New C(28) steroidal glycosides from Tubocapsicum anomalum

Three new C(28) steroidal glycosides, isotubocaposides A (1), B (2), and C (3), were isolated from the fruits of Tubocapsicum anomalum MAKINO. Their chemical structures were elucidated on the basis of spectroscopic and X-ray diffraction analysis of p-bromobenzoyl derivative (5) of isotubocaposigenin (4), the sapogenol derivative of these three glycosides. Isotubocaposides have the structural peculiarity of an unusual side chain carrying a C-21 bound to C-24 on the lactone ring.     

Kinetics of chain collapse in dilute polymer solutions: molecular weight and solvent dependences

The molecular weight and solvent dependences of the characteristic time of chain collapse were studied for poly(methyl methacrylate) (PMMA) of the molecular weight Mw=6.4x10(6) and 1.14x10(7) in pure acetonitrile (AcN) and in the mixed solvent of AcN+water (10 vol %). The size of PMMA chains was measured as a function of the time after the quench by static light scattering and the chain collapse processes were expressed by the plot of the expansion factor alpha2 vs ln t. The chain collapse in the mixed solvent AcN+water (10 vol %) was found to occur much faster than that in pure AcN, though the measurement of the former collapse process required several hours. In order to make a comparison between the rates of chain collapses, the fast chain collapse process was superposed on the slow one by scaling the time of the fast process as gammat. The scale factor gamma was determined by comparing the chain collapse processes of nearly the same equilibrium expansion factor with each other. Accordingly, the superposition of the collapse for Mw=6.4x10(6) on that for Mw=1.14x10(7) yielded gammam=4.0+/-0.6 for the process in AcN+water and 5.5+/-0.6 in AcN. The superposition of the chain collapse process in AcN+water on that in AcN yielded gammas=9.5+/-1.4 for Mw=6.4x10(6) and 12.0+/-1.8 for Mw=1.14x10(7). This analysis suggests that gammam and gammas are constant independent of each other. Thus, by assuming the molecular weight dependence of gammam approximately Mz, the characteristic time tauexp of chain collapse was conjectured as tauexp approximately kappaMz, where kappa reflects the nature of solvent species. The ratio of kappa for PMMA in AcN to that in AcN+water is given by gammas. The exponent was estimated to be z=2.4+/-0.7 for AcN+water and 3.0+/-0.7 for AcN. These values are compatible with the theoretical prediction z=3 based on a phenomenological model, though the observed characteristic times are longer by several orders of magnitude than those of the theoretical prediction.     

Facile and efficient synthesis of C-hydroxycarboranes and C,C'-dihydroxycarboranes

C-Hydroxylated carboranes, carboranols, have interesting properties resulting from their hydroxyl protons being highly acidic because of the electron-deficient nature of the carborane cage. We described here an efficient synthesis of C-hydroxycarboranes 2 and C,C'-dihydroxycarboranes 3 by the reaction of carboranyl lithium and trimethylborate, followed by oxidation with hydrogen peroxide in the presence of acetic acid, to afford the corresponding o-, m-, and p-hydroxycarboranes 2 and o-, m-, and p-dihydroxycarboranes 3 selectively in high yields through a one-pot procedure. The m- and p-carborane isomers of 2 and 3 were obtained in especially good yields (2b, 85%; 2c, 85%; 3b, 95%; 3c, 96%). DFT calculations were performed on the dihydroxycarboranes 3 to compare the geometrical features of the isomers at the same level of theory and to characterize their electronic and NMR spectroscopic (13C chemical shift) properties.     

Controlled Polymerization of Protic Ionic Liquid Monomer by ARGET‐ATRP and TERP

The direct synthesis of structurally well‐defined protic polymeric ionic liquid (PIL) with controlled molecular weight and molecular weight distribution is examined using N,N‐diethyl‐N‐(2‐methacryloylethyl) ammonium bis(tri‐fluoromethylsulfonyl)imide (DEMH‐TFSI) as a monomer. Three polymerization methods, namely, atom transfer radical polymerization (ATRP), activators regenerated by electron transfer (ARGET)‐ATRP, and organotellurium‐mediated living radical polymerization (TERP) are employed in this study. While the polymerization by ATRP is slow and does not reach high monomer conversion that under ARGET‐ATRP and TERP proceeds smoothly and affords structurally well‐defined poly(DEMH‐TFSI)s. TERP is especially efficient for the control and poly(DEMH‐TFSI)s with low to high molecular weights ( = 49 100–392 500) and narrow molecular weight distributions (/ = 1.17–1.46) are obtained. These results represent the first example of synthesis of a structurally well‐defined protic, ammonium PIL by direct polymerization of the protic ionic liquid monomer. The polymerization of N,N‐diethyl‐N‐(2‐methacryloylethyl)‐N‐methylammonium bis(trifluoromethylsulfonyl)imide (DEMM‐TFSI), which possesses a quaternary ammonium salt, also proceeds in a highly controlled manner under TERP conditions. A diblock copolymer, polystyrene‐block‐poly(DEMH‐TFSI), is also successfully synthesized by TERP.

     

Synthesis and Physicochemical Properties of Novel Liquid Crystal Compounds with Negative Dielectric Anisotropy with a Tetrahydropyran Ring: Part 2

With the aim of improving the properties of liquid crystal (LC) mixtures for VA-LCD and PSA-LCD, JNC has newly synthesized 2-(4’-ethoxy-2’,3’-difluorobiphenyl-4-yl)-5-alkenyltetrahydro-2H-pyran derivatives with alkenyl substituents as side chains, and then measured various physicochemical properties to compare their properties to LC compounds with alkyl substituents as side chains. We have shown that several LC compounds with side-chain alkenyl substituents lead to the development of a larger negative dielectric anisotropy (Δ?) than for side-chain alkyl substituents. We considered the reason for this using a quantum chemical calculation. As a result, it was found that, compared to alkylated compounds, there exist several LC compounds with side-chain alkenyl substituents, which have a higher existence probability of conformers with a β angle, making expression of a larger |Δ?| possible in an effective manner. It was understood from this study that the physicochemical properties of LC mixtures for VA-LCD and PSA-LCD, which consist of LC compounds as a structural component, newly developed by JNC, show useful properties.     

Structural comparison of n-type and p-type LaAlO3/SrTiO3 interfaces

Using a surface x-ray diffraction technique, we investigated the atomic structure of two types of interfaces between LaAlO3 and SrTiO3, that is, p-type (SrO/AlO2) and n-type (TiO2/LaO) interfaces. Our results demonstrate that the SrTiO3 in the sample with the n-type interface has a large polarized region, while that with the p-type interface has a limited polarized region. In addition, atomic intermixing was observed to extend deeper into the SrTiO3 substrate at the n-type interface compared to the p type. These differences result in distinct degrees of band bending, which likely contributes to the striking contrast in electrical conductivity between the two types of interfaces.     

Strength Function in Continuum with a Square Integrable Basis

We present a new approach to describe the three-body continuum with a square integrable basis and show some examples to assess its efficiency. The formulation is done elegantly in the hyperspherical formalism and the tail behavior is appropriately corrected with use of the Green??s function. The efficiency of this approach is shown in a simple solvable problem by calculating the electric dipole strength function of a three-body system and comparing it to that obtained with the complex scaling method, which is widely used for calculating the strength function.     

Determining the angle of repose of sand under low-gravity conditions using discrete element method

This study is a comparative investigation of data, collected through experimental and numerical means, related to the flow of sand particles through a hopper under low-gravity conditions. During a parabolic airplane flight simulating low-gravity conditions, we determined effects of gravity on the angle of repose of sand pile particles by flowing dry sand from a hopper. The gravity effects on the angle of repose of the sand were negligible. Two-dimensional discrete element method (DEM) was used to simulate the angle of repose. Results were compared to observations made during the low-gravity experiments. Effects of varying parameters such as the friction coefficient and coefficient of rolling friction were determined by running various DEM simulations. Moreover, the effect of the elemental radius on the angle of repose was investigated using DEM. The angle of repose is influenced by certain changes in the friction coefficient and rolling friction values, but the elemental radius has only a negligible effect on the angle of repose within the range of variation. Results show that the DEM model used for this study might be applicable to determine terramechanical interactions under lunar surface gravity conditions, provided that parameters are adjusted and an extended period of simulation is achieved.     

3+2] coupling of quinone monoacetals by combined acid-hydrogen bond donor

The expeditious and efficient [3+2] coupling approach of quinone monoacetals 1 with alkene nucleophiles 2 by the action of an activated Br?nsted acid in the presence of a hydrogen bond donor perfluorinated alcohol has been achieved. With the optimized combined acid, the reaction could proceed under mild conditions by only mixing the two reactants to afford the cycloadducts 3 in a short time (within 10 min) with good to quantitative yields.