Effect of annealing on structure and permeability of poly [(l-trimethylsilyl)-l-propyne]

The permeability of annealed poly (l-(trimethylsilyl)-l-propyne) was studied from the viewpoint of structural information obtained from x-ray diffraction and density. The sample cast from benzene solution had low density (0.82 g/cm³) and high permeability, whereas the annealed sample had a higher density (0.88 g/cm³) and permeability lower by two orders of magnitude. The smaller-angle x-ray diffraction peak for each sample, which was likely to reflect the distance between intermolecular chains, increased in intensity and shifted toward higher angle, corresponding to the change of the density with annealing. The logarithmic oxygen permeability was proportional to the density, namely the free volume fraction correlated with the diffusion coefficient and controlled by annealing and swelling by alcohols.     

Tensor analyzing power T 20 of the dd → 3Hen and dd → 3Hp reactions at zero angle for energies 140, 200, and 270 MeV

RIKEN Accelerator Research Facility data on the tensor analyzing power T ₂₀ of the dd → ³Hen and dd → ³Hp reactions at zero angle for deuteron kinetic energies of 140, 200, and 270 MeV are reported. The observed positive sign of T ₂₀ clearly demonstrates the sensitivity to the D/S-wave ratio in the ³He and ³H wave functions in the energy range of the experiment. Data on T ₂₀ for the ³Hen channel are in agreement with those for the ³Hp channel within the experimental errors.     

Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.     

Enantioselective ring cleavage of dioxane acetals mediated by a chiral Lewis acid: application to asymmetric desymmetrization of meso-1,3-diols

[reaction: see text]. Phenylalanine-derived B-aryl-N-tosyloxazaborolidinones selectively activate one of two enantiotopic oxygen atoms in prochiral anti dioxane acetals derived from meso-1,3-diols, leading to enantioselective formation of ring-cleavage products. The reaction is utilized as a key step in asymmetric desymmetrization of meso-1,3-diols.     

Perfectly dissolved boron nitride nanotubes due to polymer wrapping

We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions.     

The characteristic fragment ions and visualization of cationic starches on pulp fiber using ToF‐SIMS

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to investigate the distribution of cationic starch on pulp fiber. To identify the characteristic fragment ions of the cationic starches, deuterium‐labeled cationic starches were prepared and analyzed using ToF‐SIMS. The starch 2‐hydroxypropyltrimethylammonium chloride derivative generated characteristic fragments at m/z 58 and 59, which were identified as [H₂C?N(CH₃)₂]⁺ and [N(CH₃)₃]^+·, respectively. The fragmentation patterns were also suggested. From the imaging analysis, the adsorption of the cationic starch on fibers was uneven on individual fibers, as well as between fibers. This may have been on account of fiber morphology and structure. On examining scanning electron microscope (SEM) images, the quaternary ammonium starch derivative (QS) did not penetrate the fiber. No migration of cationic starch was observed under various drying conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

Molecular vibrations in a gradient extremal path

Summary The calculation of vibrational states using a gradient extremal path is discussed. Gradient extremal paths are defined by local criteria, which lead to stable solutions. This has certain advantages in comparison with a steepest-descent path, which is often difficult to determine accurately. For cases where a reaction path formalism is applicable, a path based on the gradient extremal concept gives results in close agreement with those obtained using traditional steepest-descent methods. We present algorithms for carrying out such calculations and also give some numerical results.