High pressure experiments with synchrotron radiation

Using a diamond anvil cell (DAC), high pressure ⁵⁷Fe Mössbauer spectroscopy has been performed with the nuclear forward scattering of synchrotron radiation. We used monochromatized synchrotron radiation from an in‐vacuum type undulator as a high‐density strong Mössbauer source with a quite small beam size. Pressure‐induced magnetic hyperfine interactions at ⁵⁷Fe in SrFeO_2.97 has been detected at 74 GPa by a quantum‐beat modulation of the decay rate after collective nuclear excitation with the synchrotron radiation pulse. Evidence for a transition from antiferromagnetism to ferromagnetism of Fe in SrFeO_2.97 at 74 GPa and 300 K has been obtained from the nuclear forward scattering under a transverse magnetic field.     

Eu-Doped KCl storage phosphor for erasable and rewritable optical memory utilizing photostimulated luminescence phenomenon

Intense photostimulated luminescence (PSL) with a peak at 420 nm is observed in ultraviolet (UV) Iight-irradiated europium-doped potassium chloride (KCl: Eu) crystalline phosphors. The PSL characteristics of UV-irradiated KCl: Eu phosphor for optical memory application were studied. The excitation and emission mechanisms of the 420 nm PSL, which are consistent with the results obtained, are discussed.     

57Fe Mössbauer study under high pressure; ε-Fe and Fe2O3

Using diamond anvil cell, the⁵⁷Fe Mössbauer spectra of pure iron foil and α-Fe₂O₃ powder under high pressure have been measured at room temperature.⁵⁷Fe Mössbauer spectra of α-Fe were measured from 15 GPa to 45 GPa. Isomer shift value decreased and the quadrupole splitting slightly increased as the pressure increased.⁵⁷Fe Mössbauer spectra of Fe₂O₃ under high pressure up to 72 GPa were observed. Above 52 GPa, the new lines appeared at the center portion of the spectrum corresponding to the new high pressure phase. The spectrum of new high pressure phase consisted of 6-line splitting and doublet, suggesting the existence of the two different kinds of iron states in it.     

Buffers to suppress sodium dodecyl sulfate adsorption to polyethylene oxide for protein separation on capillary polymer electrophoresis

Although polyethylene oxide (PEO) offers several advantages as a sieving polymer in SDS capillary polymer electrophoresis (SDS-CPE), solution properties of PEO cause deterioration in the electrophoresis because PEO in solution aggregates itself, degrades into smaller pieces, and forms polymer-micelle complexes with SDS. We examined protein separation on SDS-CPE with PEO as a sieving matrix in four individual buffer solutions: Tris-CHES, Tris-Gly, Tris-Tricine, and Tris-HCl buffers. The solution properties of PEO as a sieving matrix in those buffers were examined by dynamic light scattering (DLS) and by surface tension. Preferential SDS adsorption onto PEO disturbed protein-SDS complexation and impaired the protein separation efficiency. Substantial adsorption of SDS to PEO was particularly observed in Tris-Gly buffer. The Tris-CHES buffer prevented SDS from adsorbing onto the PEO. Only Tris-CHES buffer achieved separation of six proteins. This study demonstrated efficient protein separation on SDS-CPE with PEO.     

Abnormal phospholipids distribution in the prefrontal cortex from a patient with schizophrenia revealed by matrix-assisted laser desorption/ionization imaging mass spectrometry

Schizophrenia is one of the major psychiatric disorders, and lipids have focused on the important roles in this disorder. In fact, lipids related to various functions in the brain. Previous studies have indicated that phospholipids, particularly ones containing polyunsaturated fatty acyl residues, are deficient in postmortem brains from patients with schizophrenia. However, due to the difficulties in handling human postmortem brains, particularly the large size and complex structures of the human brain, there is little agreement regarding the qualitative and quantitative abnormalities of phospholipids in brains from patients with schizophrenia, particularly if corresponding brain regions are not used. In this study, to overcome these problems, we employed matrix-assisted laser desorption/ionization imaging mass spectrometry (IMS), enabling direct microregion analysis of phospholipids in the postmortem brain of a patient with schizophrenia via brain sections prepared on glass slides. With integration of traditional histochemical examination, we could analyze regions of interest in the brain at the micrometric level. We found abnormal phospholipid distributions within internal brain structures, namely, the frontal cortex and occipital cortex. IMS revealed abnormal distributions of phosphatidylcholine molecular species particularly in the cortical layer of frontal cortex region. In addition, the combined use of liquid chromatography/electrospray ionization tandem mass spectrometry strengthened the capability for identification of numerous lipid molecular species. Our results are expected to further elucidate various metabolic processes in the neural system.     

Capillary electrophoretic discrimination of single nucleotide polymorphisms using an oligodeoxyribonucleotidepolyacrylamide conjugate as a pseudo-immobilized affinity ligand: optimum ligand length predicted by the melting temperature values.

We developed a weak-affinity separation system for single-nucleotide polymorphisms (SNPs) based on capillary electrophoresis. In this approach, single-stranded DNA (ssDNA)-polyacrylamide (polyAAm) conjugate was used as a pseudo-immobilized affinity ligand to separate the target DNA, cytochrome P450 2C9 (CYP2C9), and its point mutant. The ligand DNA was designed to be complementary to the normal DNA, and the target DNA was electrophoretically separated by the difference in the affinity with the pseudo-immobilized ligand in the capillary. We showed that the separation efficiency was closely associated with the Tm value of double-stranded DNA (dsDNA) consisting of the target and ligand DNA, which depends on the measurement conditions, such as the base number of the ligand DNA and the concentration of Mg2+ in the buffer solution.     

Improvement of wettability and detergency of polymeric materials by excimer UV treatment

The 172 nm ultraviolet (UV) excimer light was exposed to polyethylene (PE), polypropylene, poly(ethylene terephthalate) and nylon 6 surfaces in ambient air. Changes in the contact angle and particle deposition in liquid due to UV treatment were investigated from the viewpoints of wettability and detergency. For all polymers, the wettability and the acid-base component of the surface free energy evaluated by the contact angle measurements increased remarkably by UV treatment of 1 min. From surface analyses of the polymer surfaces by X-ray photoelectron spectroscopy and atomic force microscopy, oxygen concentration was found to increase after UV treatment, whereas little topographical change was observed. The deposition of PE and nylon 12 particles onto the polymer surface was examined, in situ, in water, water/ethanol mixture, ethanol and n-heptane. Although the number of deposited particles was largely dependent on the kinds of the particle, the substrate and the liquid, a significant decrease in the deposition due to UV treatment was confirmed in any system.     

The three-dimensional structure of aspergilloglutamic peptidase from Aspergillus niger

Aspergilloglutamic peptidase from Aspergillus niger is a novel pepstatin-insensitive acid endopeptidase distinct from the well-studied aspartic peptidases, and thus is an interesting target for protein structure/function studies. In the present study, we have determined the three-dimensional structure of the enzyme by X-ray crystallography to a 1.4-Å resolution. The results revealed that the enzyme has a unique structure, composed of two seven-stranded anti-parallel β-sheets which form a β-sandwich structure and appear to have a partial two-fold symmetry, suggesting its possible evolution by gene duplication and that the glutamic acid-110 and glutamine-24 in the heavy chain form a catalytic dyad, consistent with our results obtained by site-directed mutagenesis.     

Development of a new traceless aniline linker for solid-phase synthesis of azomethines. Application to parallel synthesis of a rod-shaped liquid crystalline library

A new traceless linker was developed to synthesize a library of 42 compounds possessing an azomethine linkage using combinatorial solid-phase parallel synthesis. The loading of the substrates on a solid support and cleavage from the solid support were performed by an imine synthesis and by imine-exchanged process under mild conditions, respectively. Thioesters with a hydroxy group on the central core exhibited liquid crystalline properties with the widest transition temperatures in the library.     

Phase grating generation and optical phase conjugation in photorefractive polymer/dissolved liquid crystal composites

The orientational photorefractive properties of photorefractive mesogenic composites have been investigated by means of two-beam coupling and degenerate four-wave mixing. Photorefractive mesogenic composites, consisting of low molar mass liquid crystals, polymer, and photoconductive sensitizer, constitute novel organic materials possessing high performance photoreractivity. The refractive index change was estimated on the basis of the theory of two-beam coupling and four-wave mixing, and large index modulation of over 0.01 was obtained.