Effect of polymerization temperature on the original morphology of polyethylene prepared by γ-ray-induced polymerization

Polyethylene was prepared by γ-ray-induced polymerization in the temperature range 0–180°C. The morphology and the physical properties of the polymer as polymerized were studied by electron microscopy, differential scanning calorimetry, and gel permeation chromatography. Aggregates of small lamellar crystals with irregularly growing faces were produced below 55°C. Aggregates of large spherical particles were formed above 60°C together with hemispherical particles which adhered to the substrate. A few lamellar crystals of triangular or amoeba-like shapes were also found above 55°C. The polymers formed below 55°C showed a sharp single endothermic DSC peak and a bimodal molecular-weight distribution, while the sample above 60°C had a double endotherm and a unimodal molecular-weight distribution. These facts suggest that the mechanism of crystallization during polymerization below 55°C is different from that above 60°C. The melting point, however, decreased continuously with increasing polymerization temperature and was much lower than that of extended-chain crystals. The results show that the polyethylene, as polymerized, is composed of folded-chain crystals irrespective of the reaction temperature.     

Periodicity of hyperplane arrangements with integral coefficients modulo positive integers

We study central hyperplane arrangements with integral coefficients modulo positive integers q. We prove that the cardinality of the complement of the hyperplanes is a quasi-polynomial in two ways, first via the theory of elementary divisors and then via the theory of the Ehrhart quasi-polynomials. This result is useful for determining the characteristic polynomial of the corresponding real arrangement. With the former approach, we also prove that intersection lattices modulo q are periodic except for a finite number of q’s. This work was supported by the MEXT and the JSPS.     

Alkali metal salt‐catalyzed aldol addition of dimethylsilyl enolate on a polyether structure

The aldol addition of dimethylsilyl enolates to aldehydes with alkali metal salt catalysts was examined. Several kinds of polyether derivatives were employed as solid solvents without a liquid one. In the presence of the polymer (Gr) obtained from poly(ethylene glycol) methyl ether methacrylate (PEGMA) or the crosslinked derivatives (GLs) from PEGMA, the aldol addition proceeded efficiently and yielded the product. The effective catalyst was lithium bromide for Gr and potassium bromide for GLs. The crosslinked polyether GLs were easily separated from the reaction mixture by simple filtration, which was preferable to simplifying the treatments of the reaction. The results demonstrated that the presence of polyether structures provided a favorable reaction environment and enabled the reaction under solvent‐free conditions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2075–2084, 2005     

Fast magnetization tunneling in tetranickel(II) single-molecule magnets

A series of Ni(4) cubane complexes with the composition [Ni(hmp)(ROH)Cl](4) complexes 1-4 where R= -CH(3) (complex 1), -CH(2)CH(3) (complex 2), -CH(2)CH(2)(C(4)H(9)) (complex 3), -CH(2)CH(2)CH(2)(C(6)H(11)) (complex 4), hmp(-) is the anion of 2-hydroxymethylpyridine, t-Buhmp(-) is the anion of 4-tert-butyl-2-hydroxymethylpyridine, and dmb is 3,3-dimethyl-1-butanol] and [Ni(hmp)(dmb)Br](4) (complex 5) and [Ni(t-Buhmp)(dmb)Cl](4) (complex 6) were prepared. All six complexes were characterized by dc magnetic susceptibility data to be ferromagnetically coupled to give an S = 4 ground state with significant magnetoanisotropy (D approximately equal to -0.6 cm(-1)). Magnetization hysteresis measurements carried out on single crystals of complexes 1-6 establish the single-molecule magnet (SMM) behavior of these complexes. The exchange bias observed in the magnetization hysteresis loops of complexes 1 and 2 is dramatically decreased to zero in complex 3, where the bulky dmb ligand is employed. Fast tunneling of magnetization is observed for the high-symmetry (S(4) site symmetry) Ni(4) complexes in the crystal of complex 3, and the tunneling rate can even be enhanced by destroying the S(4) site symmetry, as is the case for complex 4, where there are two crystallographically different Ni(4) molecules, one with C(2) and the other with C(1) site symmetry. Magnetic ordering temperatures due to intermolecular dipolar and magnetic exchange interactions were determined by means of very low-temperature ac susceptibility measurements; complex 1 orders at 1100 mK, complex 3 at 290 mK, complex 4 at approximately 80 mK, and complex 6 at <50 mK. This confirms that bulkier ligands correspond to more isolated molecules, and therefore, magnetic ordering occurs at lower temperatures for those complexes with the bulkiest ligands.     

Lewis base catalyzed Mannich-type reactions between trimethylsilyl enol ethers and aldimines

Lewis base catalyzed Mannich-type reaction between trimethylsilyl enol ethers and N-tosylaldimines is described. Nitrogen anions generated from amides or imides such as lithium benzamide or potassium phthalimide are found to be effective Lewis base catalysts in DMF at room temperature to afford the corresponding beta-amino carbonyl compounds in good to high yields; the oxygen anion generated from carboxylic acids such as lithium acetate was also found to be effective in dry DMF. The above-mentioned lithium acetate-catalyzed Mannich-type reaction between aldimines and various trimethylsilyl (TMS) enol ethers such as silyl ketene acetal proceeded smoothly even in water-containing DMF. Then, Lewis base catalyzed three-component Mannich-type reactions of TMS enol ether, tosylamide, and aromatic aldehyde having electron-withdrawing group such as p-nitrobenzaldehyde were investigated. The reaction proceeded smoothly to afford the corresponding beta-amino ester in good yield. Further, ammonium carboxylates such as tetrabutyl ammonium acetate or tetrabutyl ammonium benzoate were found to be more effective Lewis base catalysts in the above-mentioned Mannich-type reaction. The synthesis proceeded in various solvents at lower temperatures. The reaction between aldimines and TMS enol ethers generated from thioester and various ketones such as propiophenone or cyclohexanone also proceeded smoothly to afford the corresponding beta-amino carbonyl compounds in high yields with good to high anti-selectivities.     

Dependence of electron spin g-factor on magnetic field in quantum wells

The dependence of electron spin g-factor on magnetic field has been investigated in GaAs/AlGaAs quantum wells. We have estimated the electron g-factor from spin precession frequency in time-resolved photoluminescence measurements under a magnetic field in different configurations; the magnetic field perpendicular (g_⊥) and parallel (g_∥) to the quantum confinement direction. When the angle between the magnetic field and the confinement direction is 45°, we have found that g-factor varies depending on the direction of magnetic field and the circular polarization type of excitation light (σ⁺ or σ^?). These dependences of g-factor exhibit main features of Overhauser effect that nuclear spins react back on electron spin precession. The value of g_⊥ and g_∥ corrected for the nuclear effects agree well with the results of four-band k·p perturbation calculations.     

Solvent Effects in Optical Spectra of ortho-Aminobenzoic Acid Derivatives

We investigated three amino derivatives of ortho-aminobenzoic or anthranilic acid (o-Abz): a) 2-Amino-benzamide (AbzNH₂); b) 2-Amino-N-methyl-benzamide (AbzNHCH₃) and c) 2-Amino-N-N′-dimethyl-bezamide (AbzNH(CH₃)₂), see Scheme 1. We describe the results of ab-initio calculations on the structural characteristics of the compounds and experimental studies about solvent effects in their absorption and steady-state and time-resolved emission properties. Ab-initio calculations showed higher stability for the rotameric conformation in which the oxygen of carbonyl is near to the nitrogen of ortho-amino group. The derivatives present decrease in the delocalization of π electron, and absorption bands are blue shifted compared to the parent compound absorption, the extent of the effect increasing from to Abz-NH₂ to Abz-NHCH₃ Abz-NH(CH₃)₂. Measurements performed in several solvents have shown that the the dependence of Stokes shift of the derivatives with the orientational polarizability follows the Onsager-Lippert model for general effects of solvent. However deviation occurred in solvents with properties of Bronsted acids, or electron acceptor characteristics, so that hydrogen bonds formed with protic solvents predominates over intramolecular hydrogen bond. In most solvents the fluorescence decay of AbzNH₂ and AbzNHCH₃ was fitted to a single exponential with lifetimes around 7.0 ns and no correlation with polarity of the solvent was observed. The fluorescence decay of AbzN(CH₃)₂ showed lifetimes around 2.0 ns, consistent with low quantum yield of the compound. The spectroscopic properties of the monoamino derivative AbzNHCH₃ are representative of the properties presented by Abz labelled peptides and fatty acids previously studied.     

Noncommutative Riemann Surfaces by Embeddings in $${\mathbb{R}^{3}}$$

We introduce C-Algebras of compact Riemann surfaces as non-commutative analogues of the Poisson algebra of smooth functions on . Representations of these algebras give rise to sequences of matrix-algebras for which matrix-commutators converge to Poisson-brackets as N → ∞. For a particular class of surfaces, interpolating between spheres and tori, we completely characterize (even for the intermediate singular surface) all finite dimensional representations of the corresponding C-algebras.