Effect of temperature on intrinsic permeation properties of 6FDA-Durene/1,3-phenylenediamine (mPDA) copolyimide and fabrication of its hollow fiber membranes for CO2/CH4 separation

We have determined the effect of temperature on intrinsic permeation properties of 6FDA-Durene/1,3-phenylenediamine (mPDA) 50/50 copolyimide dense film and fabricated high performance hollow fiber membranes of the copolyimide for CO₂/CH₄ separation. The hollow fiber membranes were wet-spun from a tertiary solution containing 6FDA-Durene/mPDA (PI), N-methyl-pyrrolidone (NMP) and tetrahydrofuran (THF) with a weight ratio of 20:50:30 at different shear rates within the spinneret. We observed the following facts: (1) the CO₂/CH₄ selectivity of the copolyimide dense film decreased significantly with an increase in temperature; (2) the performance of as-spun fibers was obviously influenced by the shear rate during spinning. For uncoated fibers, permeances of CH₄ and CO₂ decreased with increasing shear rate, while selectivity of CO₂/CH₄ sharply increased with shear rate until the shear rate reached 2169 s⁻¹ and then the selectivity leveled off; (3) After silicone rubber coating, permeances of CH₄ and CO₂ decreased, the selectivity of CO₂/CH₄ was recovered to the inherent selectivity of its dense film. Both the permeances and selectivity with increasing shear rate followed their same trends as that before the coating; (4) there was an optimal shear rate at which a defect-free fiber with a selectivity of CO₂/CH₄ at 42.9 and permeance of CO₂ at 53.3 GPU could be obtained after the coating; and (5) the pressure durability of the resultant hollow fiber membranes could reach 1000 psia at room temperature.     

Rhodium catalyzed hydroacylation of ethylene with 4-pentenals. reactions of 4-hexenal-1-d

A catalyst derived from 2,4-pentanedionatobis(ethylene)rhodium(I), I, promoted the addition of 4-pentenal to ethylene. The reaction was accompanied by the formation of double bond migration products derived from the 4-pentenal reactant and from the 6-hepten-3-one primary product. Compound I accomplished the addition of 4-hexenal to ethylene to afford high yields of 6-octen-3-one. The fate of the aldehyde hydrogen in this transformation has been determined in experiments employing 4-hexenal-1-d as reactant. Treatment of 4-hexenal-1-d with I in CHCl₃ and CDCl₃ afforded 6-octen-3-one possessing >50% d_o molecules while the isotopic composition of recovered unexpended 4-hexenal remained >96% d₁. 6-Octen-3-one products with isotopic compositions of >66% d_o were afforded when ethylene was introduced to reaction mixtures. The location of deuterium in 6-octen-3-one, derived from treatment of 4-hexenal-1-d with I in the absence of added C₂H₄, was determined to be distributed at C-1 and C-2 and at the CC bond by analysis of the ¹H and ²H NMR spectra. Unexpended ethylene was recovered and was found to contain a substantial amount of deuterium. Mechanistic implications of these results are discussed.     

Gitterparameter und thermische Ausdehnungskoeffizienten des CdO zwischen 40 und 1300°K. Fehlbau des Oxids

The influence of excess Cd in CdO on the lattice parameter, color and density was explored. Eight samples were prepared by various methods and the lattice parameter determined. The oxides, showing no excess of Cd (as tested with KMnO₄) had all nearly the same a₂₅ = 4,6951 ± 0,0002 Å. The color of the samples varied from reddish brown to black; however, in transmitted light at high microscopic magnification, all of them appeared red. These and other facts led to the conclusion that Cd, if dissolved at elevated temperatures in CdO, segregates to a certain degree upon cooling. Hence, the lattice parameter increase due to solubility of Cd in CdO, had to be subtracted from the total to obtain the pure thermal expansivity: a straight line for a versus t between 300 and 1000°K resulted, α = 1,15 · 10^?5 deg^?1 was obtained. α started to decrease below 300° and became zero at 40°K. The density of the CdO heated in air was larger (99,67% of the theoretical 8.2375 gcm^?3 at 25°C) than that of the excess Cd containing oxide, indicating the presence of vacancies in larger amounts in the latter preparation.     

Pyrene functionalized oxacalix[4]arene architecture as dual readout sensor for expeditious recognition of cyanide anion

A pyrene functionalized oxacalix[4]arene architecture (DPOC) was utilized as a fluorescence probe for selective recognition of cyanide ions. The receptor DPOC shows excellent selectivity towards cyanide ion with a red shift of 108 nm in absorption band along with a significant change in colour from light yellow to pink. The fluorescence titration experiments further confirm the lower limit of detection as 1.7µM with no significant influences of competing anions. ¹ H-NMR titration experiments support the deprotonation phenomena, as the -NH proton disappears upon successive addition of cyanide ions. The DFT calculation also indicates a certain increment of -NH bond length upon interaction with cyanide ions. The spectral properties as well as colour of DPOC-CN^? system may be reversed upon the addition of Ag⁺/ Cu²⁺ ions up to 5 consecutive cycles. Moreover, DPOC coated “test strips” were prepared for visual detection of cyanide ions.

     

Vibrational dynamics of Fe-based glassy alloys

The well recognized model potential is used to investigate the vibrational properties of four Fe-based binary glassy alloys viz. Fe₉₀Zr₁₀, Fe₈₀B₂₀, Fe₈₃B₁₇ and Fe₈₀P₂₀. The thermodynamic and elastic properties are also computed from the elastic limits of the phonon dispersion curves (PDC). Three theoretical approaches given by Hubbard-Beeby (HB), Takeno-Goda (TG) and Bhatia-Singh (BS) are used in the present study to compute the PDC. Six local field correction functions proposed by Hartree (H), Taylor (T), Ichimaru-Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) and Sarkar et al.’s local field factor (SLFF) based excgange and correlation function are employed to see the effect of exchange and correlation in the aforesaid properties.     

New mesogens with a fluoro-substituted bent core

Ferroelectric properties in liquid crystals are no longer restricted to materials with a chiral molecular structure; ferroelectricity has been observed in a smectic phase formed by bent achiral molecules. Accordingly, two homologous series possessing a central biphenyl methane core have been synthesized, the central core having two lateral fluoro substituents. Both the series have six-ring structures and exhibit smectic mesophases of high thermal stability. The flexible biphenyl methane core imparts a slight curve to the molecules, giving them a bent shape.     

Novel Azoester Compounds with a Lateral Methyl Substituent

Twelve novel homologues with an azo linkage of the series 4-carbethoxy-[3′methyl-4′ (4^″-n-alkoxy benzoyloxy)] azobenzenes have been synthesized. The methyl to n-hexyl homologues exhibit only nematic mesophases, while the n-heptyl to n-tetradecyl homologues exhibit both smectic and nematic mesophases. The n-hexadecyl homologue exhibits only a smectic mesophase. The plot of transition temperatures versus number of carbon atoms in alkoxy chain exhibits an odd-even effect for the nematic-isotropic transitions. The mesogenic behavior of present series is explained by comparing each homolog of the related mesogenic series. The synthesized compounds were characterized by a combination of elemental analysis and standard spectroscopic methods. For the exhibition of mesomorphic property the role of ester and azo linkages has been discussed. The impact of the lateral methyl group on mesomorphism is also discussed.     

Host–guest complexes of the antituberculosis drugs pyrazinamide and isoniazid with cucurbit[7]uril

The potential use of cucurbit[7]uril (CB[7]) as an excipient in oral formulations for improved drug physical stability or for improved drug delivery was examined with the antituberculosis drugs pyrazinamide (pyrazine-2-carboxamide) and isoniazid (isonicotinohydrazide). Both drugs form 1:1 host–guest complexes with CB[7] as determined by ¹H nuclear magnetic resonance spectrometry, electrospray ionisation mass spectrometry and molecular modelling. Drug binding is stabilised by hydrophobic effects between the pyridine and pyrazine rings of isoniazid and pyrazinamide, respectively, to the inside cavity of the CB[7] macrocycle as well as hydrogen bonds between the hydrazide and amide groups of each drug to the CB[7] carbonyl portals. At pH 1.5, isoniazid binds CB[7] with a binding constant of 5.6 × 10⁵ M^?1, whilst pyrazinamide binds CB[7] at pH 7 with a much smaller binding constant (4.8 × 10³ M^?1). Finally, CB[7] prevents drug melting through encapsulation. Where previously pyrazinamide displays a typical melting point of 189 °C and isoniazid 171 °C, by differential scanning calorimetry, no melting or degradation at temperatures up to 280 °C is observed for either drug once bound by CB[7].     

An experimental study and theoretical analysis of the mode characteristics of a narrow line-width,pulsed dye laser oscillator at different pump powers

This paper presents an experimental study and theoretical analysis on the effect of pump power on the divergence, pointing, line-width and wavelength stability of a narrow line-width, high repetition rate dye laser oscillator. The dye laser oscillator, based on the hybrid multiple-prism grazing-incidence grating cavity, was pumped by copper vapor laser (CVL). The dye laser mode characteristics were studied at CVL average pump powers of 2, 4 and 8 W. The single pulse dye laser divergence/pointing stability was studied by far-field intensity distributions. The line-width and wavelength stability were studied using a high resolution wave-meter. The experimental results were theoretically analyzed in terms of dye laser mode structure drift induced by beam pointing instability, beam divergence and thermally induced optical path length fluctuation. A comprehensive theoretical treatment on pointing stability of dye laser beam and its influence in the dye laser wavelength stability is presented. The theoretical and experimental trends were found to be in good agreement.