Simple and Convenient Synthesis of 21‐Thioalkylether Derivatives of Methyl 16‐Prednisolone Carboxylates

The antedrug approach for corticosteroids has been described as a fundamentally sound approach for the development of safer anti‐inflammatory and anti‐asthmatic therapy. However, the derivatization of prednisolone and its congeners have been considered to be major pitfalls, because their syntheses are complicated by the presence of numerous carboxylate esters and hydroxyl functions in the steroid nucleus. A simple and direct synthesis of 21‐thioalkylether derivatives of methyl 16‐prednisolonecarboxylates is described. The 21‐mesylate of the methyl 16‐prednisolonecarboxylate and 9‐fluoro‐17‐dehydro methyl 16‐prednisolonecarboxylate were reacted with Na‐thioalkoxides to furnish the desired thioethers in good yields. A previously published method for the methanolysis of 16‐cyanoprednisolone to methylcarboxylate has been reexamined, and the conditions are explained clearly. The reaction conditions for all these reactions were critical.     

Estimation of the surface energetic heterogeneity of fillers by inverse gas chromatography

The surface properties of the fillers are determining for obtaining high performance filled polymers. Yet, their determination is most difficult. This paper proposes to use inverse gas chromatography, either at infinite dilution or finite concentration conditions, to estimate surface energy and nanomorphological characteristics, but also surface heterogeneity of different clays, talcs of various origins and ground muscovites.     

High-temperature heat capacity,thermodynamic properties and debye temperature of CuGe2P3

The heat capacity at constant pressure of CuGe₂P₃ is measured in the temperature range from 180 to 550 K. Standard enthalpies and entropies relative to 298.15 K are calculated from the heat capacity data. The Debye temperature in the high-temperature limit is estimated to be about 710 K.     

Cross-gain modulation in closely spaced energy states quantum dash semiconductor optical amplifiers

A detailed small-signal analysis of cross-gain modulation is performed for closely spaced energy state quantum dash (QDsh) semiconductor optical amplifier (SOA). The analysis takes into account the carrier transition in all electron and hole states, the gain dispersion of the active layer, the effect of the energy detuning between the probe and pump signals and the effect of doping on the characteristics of cross-gain wavelength conversion. Our analysis reveals that broadband conversion efficiency can be obtained in QDsh SOA when the energy of the pump signal is at − 20 meV below the ground state. Also we find that large 3 dB bandwidth can be achieved when the energy of the pump and the probe signals is at + 30 meV. Our analysis shows that doping the dashes with P-type concentration can enhance the efficiency and the intrinsic 3 dB bandwidth of cross-gain wavelength conversion.     

Contrast ratio and hysteresis width of optical bistability in quantum-dot vertical-cavity semiconductor optical amplifiers integrated with MEMS membrane

The characteristics of optical bistability in quantum dot vertical cavity semiconductor optical amplifier integrated with MEMS membrane have been investigated, and a closed-form model is derived taking into account the effect of the quantum dot discrete states and the membrane deflection and reflectivity. We show that small membrane deflection significantly adjusts the resonant wavelength, the contrast ratios and the hysteresis width. The shape of the input–output characteristics of the device can be adjusted to display clockwise, butterfly and counterclockwise hysteresis loops depending on the membrane deflection and the initial wavelength detuning. Our analysis reveals that the contrast ratios of the upper and lower bistable levels are totally different. Also, it has been shown that the characteristics of the bistability are strong function of the active layer linewidth enhancement factor and the membrane reflectivity.     

Validation and Correction for 208Tl Activity to Assay 232Th in Equilibrium with Its Daughters

Physics of Particles and Nuclei Letters - The natural radioactivity measurements and analysis of 232Th have been studied using γ-ray spectroscopy depending on its decay daughters in...     

Auger electron emission in proton-induced interactions in living matter: A TILDA-V Monte Carlo tracking

The present work focuses on studying the contribution of the Auger electron emission in proton-induced interactions in biological matter. The Monte Carlo track-structure code, TILDA-V, was then used for modeling the protons beams of 10 keV to 100 MeV in biological matter, namely, water vapor and hydrated DNA. The main ionizing processes are described by means of an extensive set of ab initio differential and total cross sections computed within a quantum-mechanical CDW-EIS approximation.     

Solvatochromism of 2‐(N,N‐dimethylamino)‐7‐nitrofluorene and the natural dye β‐carotene: application for the determination of solvent dipolarity and polarizability

The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd.     

The Field-Dependent Magnetization of d5–d7 Metal β−Diketonate Complexes and Their Macromolecular Polymers

A vibrating sample magnetometer (VSM) has been used to study the field-dependent magnetization, M(H), of the d⁵?d⁷ metal acetates [M(OAc)₂.nH₂O], metal β?diketonate complexes [M(tba)₂(H₂O)₂] and the macromolecular polymers [M(tba)₂(4,4-bipy)]_n (where, M = Mn(II), Fe(II), and Co(II), OAc = O₂CCH₃, tba = deprotonated 3-benzoyl-1.1.1-trifluoroacetone, and 4,4-bipy = 4,4′-bipyridine). The magnetic field strength (H) was applied in the range of 0?10⁴ O_e at ambient temperature (ca. 23°C). The experimental results showed that the d⁵?d⁷ metal acetate, complexes and polymers exhibit low paramagnetic properties excepting [Fe(tba)₂(4,4-bipy)]_n polymer, which had negative magnetization M(emu/g) showing diamagnetic properties in the range 0?10⁴ O_e. The magnetization was almost equal to zero without an applied magnetic field (H(O_e)) for each d⁵?d⁷ metal acetate, complex, and polymer. The linear M(H) curve had a magnetic saturation for iron and manganese acetate species at the magnetic field strengths of 3.1 × 10³ and 4.7 × 10³ Oe, respectively. The external magnetic field reached 9.0 × 10³ O_e without any saturation magnetization for the cobalt compounds. The coordination effect of 3-benzoyl-1.1.1-trifluoroacetone (H-tba) and 4,4′-bipyridine (4,4′-bipy) ligands on the field-dependent magnetization M(H) and paramagnetic behavior of d⁵?d⁷ metal atoms is discussed. The field-dependent magnetization M(H) curves of metal β?diketonate complexes and the polymers including d⁵?d⁷ metal acetates showed a weak field octahedral geometry.