Nuclear magnetic resonance studies for the chiral recognition of the novel chiral stationary phase derived from 18-crown-6 tetracarboxylic acid

Enantioselectivities observed in high-performance liquid chromatography (HPLC) with the novel chiral stationary phase (CSP-18C6I) derived from (+)-18-crown-6 tetracarboxylic acid (18C6H₄) were investigated by using nuclear magnetic resonance (NMR) spectrometry. The elution orders in CSP-18C6I, that is, the S-enantiomer of 1-(1-naphthyl)ethylamine (1-NEA) and the

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-enantiomer (S-form) of alanine-β-naphthylamide (Ala-β-NA) eluted prior to each corresponding enantiomer, were successfully explained on the basis of the apparent binding constants (K_a) of the enantiomers to the CSP moiety which were calculated from ¹H-NMR experiments. Detailed HPLC and NMR studies for the chiral recognition of racemic amino compounds with 18C6H₄ hosts showed that ¹H-NMR spectrometry is a useful technique for the investigation of the chiral recognition mechanism in HPLC. Additionally, it was found 18C6H₄ can be recommended as a useful chiral shift reagent for the enantiomeric excess determination by ¹H-NMR.     

The study of a two-dimensional polar representation of the cardiac SPECT image--a new method of displaying left ventricular wall motion

A new method was developed to display left ventricular wall motion using two dimensional polar representation of cardiac SPECT image. After intravenous administration of 740 MBq (20 mCi) 99mTc (in vivo labeling of red blood cell), ECG-gated SPECT image of cardiac pool was recorded (32 directions, 180 degrees). The short axis images of left ventricle were constructed at end-diastole (ED) and end-systole (ES). Then the functional images of (ED-ES)/ED were calculated at each compatible slices and displayed in color according the degree of wall motion. In 8 cases with cardiac diseases this method was applied and clinically useful functional images could be obtained. The area of akinesia or hypokinesia are successfully demonstrated clearly separated from the area of normokinesia. We conclude that this method is useful to show left ventricular wall motion and to evaluate the segment and grade of abnormal wall motion of left ventricle.     

Probe of bending motion following the 1s(-1)pi* excitation of N2O

The doubly degenerate core-excited Pi state of N2O splits into two due to the static Renner-Teller effect. The lower state, A1, has a bent stable geometry and the molecule excited to this state starts to deform itself toward this bent geometry. To probe the effect of the potential energy surfaces of the core-excited A1 states on the nuclear motion, we measure the momenta of the three atomic ions in coincidence by means of the ion momentum imaging technique. We find that the potential energy surface affects the molecular deformation significantly. N2O in the terminal N 1s(-1)3piA1 excited state is observed to be bent more than that in the central N 1s(-1)3piA1 excited state. This means that N2O in the terminal N 1s(-1)3piA1 excited state bends faster than that in the central N 1s(-1)3piA1 excited state. When the excitation energy is decreased within the 1s(-1)3pi resonances, the nuclear motion in the A1 states becomes faster. This is interpreted by the notion that the excitation occurs onto the steeper slope part of the potential energy surface of the excited state for the lower excitation energy. The branching ratio of the A1 excitation increases with the decrease in the excitation energy.     

Factors affecting prednisolone release from hydrogels prepared with water-soluble dietary fibers, xanthan and locust bean gums.

The release behavior of prednisolone from hydrogels prepared with xanthan and locust bean gums was investigated. Newly developed equipment was employed in order to increase the gum concentration in the hydrogels. The apparent release rate of prednisolone from the hydrogels decreased with increasing gum concentration, suggesting that the diffusion of drug molecules was mainly controlled by the density of the three-dimensional network structure in the matrix. The effect of additives such as glycerin and sucrose on the release behavior of prednisolone was also investigated in detail. Drug release was significantly lowered by the addition of these compounds to these hydrogels. A linear relation was observed between the apparent release rate of prednisolone and microscopic viscosity of the hydrogels. These results indicated that the drug release could be controlled not only by the density of the network structure but also by the microscopic viscosity of the hydrogels.     

Unveiling the Biosynthetic Pathway of the Ribosomally Synthesized and Post‐translationally Modified Peptide Ustiloxin B in Filamentous Fungi

The biosynthetic machinery of the first fungal ribosomally synthesized and post‐translationally modified peptide (RiPP) ustiloxin B was elucidated through a series of gene inactivation and heterologous expression studies. The results confirmed an essential requirement for novel oxidases possessing the DUF3328 motif for macrocyclization, and highly unique side‐chain modifications by three oxidases (UstCF1F2) and a pyridoxal 5′‐phosphate (PLP)‐dependent enzyme (UstD). These findings provide new insight into the expression of the RiPP gene clusters found in various fungi.     

Application and mechanism of inhalation profile improvement of DPI formulations by mechanofusion with magnesium stearate

In our previous paper, we reported the inhalation properties of dry powder inhaler (DPI) formulations containing Compound A and mechanofusion-processed lactose carriers. The mechanofusion process with magnesium stearate (Mg-St) on the lactose carrier enhanced the fine particle fraction (FPF) value of the Andersen cascade impactor (ACI) study. The increase of FPF seemed to be associated with the increase of the dispersibility of drug particles. The objectives of this study were (1) to evaluate the applicability of lactose carrier mechanofusion-processed with Mg-St and (2) to examine the mechanism of FPF alteration by the mechanofusion process applied on the lactose carrier with or without additive. The inhalation profiles of DPI formulations containing four different pharmaceutical compounds were evaluated with an ACI. The dispersibility of the formulations was observed by particle size distribution measurement in the air stream and the adhesive force was measured bydirect separation method. It was found that higher FPF was obtained with lactose mechanofusion-processed with Mg-St as compared to control lactose carriers for all four compounds. This suggested that mechanofusion process with Mg-St is widely applicable in DPI formulations. The homogenization of surface adhesiveness was attributed to the increased FPF of the DPI including lactose mechanofusion-processed with Mg-St, as suggested by the combination of several physicochemical characteristics. Combination of different characterization methods would be of help to clarify the whole mechanism which defines the inhalation properties of DPI formulations.     

Crystal structure of a high‐pressure phase of magnesium chloride hexahydrate determined by in‐situ X‐ray and neutron diffraction methods

A high‐pressure phase of magnesium chloride hexahydrate (MgCl₂·6H₂O‐II) and its deuterated counterpart (MgCl₂·6D₂O‐II) have been identified for the first time by in‐situ single‐crystal X‐ray and powder neutron diffraction. The crystal structure was analyzed by the Rietveld method for the neutron diffraction pattern based on the initial structure determined by single‐crystal X‐ray diffraction. This high‐pressure phase has a similar framework to that in the known ambient‐pressure phase, but exhibits some structural changes with symmetry reduction caused by a subtle modification in the hydrogen‐bond network around the Mg(H₂O)₆ octahedra. These structural features reflect the strain in the high‐pressure phases of MgCl₂ hydrates.     

Electronic properties of nano-structured anisotropic superconductors

Using the Bogoliubov-de Gennes equation on the tight-binding electron model, we have investigated nano-structured anisotropic superconductors. For a π/4-rotated square d-wave superconducting plate, the superconducting symmetry becomes s+id, not only at the surfaces, but over the whole superconductor. Also we have investigated quasi-particle structures of this superconducting state.     

Majorana bound state in rotating superfluid 3He-A between parallel plates

A concrete and experimentally feasible example for testing the putative Majorana zero-energy state bound in a vortex is theoretically proposed for a parallel plate geometry of superfluid 3He-A phase. We examine the experimental setup in connection with ongoing rotating cryostat experiments. The theoretical analysis is based on the well-established Ginzburg-Landau functional, supplemented by microscopic calculations of the Bogoliubov-de Gennes equation, both of which allow the precise location of the parameter regions of the Majorana state to be found in realistic situations.     

Hole localization in the one-dimensional doped Anderson-Hubbard model

We study an interplay of disorder and correlation in the one-dimensional hole-doped Hubbard-model with disorder (Anderson-Hubbard model) by using the density-matrix renormalization group method. Concentrating on the doped-hole-density profile, we find in a large U/t regime that the clean system exhibits a simple fluidlike behavior whereas finite disorders create locally Mott regions which expand their area with increasing the disorder strength contrary to the conventional sense. We propose that such an anomalous Mott phase formation assisted by disorder is easily observable in atomic Fermi gases by setting up the box-shape trap.