWCNT, and Au-Bi/MWCNT) nanocatalysts were prepared with NaBH₄ reduction method at varying molar atomic ratio for glucose electrooxidation (GAEO). The synthesized nanocatalysts at different Au: Bi atomic ratios are characterized via x - ray diffraction (XRD), transmission electron microscopy (TEM), and N₂ adsorption-desorption. For the performance of AuBi/MWCNT for GAEO, electrochemical measurements are performed by using different electrochemical techniques namely cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Monometallic Au/MWCNT exhibits higher activity than Bi/MWCNT with 256.57 mA/mg (0.936 mA/cm²) current density. According to CV results, Au₈₀Bi₂₀/MWCNT nanocatalyst has the highest GAEO activity with the mass activity of 320.15 mA/mg (1.133 mA/cm²). For Au₈₀Bi₂₀/MWCNT, central composite design (CCD) is utilized for optimum conditions of the electrode preparation. Au₈₀Bi₂₀/MWCNT nanocatalysts are promising anode nanocatalysts for direct glucose fuel cells (DGFCs).     

Stress-Dependent Porosity and Permeability of Porous Rocks Represented by a Mechanistic Elastic Cylindrical Pore-Shell Model

The stress dependency of the porosity and permeability of porous rocks is described theoretically by representing the preferential flow paths in heterogeneous porous rocks by a bundle of tortuous cylindrical elastic tubes. A Lamé-type equation is applied to relate the radial displacement of the internal wall of the cylindrical elastic tubes and the porosity to the variation of the pore fluid pressure. The variation of the permeability of porous rocks by effective stress is determined by incorporating the radial displacement of the internal wall of the cylindrical elastic tubes into the Kozeny–Carman relationship. The fully analytical solutions of the mechanistic elastic pore-shell model developed by combining the Lamé and Kozeny–Carman equations are shown to lead to very accurate correlations of the stress dependency of both the porosity and the permeability of porous rocks.