Pseudohexagonal crystallinity and thermal and tensile properties of ethene–propene copolymers

Structural (X‐ray diffraction), melting (differential scanning calorimetry), as well as mechanical (tensile tests) characterizations on uncrosslinked ethene–propene copolymer samples, obtained using a metallocene‐based catalytic system and having an ethene content in the range 80–50% by mol, are reported. Samples with an ethene content in the range 80–60% by mol present a disordered pseudohexagonal crystalline phase, whose melting moves from ≈ 40°C down to ≈ −20°C as the ethene content is reduced. The dramatic influence of the crystalline phase on tensile properties of uncrosslinked ethene–propene copolymers is shown. In particular, highest elongation at break values are obtained for samples being essentially amorphous in the unstretched state and partially crystallizing under stretching. On the other hand, lowest tension set values (most elastic behavior) are observed for samples presenting, already in the unstretched state, microcrystalline domains acting as physical crosslinks in a prevailing amorphous phase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1095–1103, 1999     

The NMR spectrum and conformation of 2,3-difluoropropionic acid ethyl ester

The ¹H and ¹⁹F NMR spectra of the CH₂FCHF group in FCH₂CHFCO₂C₂H₅ were analysed on the basis of an ABCXY spin system. The non-equivalence of the methylene protons is discussed in terms of rotational isomerism. It is concluded that the dominant rotamer is probably considerably distorted from a perfectly staggered orientation. The variation of ³J_HF with substituent electronegativity is reviewed.     

Liver metastases from unknown primary site: demonstration on MR images

To demonstrate the MR imaging features of liver metastases in patients with the clinical and histologic diagnosis of tumors of unknown primary tumors, a retrospective 7-year study was performed that included a total of 14 consecutive patients (7 men and 7 women; age range, 39-82 years; mean age, 60.6 years) with liver metastases from unknown primary site who had undergone MR imaging. The following lesion features were evaluated: a) number, b) diameter, c) signal intensity on T1 and T(2)-weighted images, and d) pattern of enhancement on immediate, 45 s and 90 s post gadolinium images. Lesions were classified as hypovascular, hypervascular and nearly isovascular relative to liver parenchyma as shown on immediate post gadolinium images. Patients were separated into four major groups, related to the histologic diagnosis of the lesions: (I) poorly differentiated neoplasms; (II) well-differentiated and moderately differentiated adenocarcinoma; (III) squamous cell carcinoma; (IV) combined poorly differentiated carcinoma and poorly differentiated adenocarcinoma. MRI findings were correlated with histologic information obtained by chart review and confirmed by retrospective histopathology review. All patients had the histologic diagnosis of adenocarcinoma: 8 patients belonged to group II (1 patient with the subtype well-differentiated and 7 patients with the subtype moderately differentiated) and 6 patients to group IV. Eleven patients (79%) presented with multiple lesions distributed throughout both hepatic lobes; 3 patients exhibited solitary lesions. All solitary metastases possessed a diameter equal or larger than 5 cm. Patients with multiple metastases demonstrated a wide range of diameter, ranging from less than 1.5 cm to more than 5 cm. Regarding lesion vascularity, 4 of 13 of the patients had hypovascular metastases and 9 of 13 of the patients had hypervascular lesions. One patient demonstrated both types of lesions. Five of six patients with the histopathologic diagnosis of poorly differentiated adenocarcinoma demonstrated hypervascular metastases. Solitary metastases were most often hypovascular (2 of 3); however no correlation with the histologic subtype was possible. Liver metastases from unknown primary site are often multiple and often hypervascular. Poorly differentiated tumors are the most common histologic type. Metastases are not uncommonly hypovascular, and these are often solitary.     

Symmetry in a free boundary problem for degenerate parabolic equations on unbounded domains

We use the method of Alexandroff-Serrin to establish the spherical symmetry of the ground domain and of the weak solution to a free boundary problem for a class of quasi-linear parabolic equations in an unbounded cylinder , where , with a simply connected bounded domain. The equations considered are of the type , with modeled on . We consider a solution satisfying the boundary conditions: for , and , as . We show that the overdetermined co-normal condition for , with 0$"> for at least one value , forces the spherical symmetry of the ground domain and of the solution.

     

Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application

Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity.     

Simulation of Ion Motion at Atmospheric Pressure: Particle Tracing Versus Electrokinetic Flow

Results obtained with two computational approaches for the simulation of ion motion at elevated pressure are compared with experimentally derived ion current data. The computational approaches used are charged particle tracings with the software package SIMION ver. 8 and finite element based calculations using the software package Comsol Multiphysics ver. 4.0/4.0a. The experimental setup consisted of a tubular corona discharge ion source coupled to a cylindrical measurement chamber held at atmospheric pressure. Generated ions are flown into the chamber at essentially subsonic laminar isothermal conditions. In the simulations, strictly stationary conditions were assumed. The results show very good agreement between the SIMION/SDS model and experimental data. For the Comsol model, only qualitative agreement is observed.     

Poly(ester urethane) guides for peripheral nerve regeneration

A biocompatible and elastomeric PU was synthesized from low-molecular-weight PCL as macrodiol, CMD as chain extender and HDI as chain linker for applications in the field of peripheral nerve repair. PU cast films supported in vitro attachment and proliferation of NOBEC. The in vitro adhesion and proliferation of S5Y5 neuroblastoma cells on the inner surface of uncoated, gelatin- and PL-coated PU guides were compared. Due to their superior in vitro performance, PL-coated PU guides were tested in vivo for the repair of 1.8 cm-long defects in rat sciatic nerves. The progressive regeneration was confirmed by EMG and histological analysis showing the presence of regenerating fibers in the distal stumps.