Debye process and dielectric state of an alcohol in a nonpolar solvent

To investigate the origin of the first order molecular kinetics of the most prominent, Debye-type polarization, a detailed dielectric relaxation study of 66.5, 40, and 20 mole% solutions of 5-methyl-2-hexanol in 2-methylpentane (2:1, 0.67:1, and 0.25:1 molar ratios) was performed. The Debye-type polarization remains prominent in the solutions, despite the extensive loss of intermolecular hydrogen bonds. At high temperatures, its contribution to permittivity extrapolates close to the statistically scaled values for the 2:1 solution. For others, the measured values of its contribution crossover the scaled values in a temperature plane. The faster relaxation process of about 4% magnitude has an asymmetric distribution of times in the solutions and, relative to those of the pure alcohol, their values decrease on heating more at high temperatures and less at low. This is attributed to an increase in the alcohol cluster size by consumption of monomers as well as the growth of smaller clusters as the solution is cooled. It is argued that structural fluctuation in solutions, as in the pure alcohol, is determined by the rates of both the Debye-type and the faster polarizations in the ultraviscous state.     

Synthesis, characterization, mechanochromism and photochromism of [Fe(dm4bt)3][FeCl4]2 and [Fe(dm4bt)3][FeBr4]2, along with the investigation of steric influence on spin state

The complexes [Fe(dm4bt)(3)][FeCl(4)](2) (1) and [Fe(dm4bt)(3)][FeBr(4)](2) (2) were prepared from the reaction of 2,2'-dimethyl-4,4'-bithiazole (dm4bt) with FeCl(3)·6H(2)O and FeBr(3), respectively, in methanol. Both complexes were characterized by IR, UV-Vis and (1)H NMR spectroscopy and their structures were studied by single-crystal diffraction. The methylated bithiazole led to high spin Fe(II) centers in the octahedral cation part of complexes 1 and 2 with Fe-N distance of 2.220 ?, in spite of the low spin octahedral Fe(II) complexes with unsubstituted bithiazole ligands. Crystal structure determination of 2 was performed at 90, 120 and 298 K. Temperature reduction to 90 K resulted in a decrease in the Fe-N bond length to 2.206 ? which is still in the range of high spin Fe(II). Complex 1 shows a reversible mechanochromic effect from the crystalline phase to powder form from red to yellow; it also displays reversible photochromism from yellow to green in solution under sunlight. The magnetic behaviour of the complexes was also studied at 2-300 K. The temperature dependence of χ(m)T curves for the two forms of 1, crystal and powder, demands some changes in their magnetic behavior, causing different colors i.e. red and yellow. At low temperatures, χ(m)T decreases where the decrease starts at around 65 K for compound 1, and at around 100 K for compound 2, due to different counterions. The two complexes exhibit antiferromagnetism at around 4 K.     

Microextraction of phenolic compounds using a fiber coated with a polyaniline-montmorillonite nanocomposite

Microchimica Acta - A highly porous fiber coated polyaniline/montmorillonite clay was prepared for solid-phase microextraction. The nanocomposite was synthesized by in-situ polymerization. The...     

Polypyrrole–montmorillonite nanocomposite as sorbent for solid‐phase microextraction of phenolic compounds in water

A fiber‐coated polypyrrole–montmorillonite nanocomposite was prepared for solid‐phase microextraction. The fiber coating can be prepared easily; it is mechanically stable and exhibits relatively high thermal stability. The prepared fiber was evaluated for the extraction of some phenolic compounds from aqueous sample solutions by gas chromatography–mass spectrometry. The effects of the extraction and desorption parameters including extraction time, extraction temperature, stirring rate, ionic strength, pH and desorption temperature and time have been studied. At optimum conditions, the repeatability for one fiber (n = 5), expressed as % relative standard deviation was between 6.5 and 7.8% for the phenolic compounds. The detection limits for the studied phenolic compounds were between 0.05–1.3 ng/mL. The developed method offers the advantage of being simple to use, with shorter analysis time, lower cost, thermal stability of the fibers, and high relative recovery in comparison to conventional methods of analysis.     

Detection of Dexamethasone Sodium Phosphate in Blood Plasma: Application of Hematite in Electrochemical Sensors

We studied sensor application of a graphene oxide and hematite (α‐Fe₂O₃/GO) composite electrode well‐characterized by the SEM and XRD. Through differential pulse voltammetry (DPV), oxidation of dexamethasone sodium phosphate (DSP) was studied at the surface of a glassy carbon electrode (GCE) modified with graphene oxide nanosheets (GO) and the α‐Fe₂O₃/GO composite. The values of the transfer coefficient (α) and the diffusion coefficient (D) of DSP were 0.5961 and 4.71×10^?5 cm² s^?1 respectively. In the linear range of 0.1–50 μM, the detection limit (DL) was 0.076 μM. In the second step, a GCE was modified with α‐Fe₂O₃/GO composite and the DSP measurement step was repeated to analyzed and compare the effects of hematite nanoparticles present on graphene oxide surfaces. According to the results, α and D were 0.52 and 2.406×10^?4 cm² s^?1 respectively and the DL was 0.046 μM in the linear range of 0.1–10.0 μM. The sensor is simple, inexpensive and uses blood serum.     

C-H activation in bithiazole ring with thallium(III) ion

Two novel organometallic complex of 2,2′-dimethyl-4,4′-bithiazole (dm4bt) ligand (L) with formula [Tl(dm4bt)₂(NO₃)(H₂O)] (1) and [Tl(dm4bt)₂(NO₃)(DMSO)] (2) have been synthesized and structurally characterized by elemental analysis, FT-IR, ¹H NMR spectra and X-ray crystallography. These complexes also display the first transoid conformation in bithiazole ligands in which C-H bond activation in bithiazole ring is observed with Tl(III) ion.     

A dielectric study of chain motions in poly(vinyl methyl ether)

The dielectric permittivity and loss of poly(vinyl methyl ether) (mol. wt. 30,000) have been measured from 12 Hz to 100 kHz at temperatures from 77 K to 320 K. Two relaxation processes, γ and β, are observed at T < T_g (245 K), and one above T_g. The Arrhenius plots of the γ and β processes have activation energies of 20 and 41 kJ mole^?1 respectively. The relaxation rate of the α process is described by the Vogel-Fulcher-Tamman equation or the William-Landel-Ferry equation. The relaxation rates of γ and β processes evaluated from the isochrones differ from those evaluated from the isothermal spectrum. The features of chain motions observed are similar to those in other polymer and rigid molecular glasses.     

Comment on “Delayed luminescence of biological systems in terms of coherent states” [Phys. Lett. A 293 (2002) 93]

Popp and Yan [F.A. Popp, Y. Yan, Phys. Lett. A 293 (2002) 93] proposed a model for delayed luminescence based on a single time-dependent coherent state. We show that the general solution of their model corresponds to a luminescence that is a linear function of time. Therefore, their model is not compatible with experimental delayed luminescence. Moreover, the functions that they use to describe the oscillatory behaviour of delayed luminescence are not solutions of the coupling equations to be solved.     

Hybrid Proximal Point Algorithm and Applications to Equilibrium Problems and Convex Programming

The problem of finding minima of weakly sequentially lower semicontinuous functions on reflexive Banach spaces is studied by means of convex and nonconvex subdifferentials. Finding a descent direction for a non-stationary point is a question of importance for many optimization algorithms. The existence or non-existence of such a direction is clarified through several theorems and a series of selective examples. For the general problem, a notion called radius of descent is proposed and shown to be useful for the analysis related to descent directions.