Self-diffusion of water-ethanol mixtures in polyacrylic acid-polysulfone composite membranes obtained by pulsed-field gradient nuclear magnetic resonance spectroscopy

The self-diffusion of water, ethanol and water-ethanol mixtures in polyacrylic acid (PAA) and PAA-polysulfone (PSF) composite membranes was measured with pulsed-field gradient (PFG)-nuclear magnetic resonance (NMR) spectroscopy. The partial solubilities and self-diffusion coefficients were obtained. An attempt was made to explain the transport properties of water and ethanol through the PAA layer and PAA-PSF composite membranes. It was concluded that there are two types of channels for diffusate transfer in PAA: an ionogenic hydrophilic channel which is selective for water and a hydrophobic channel which contains a predominance of ethanol molecules. The existence of aluminum nitrate in PAA influences the morphology of the latter channel. There is a good agreement between of the separation factors estimated from PFG-NMR data and those obtained by pervaporation testing.     

NMR-ON measurements of187WFe,182,183,186ReNi,186ReFe and203PbFe

The magnetic hyperfine splitting frequencies of¹⁸⁷WFe,¹⁸²Re(j ^π=2⁺)Ni,¹⁸³ReNi,¹⁸⁶ReNi,¹⁸⁶ReFe and²⁰³PbFe in a zero external magnetic field have been determined by the NMR-ON method at about 7 mK as 225.56(6), 130.9(1), 98.17(4), 136.6(4), 1007.0(3) and 58.43(3) MHz, respectively. With the knowng-factors ofg(¹⁸⁶Re, 1⁻)=1.739(3) andg(²⁰³Pb, 5/2⁻)=0.27456(20), the following hyperfine fields were deduced:B _HF(¹⁸⁶ReNi)=−103.05(35) kG;B _HF(¹⁸⁶ReFe)=−759.7(13) kG;B _HF(²⁰³PbFe)=+279.18(25) kG. Taking hyperfine anomalies into account, theg-factor of¹⁸³Re was deduced as |g(¹⁸³Re, 5/2⁺)|=1.267(6). With the assumption of Knight shift factorK=0, theg-factors of¹⁸²Re and¹⁸⁷W and the hyperfine field of¹⁸⁷WFe were determined as |g(¹⁸²Re, 2⁺)|=1.63(5), |g(¹⁸⁷W, 3/2⁻)|=0.414(10) andB _HF(¹⁸⁷WFe) =−714(18) kG. The large hyperfine anomaly was deduced to be¹⁸³W Δ¹⁸⁷W =−0.124(22).     

Photoreflectance and photoluminescence study of short period (GaAs)n/(AlAs)n superlattices with n = 1 – 15

Photoreflectance and photoluminescence measurements were performed in (GaAs)_n/(AlAs)_n (n = 1 – 15) short-period superlattices in the temperature range from 25 K to 275 K. Weak signals of photoreflectance associated with the critical point of the pseudodirect transition, weakly allowed direct transition arising from the zone-folding effect, have been observed as well as main signals associated with the direct allowed transitions. This assignment is supported by the measurement and analysis of the temperature dependence of the photoluminescence intensity.     

Orientation of polymer molecules during melt spinning. II. Orientation of crystals in as-spun polyolefin fibers

Three different polyolefins, a linear polyethylene, an isotactic polypropylene, and an isotactic polybutene-1, were melt-spun into filaments. The degree of orientation of the filaments was measured by polarized-light microscopy, x-ray diffraction, and a retraction technique, and the results were then related to the melt-draw ratio. The increase in the elastic deformation ratio of polymer chains by spin-stretching, estimated by thermal retraction at a temperature above T_m, was monotonic with respect to the melt-draw ratio. On the other hand, as-spun filaments of polyethylene and polypropylene were characterized by a plateau in birefringence over the range of melt-draw ratios from 8 to 80. The change in orientation functions for crystals in these filaments was similar to the change of birefringence. On the other hand, the birefringence and the crystalline orientation functions for polybutene-1 increased smoothly with increasing melt-draw ratio. The most highly melt-drawn filaments of these polymers had a strongly oriented structure, corresponding to that in highly cold-drawn specimens.     

McMillan type convergence for quantum Gibbs states

Partially supported by the Hungarian National Foundation of Scientific Research, grant No. 1900.     

Effect of solid walls on spontaneous wave formation at water/oil interfaces

The regulation of spontaneous waves at water/oil interfaces was investigated, focusing on effects of materials and sizes of containers. Trimethylstearylammonium chloride was dissolved in an aqueous phase. Nitrobenzene with potassium iodide and iodine was used as an organic phase. Rotation of interfacial waves with almost triangular shape was observed only in containers made of glass. The nature of interfacial waves is sensitive to container size. There was no interfacial wave in PFA (Teflon) containers. However, when a glass plate was soaked vertically to the interface, oscillation of contact angles of water/oil interfaces to glass plates was observed. The oscillation generated wave propagation along the plate. Dynamic interfacial tension was measured by Wilhelmy method and the pendant drop technique. Results with the Wilhelmy method in small glass containers exhibited spontaneous oscillation. However, oscillations in dynamic interfacial tension were not observed for other cases, i.e., the Wilhelmy method for large glass containers, for PFA containers, and for the pendant drop technique. It was concluded that all nonlinear behavior such as wave generation and apparent tension oscillation could be attributed to the effect of the sidewalls of container on the adsorption/desorption kinetics of the surfactant. We propose a possible scenario which can explain all of the qualitative features of the present experimental findings.     

Cyclization/acylation reactions by nickel-catalyzed reactions of 1,6-ynal and 1,6-enyne derivatives with acylzirconocene chloride

NiCl₂(PPh₃)₂-catalyzed reactions of 1,6-ynal or 1,6-enyne compounds with n-nonanoylzirconocene chloride afforded stereoselectively cyclopentane derivatives or bicyclo[3.1.0] compounds by catalytic cyclization/acylation reactions, which would involve (i) the primary formation of a metallacycle followed by (ii) the transfer of an acyl group from the acylzirconocene complex (transmetalation).     

Synthesis of (+)-conagenin

An efficient total synthesis of (+)-conagenin was achieved. The right fragment of conagenin, alpha-methylserine containing a quaternary stereocenter attached to nitrogen, was synthesized using allyl cyanate-to-isocyanate rearrangement. The left fragment, 2,4-dihydroxy-3-methylpentanoic acid, has three contiguous stereogenic centers, which was efficiently constructed by enantioselective monoreduction of 2-alkyl-1,3-diketones reported by Cossy, and chelation-controlled stereoselective reduction of beta-hydroxy ketone. These two fragments were coupled through intramolecular amide bond formation with high efficiency.     

Pyrolysis reaction of carpronium chloride and its structurally related compounds. 1—electronic and steric effects on the orientation of the pyrolysis reaction

The pyrolysis reaction of carpronium chloride and its structurally related compounds, which were trimethyl-aminoalkyl acid alkyl esters involving two, three or four skeletal methylene groups, have been investigated by pyrolysis gas chromatography mass spectrometry. The results indicated that the reaction modes of these ammonium compounds were essentially dependent on the number of skeletal methylene groups, and secondarily on the length of the carbon chain of the ester group. These phenomena have been interpreted in terms of electronic and steric contributions for the ionic elimination reaction. The electronic and steric effects on the orientation of the reaction are discussed on the basis of the atomic population calculated by the CNDO/2 method.