Overlapping chemical and genetic diversity in Ligularia lamarum and Ligularia subspicata. Isolation of ten new eremophilanes and a new seco-bakkane compound

Root chemicals and DNA sequences were analyzed for Ligularialamarum samples collected in Yunnan and Sichuan Provinces of China and the relationship between the plant and Ligulariasubspicata, its taxonomically closest species, was examined. Both species produce furanoeremophilanes and eremophilan-8-one derivatives as the major components. Eleven new compounds, including a new seco-bakkane compound, were isolated. The two species were found to harbor overlapping intra-specific diversities with respect to the chemicals and the DNA sequences.     

Synthesis of the sphingolipid activator protein, saposin C, using an azido-protected O-acyl isopeptide as an aggregation-disrupting element

In order to achieve an efficient synthesis of highly hydrophobic proteins by the native chemical ligation (NCL) reaction, we examined to incorporate the O-acyl isopeptide method, which is known to improve the solubility of the segment, to the NCL reaction: a peptide thioester having O-acyl isopeptide structures is prepared by the Boc mode solid-phase method using an azido group as a protecting group for the isopeptide site, and then ligated with C-terminal segment with an in situ reduction of the azido group followed by an O- to N-acyl shift. This method was successfully applied to the synthesis of the sphingolipid activator protein, saposin C.     

Thermally induced transformations of calcium carbonate polymorphs precipitated selectively in ethanol/water solutions

For the precipitation of calcium carbonate polymorphs in ethanol/water solutions of calcium chloride by the diffusion of the gases produced by sublimation–decomposition of solid ammonium carbonate, polymorph selection and morphology control of the precipitates were demonstrated by the effect of ethanol/water ratio in the mother liquor. The precipitated phases change systematically from gel-like aggregates of hydrated amorphous calcium carbonate in the absolute ethanol solution to well-shaped rhombohedral particles of calcite in the absolute aqueous solution via almost pure phase of vaterite with dendrite structure in 75%-ethanol/25%-aqueous and 50%-ethanol/50%-aqueous solutions. On heating the precipitated sample in flowing dry nitrogen, all the samples transformed to calcite before the thermal decomposition, where the thermal decomposition temperature shifts to higher temperatures with increasing the water content in the mother liquor due to the systematic increase in the particle size of calcite. Accordingly, the present method of controlled precipitation of calcium carbonate polymorphs is also useful to control the particle size and reactivity of calcite produced by heating the precipitates. Selecting vaterite with dendrite structure from the present series of precipitated samples, the structural phase transition to calcite was characterized as the three-dimensional growth of rhombohedral particles of calcite with the enthalpy change ΔH = ? 2.8 ± 0.1 kJ mol^?1 and the apparent activation energy E_a = 289.9 ± 5.8 kJ mol^?1.     

A hypervalent pentacoordinate boron compound with an N-B-N three-center four-electron bond

For the purpose of synthesizing and characterizing hypervalent boron compounds with strong hypervalent interaction, we have prepared a boron compound with a tridentate ligand bearing two pyrimidine rings as nitrogen donors. X-ray analysis and molecular orbital calculations suggested that the boron compound was of hypervalent pentacoordinate structure with an N-B-N hypervalent bond. Thus, we have prepared the first hypervalent second row element compound with apical N coordination. A breakdown of energy contributions by DFT calculations revealed that the N-B-N bond energy of the pentacoordinate state ground state (13) was 2.8 kcal mol(-1). Implications were that the conjugation energy difference of 6.6 kcal mol(-1) (14.2-7.6 kcal mol(-1)) with the tetracoordinate state was a crucial factor for shifting stability toward the pentacoordinate structure.     

Structural concept of nitroxide as a lipid peroxidation inhibitor

Nitroxides have antioxidative activities toward lipid peroxidation, but the influence of steric factors is not known. We synthesized alkyl-substituted nitroxides at the α-position of the N-O moiety to enhance lipophilicity and the bulk effect. There was good correlation between the IC(50) and lipophilicity (log P(o/w)) of nitroxides with use of the thiobarbituric acid-reactive substances (TBARS) assay. Furthermore, an inhibitory effect on the TBARS assay was dependent upon the number and length of alkyl groups, though nitroxides had almost identical lipophilicity.     

Superconducting gap in iron pnictides studied by optical spectroscopy

We investigated the in-plane optical spectrum of a Co-doped Ba(Fe_0.94Co_0.06)₂As₂ single crystal showing superconductivity below . In the normal state, the low-energy optical conductivity spectrum can be decomposed into a sharp Drude term and a broad “incoherent” term. Below T_c, an s-wave-like superconducting gap appears in both components. We also investigated a magnetic or spin-density-wave gap in the detwinned parent compound.     

Distribution measurement of amphetamine-type stimulants in organs using micropulverized extraction and liquid chromatography/tandem mass spectrometry to complement drug distribution using mass spectrometry imaging

Amphetamine-type stimulants (ATS) such as methamphetamine are widely abused and can cause toxic effects in the body. In this study, a simple and accurate analytical method for distribution measurement of drugs in organs was developed to visualize localization of ATS in organs and to complement drug distribution by mass spectrometry imaging (MSI). The brain, liver and kidney from rats to which ATS had been administered were segmented into blocks of 2×2×2 mm3 at -30°C. Each organ block was micropulverized with a stainless-steel bullet at -80°C. The concentrations of drugs in each block were measured by liquid chromatography/tandem mass spectrometry. The three-dimensional distribution of drugs in a whole organ was expressed using color gradation of drug concentration after reconstruction of all blocks to the original locations. The distribution was also compared with that obtained by MSI. This method enabled measurement of drug distribution in organs with simple and clean procedures and accurate quantification unlike autoradiography and MSI. The methamphetamine concentrations were different between parts in an organ, particularly in the kidney. This method could be applicable to the measurement of the distribution of compounds in various solid samples and could be used as a complementary method for the measurement of the distribution of compounds by MSI.     

Notes on the Kernels of Locally Finite Higher Derivations in Polynomial Rings

Let A = k^[3] be the polynomial ring in three variables over a field k, and let D be a nontrivial locally finite iterative higher derivation on A. Let A^D denote the kernel of D. In this note, we prove that, if chark > 0 and ML(A^D) ≠ A^D, then A^D ? k^[2]. As a consequence of this result, we give another proof of the cancellation theorem for k^[2] over any field k of positive characteristic.     

Enclosing ellipsoids and elliptic cylinders of semialgebraic sets and their application to error bounds in polynomial optimization

This paper is concerned with a class of ellipsoidal sets (ellipsoids and elliptic cylinders) in ${\mathbb{R}^m}$ which are determined by a freely chosen m × m positive semidefinite matrix. All ellipsoidal sets in this class are similar to each other through a parallel transformation and a scaling around their centers by a constant factor. Based on the basic idea of lifting, we first present a conceptual min-max problem to determine an ellipsoidal set with the smallest size in this class which encloses a given subset of ${\mathbb{R}^m}$ . Then we derive a numerically tractable enclosing ellipsoidal set of a given semialgebraic subset of ${\mathbb{R}^m}$ as a convex relaxation of the min-max problem in the lifting space. A main feature of the proposed method is that it is designed to incorporate into existing SDP relaxations with exploiting sparsity for various optimization problems to compute error bounds of their optimal solutions. We discuss how we adapt the method to a standard SDP relaxation for quadratic optimization problems and a sparse variant of Lasserre’s hierarchy SDP relaxation for polynomial optimization problems. Some numerical results on the sensor network localization problem and polynomial optimization problems are also presented.