Permeability,permselectivity, and penetrant‐induced plasticization in fluorinated polyimides studied by positron lifetime measurements

The ortho‐positronium (o‐Ps) lifetime τ₃ and its intensity I₃ in various fluorinated polyimides were determined by the positron annihilation technique and were studied with the spin–lattice relaxation time T₁ and the propylene permeability, solubility, diffusivity, and permselectivity for propylene/propane in them. τ₃, I₃, and the distribution of τ₃ changed when the bulky moieties in the polyimides were changed. The polyimides, having both large τ₃ and I₃ values, exhibited a short T₁ and a high permeability with a low permselectivity. The propylene permeability and diffusivity were exponentially correlated with the product of I₃ and the average free‐volume hole size estimated from τ₃. In highly plasticized states induced by the sorption of propylene, the permeability increased with the propylene pressure in excellent agreement with the change in the free‐volume hole properties probed by o‐Ps. The large and broad distribution of the free‐volume holes and increased local chain mobility for the 2,2‐bis(3,4‐decarboxyphenyl) hexafluoropropane dianhydride‐based polyimides are thought to be important physical properties for promoting penetrant‐induced plasticization. These results suggest that o‐Ps is a powerful probe of not only the free‐volume holes but also the corresponding permeation mechanism and penetrant‐induced plasticization phenomenon. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 308–318, 2003     

Integral Method o Reciprocity in the Spectroscopy of Laser Crystals with Impurity Centers

A new method of determining the stimulated emission cross-section spectra from the absorption cross-section spectra, which we call the integral method of reciprocity, is suggested it does not require knowledge of the structure of the impurity-center electron levels. Based on this method, formulas for calculating the radiation lifetime of impurity centers in crystals have been derived. The effectiveness of the integral method of reciprocity was demonstrated in determining the stimulated emission cross sections and radiation lifetime of an ytterbium ion in the laser crystals Yb³⁺:KYW and Yb³⁺:KGW.     

Complete assignment of the 1H and 13C NMR spectra of four 2‐substituted 4a,8a‐cis‐endo‐5,8‐methano‐4a,5,8,8a‐tetrahydronaphthalene‐1,4‐diones

The complete assignment of the ¹H and ¹³C NMR spectra of the title enediones, bearing as substituents N‐aziridinyl (a novel compound), methoxy, chloro and methylsulfanyl, is reported. Copyright © 2002 John Wiley & Sons, Ltd.     

Morphology and spectral properties of thin films of benzoxazole derivatives of biphenyl

We have studied the spectral properties and morphology of thin films (TVD films) formed by thermal vacuum deposition of 4,4′-bis[(E)-1-(1,3-benzoxazol-2-yl)-2-ethenyl]-1,1′-biphenyl and its substituted derivatives. We have shown that introducing bulky 2,2′-oxyhexyl substituents into the biphenyl units leads to a shift of the fluorescence maximum for the TVD films toward shorter wavelengths, a decrease in their photostability, and aggregation of the films during storage. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 300–303, May–June, 2007.     

五种氨基酸钆络合物的ESR波谱

迄今未见任何稀土氨基酸络合物的ESR波谱报道,本文在合成Gd³⁺分别与甘氨酸、β-丙氨酸、谷氨酸、天冬氨酸和天冬酰胺五种氨基酸络合物的基础上,测定了不同温度下,水溶液、粉末及分子筛吸附样品的ESR谱,讨论了络合物中晶体场强,对称性及成键特性。     

Darstellung und Molekülstrukturen von oligofunktionalen Dirheniumcarbonylderivaten aus Dirheniumnonacarbonylphosphan

Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re₂(CO)₉NCCH₃ was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re₂(CO)₉PH₃, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re₂(CO)₉PH₃ led to the new bi- and trinuclear complexes Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈, Re₂(μ-PH₂)₂(CO)₈ and Re₂(μ-H) · (μ-PH₂)(CO)₈, which were characterized by IR-, ¹H- and ³¹P-NMR spectroscopy. The structures of ax-Re₂(CO)₉PH₃, Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈ and Re₂(μ-PH₂)₂(CO)₈ were confirmed by single-crystal X-ray analysis. ax-Re₂(CO)₉PH₃ has a very short Re? P bond length of 228(2) pm.     

Cellulose-polyamide 66 blends. Part II: Mechanical behavior

Blends of the natural polymer cellulose with a synthetic polymer, polyamide 66, are studied in order to determine if the expected strong interaction between them, due to hydrogen bonds, could improve their mechanical properties such as strength and elongation at break. In a previous work {Part I, J. Polym. Sci. Polym. Phys., 32 , 1437 (1994)}, the preparation technique and the characterization of cellulose-polyamide 66 (PA66) blends were described in detail. Several samples in the composition range between 0 to 70 wt % of PA66 were carefully dried and examined using dynamic mechanical and tensile tests. Based on previous work a new percolation model has been developed. It takes both linear and nonlinear mechanical behaviors into account and allows for the effect of adhesion between material domains. From comparison between experimental and predicted data, it is concluded that a partial miscibility between the amorphous phases of cellulose and PA66 exists and is responsible for a strong adhesion at their interface. Solid-state ¹³C nuclear magnetic resonance has also been used to study these samples and supports the existence of strong interactions between both homopolymers. © 1995 John Wiley & Sons, Inc.     

Hybrid inorganic/organic interpenetrating polymer networks based on zeolite 13x and polystyrene

A hybrid inorganic/organic interpenetrating polymer network (IPN) of a three-dimensional network structure zeolite crystal (13X, powder) and crosslinked or linear polystyrene (PS) was prepared and characterized by differential scanning calorimetry (DSC), solid-state¹³C-NMR, and scanning electron microscopy (SEM). The size and shape of the crystalline zeolite particles were revealed on SEM micrographs in both the pure zeolite and the IPNs. Solubility tests and the results of DSC with solid-state ¹³C-NMR confirm that some organic PS chains are incorporated within the internal three-dimensional channels of the zeolite particles. We speculate that the internal PS chains may adopt an extended “one-dimensional” conformation and exhibit no bulk polymer glass transition. These novel hybrid inorganic/organic IPNs are a new kind of IPN structure. © 1995 John Wiley & Sons, Inc.     

Spectroscopic Studies of 1-Aryl-2,2-Dichlorocyclopropanes

Seventeen 1-aryl-2,2-dichlorocyclopropanes were examined by using IR, ¹³C NMR, and mass spectrometry. The data obtained from IR and ¹³C NMR spectra indicate that the bond strength of carbon-chlorine on the cyclopropane ring and the electron density of that carbon depend on the substituent. The mass fragmentation patterns of compounds in this series resemble those of the dibromo analogues. The fragmentation mechanism is proposed to involve the formation of indenium ion through an electrocyclization.     

二茂铁有机锡衍生物的13C,119Sn NMR研究

本文测定了几种二茂铁有机锡衍生物的¹¹⁹Sn,¹³C NMR谱。对其中几种衍生物的¹³C NMR谱进行了归属,从而进一步验证了这类化合物的结构。着重讨论了结构如化合物中取代基X的改变对¹¹⁹Sn化学位移的影响。并对结构如 类化合物N→Sn异侧配位的问题进行了讨论。