Ionic conduction of the perovskite-type halides

The ionic conduction in the perovskite-type halides, CsPbCl₃, CsPbCl₃ and KMnCl₃, was studied. Measurements were made of ac conductivity at temperatures from 150°C to the melting point, and of ionic transport number using the Tubandt, EMF and ion-blocking methods. The effects of impurity doping on the ionic conductivity of CsPbCl₃ were also studied using the samples of composition, CsPb_0.99M_0.01Cl_2.99 (M = Li, Na, K, Ag). It was concluded that these materials are halide-ion condcutors. The ionic conductivities of CsPbCl₃ and CsPbBr₃ are close to those of the well known halide-ion conductors, PbCl₂ and PbBr₂. The ionic transport numbers were found to be > 0.9 for CsPbCl₃ and CsPbBr₃, and about 0.99 for KMnCl₃. The conduction was considered to be caused by the migration of halide-ion vacancies V_X (X = Cl, Br). The activation energies for the migration of V_X were 0.29 eV for CsPbCl₃, 0.25 eV for CsPbBr₃ and 0.39 eV for KMnCl₃. The vacancy diffusion coefficients of these materials were found to be verylarge. However, the impurity doping did not increase the ionic conductivity markedly because of small dopant solubility.     

Biosynthesis of Indole Diterpene Lolitrems: Radical‐Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Pd- and Cu-catalyzed C–H arylation of indazoles

The palladium- and copper-catalyzed C–H arylation reactions of 1H- and 2H-indazoles with haloarenes are described. A PdCl₂/phen/Ag₂CO₃/K₃PO₄ catalytic system is effective for the C–H arylation of 1H- and 2H-indazoles with haloarenes, whereas a less expensive CuI/phen/LiOt-Bu catalytic system is applicable to the C–H coupling of substituted 2H-indazoles and iodoarenes. The utility of newly developed catalyst was demonstrated in the rapid synthesis of YC-1 (an antitumor agent) and YD-3 (platelet anti-aggregating agent). These new reactions represent important direct functionalization tools of indazoles, well-known bioisosteres of pharmaceutically important indole core.     

A novel action of terpendole E on the motor activity of mitotic Kinesin Eg5

To reveal the mechanism of mitosis, the development of M phase-specific inhibitors is an important strategy. We have been screening microbial products to find specific M phase inhibitors that do not directly target tubulins, and rediscovered terpendole E (TerE) as a novel Eg5 inhibitor. TerE did not affect microtubule integrity in interphase, but induced formation of a monoastral spindle in M phase. TerE inhibited both motor and microtubule-stimulated ATPase activities of human Eg5, but did not affect conventional kinesin from either Drosophila or bovine brain. Although terpendoles have been reported as inhibitors of acyl-CoA:cholesterol O-acyltransferase (ACAT), the Eg5 inhibitory activity of TerE was independent of ACAT inhibition. Taken together, we demonstrate that TerE is a novel Eg5 inhibitor isolated from a fungal strain.     

1,6,11,16‐Tetra­oxacyclo­eicosane‐2,5,12,15‐tetra­one

The 20‐membered ring of the title compound, C₁₆H₂₄O₈, adopts an approximately flat rectangular structure with three‐ and seven‐bond sides and lies across a crystallographic center of inversion. The corners of the ring occur at both ends of one of the planar ester segments. All of the carbonyl O atoms are involved in inter­molecular C—H⋯O hydrogen bonds.     

Nuclear quadrupole resonance of norephedrine

Toward searching for illegal drugs, we investigated the pulsed nuclear quadrupole resonance (NQR) response of ¹⁴N in (1R,2S)-(-)-norephedrine, based on the predictions of quantum chemical calculations. Two pairs of spectral lines (ν₊=3.089, 3.093 MHz and ν₋=2.594, 2.608 MHz) were observed despite its molecule structure having only a single nitrogen atom. This indicates that the molecular crystal has two nonequivalent nitrogen atoms in the unit cell. The temperature dependence of the NQR frequencies and relaxation properties were investigated for the purpose of accurate remote sensing of the drugs. The NQR frequency shift was approximately 0.23 kHz/K around room temperature. The spin-lattice relaxation and spin-phase memory times were 5.2–10.2 ms and 0.6–1.5 ms, respectively.     

Phase transition behavior and proton conduction mechanism in cesium hydrogen sulfate/silica composite

Proton conduction and crystal structure in CsHSO₄/SiO₂ composite composed of polycrystalline CsHSO₄ and mesoporous silica particles were investigated based on conductivity measurement and characterizations using Raman spectroscopy, XRD, and differential thermal analysis. The conductivity of pure CsHSO₄ abruptly changes at around 414 K (superprotonic phase transition), being accompanied with the structural transformation from a monoclinic phase to a tetragonal phase, while the conductivity of CsHSO₄/SiO₂ composite is significantly larger by over three orders of magnitude than that of pure CsHSO₄ below the critical temperature of the superprotonic phase transition (353-414 K). Raman spectroscopy and XRD indicate that this remarkable conductivity-enhancement in the composite is not due to the stabilization of the tetragonal phase (superprotonic phase) below its critical temperature. The line-broadening of the internal modes in the Raman spectra suggests that the rapid reorientational motion of the HSO₄⁻ ion, which leads to superprotonic conduction, is induced in the composite even below the critical temperature. The reorientational motion of the HSO₄⁻ ion below the critical temperature will occur at the interfacial phase which is structurally disordered and forms between CsHSO₄ and SiO₂ in the mesopores and/or on the surfaces of silica particles. Proton transfer will be accelerated via the interfacial conduction-pathway in the composite.     

Control of a class of underactuated mechanical systems

In this paper a new control methodology for underactuated mechanical systems is proposed. The basic idea of this method is to combine passive velocity field control with decoupling vector field. In order that the underactuated mechanical systems can be stabilized at the desired position after settling on the desired velocity vector field, novel control strategies are proposed. Proposed control strategies are applied to the underactuated planar three-link manipulator and underactuated planar body. Simulations demonstrate the usefulness and effectiveness of the proposed control methodology.