Laser deposition of iron on graphite substrates

Pulsed laser deposition of iron atoms on graphite substrates was performed to produce iron carbide films. Mössbauer spectra of the sample revealed that iron carbide was produced on the substrate surface and that an α-Fe layer was produced above the iron carbide layer. When the substrate temperature was maintained at 300 K, the iron carbide layer had a hyperfine magnetic distribution because it contained high density of defects. Laser deposition of Fe at 570 K produced cementite Fe₃C with fewer defects due to enhancement of thermal reactions or annealing of the films. The orientation of hyperfine field of the Fe₃C film was parallel to the substrate surface.     

Nine new secoiridoid glucosides from Jasminum nudiflorum

Phytochemical study of the leaves of Jasminum nudiflorum has led to the isolation of nine new secoiridoid glucosides, jasnudiflosides F-L (1-7), nudifloside D (8) and isooleoacteoside (9). The structures of these compounds were elucidated on the basis of chemical and spectroscopic evidence.     

Fullerene sensors based on calix[5]arene

A new class of fullerene sensors based on calix[5]arenes has produced the highly sensitive detection of C60 and C70.     

Metal-induced regulation of fullerene complexation with double-calix[5]arene

The metal-induced regulation of fullerene complexation with double-calix[5]arene is described. The receptor shows strong binding to C70 only in the presence of Cu+.     

Memory effect on the glass transition in vulcanized rubber

The memory effect upon glassification is studied in the glass-to-rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed, taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model.     

(15N) acetamide in polar solvents: Hindered internal rotation and intermolecular interactions

The ¹H spectrum of (¹⁵N)acetamide has been measured in dimethyl sulphoxide (DMSO), methyl propyl ketone (MPK), 1,3-dioxane, 1,4-dioxane, D₂O, acetonitrile and pyridine-d₅ at various temperature intervals within the range of 278–343 K. From the temperature dependence of the NMR spectra of the amide protons, the free energy of activation, ΔG^≠, for hindered rotation about the central C? N bond was determined by means of total line shape analysis in the four solvents DMSO, MPK and the two dioxanes. Observed values of ΔG^≠ (298 K) (72.7 in DMSO, 70.1 in MPK, 70.0 in 1,3-dioxane and 70.1 kJ mol¹ in 1,4-dioxane) were not very sensitive to the choice of solvent or concentration. The concentration dependence of the internal chemical shift between the amide protons was studied in MPK, D₂O, acetonitrile and pyridine-d₅. The free energy of activation and the internal chemical shift are discussed on the basis of solvent-amide and amide–amide specific hydrogen bonding interactions, and in comparison to the results of molecular orbital calculations.     

Phase diagram of the square-lattice three-state Potts antiferromagnet with a staggered polarization field

We study a square-lattice three-state Potts antiferromagnet with a staggered polarization field at finite temperature. Numerically treating the transfer matrices, we determine two phase boundaries separating the model-parameter space into three parts. We confirm that one of them belongs to the ferromagnetic three-state Potts criticality, which is in accord with a recent prediction, and another to the Ising-type; these are both corresponding to the massless renormalization-group flows stemming from the Gaussian fixed points. We also discuss a field theory to describe the latter Ising transition.     

Contributions of short-range and excluded-volume interactions to unperturbed polymer chain dimensions

A Monte Carlo study is made of the mean-square radius of gyration for the freely rotating chain with such fictitious excluded-volume interactions that the Lennard-Jones 6-12 potentials at the Theta temperature act only between the fourth-through (3+Delta)th-neighbor beads (Delta > or = 1) along the chain. The behavior of the asymptotic value (/n)infinity of the ratio /n as a function of the number n of bonds in the chain in the limit of n --> infinity is examined as a function of Delta. It is shown that the approach of (/n)infinity to its value for the real unperturbed chain with Delta = infinity is so slow that the interactions between even up to about 100th-neighbor beads should be taken into account in order to reproduce nearly its dimension. The result implies that the unperturbed polymer chain dimension as experimentally observed at the Theta temperature depends not only on short-range interactions but also to a considerable extent on the long-range excluded-volume interactions, and that the asymptotic value Cinfinity of the characteristic ratio Cn for the rotational isomeric state model in the limit of n --> infinity, which is determined only by the very local conformational energy, cannot be directly compared with the corresponding experimental value.     

Acid-catalyzed transformation of rubrene to indenonaphthacene and its paired interacting orbital (PIO) analysis

Treatment of rubrene (5,6,11,12-tetraphenylnaphthacene) with trifluoroacetic acid in dichloromethane gives 4b,9,10-triphenyl-4b,9-dihydroindeno[1,2,3-fg]naphthacene (1) as the sole isolable product. Paired interacting orbital (PIO) analysis indicates that the reaction is initiated by preferential attack of H⁺ at C(11) position of rubrene.     

Temperature effect on solubilization of n-alkylbenzenes into sodium cholate micelles

The solubilization of n-alkylbenzenes (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, n-pentylbenzene, n-hexylbenzene) into an aqueous micellar solution of sodium cholate was carried out. Solubilizate concentrations at equilibrium were determined spectrophotometrically at 293.2, 298.2, 303.2, 308.2, and 313.2 K. The first stepwise association constants (K(1)) between solubilizate monomers and vacant micelles were evaluated from the equilibrium concentrations and found to increase with increasing hydrophobicity of the solubilizate molecules. From the Gibbs energy change for solubilization at different micelle aggregation numbers and from the molecular structure of the solubilizates, the function of sodium cholate micelles as solubilizer was discussed. Enthalpy and entropy changes of solubilization were calculated from the temperature dependence of the K(1) values, and the solubilization was found to be enthalpy-driven for the solubilizates with shorter alkyl chains. The results obtained were also compared with those for conventional aliphatic micelles.