Development of pyrrole-imidazole polyamide for specific regulation of human aurora kinase-A and -B gene expression

Pyrrole-imidazole polyamide (PIP) is a nuclease-resistant novel compound that inhibits gene expression through binding to the minor groove of DNA. Human aurora kinase-A (AURKA) and -B (AURKB) are important regulators in mitosis during the cell cycle. In this study, two specific PIPs (PIP-A and PIP-B) targeting AURKA and AURKB promoter regions were designed and synthesized, and their biological effects were investigated by several in vitro assays. PIP-A and PIP-B significantly inhibited the promoter activities, mRNA expression, and protein levels of AURKA and AURKB, respectively, in a concentration-dependent manner. Moreover, 1:1 combination treatment with both PIPs demonstrated prominent antiproliferative synergy (CI value [ED(50)] = 0.256) to HeLa cells as a result of inducing apoptosis-mediated severe catastrophe of cell-cycle progression. The novel synthesized PIP-A and PIP-B are potent and specific gene-silencing agents for AURKA and AURKB.     

Energy-saving drying technology for porous media using liquefied DME gas

Process design and energy requirement for a practical plant are investigated for an energy-saving drying (dewatering) process invented by the authors in 2002 for high-moisture porous materials. The basic concept of the process involves the extraction of water from a high-moisture porous material by bringing it in physical contact with liquefied dimethyl ether (DME) at room temperature. Water content of DME asymptotically increases to the saturation value and the high-moisture porous material is dried almost perfectly. DME from the DME-water mixture is vaporized by decompression. DME and water are separated by flash distillation. DME vapor is compressed and cooled in a heat exchanger, and the latent heat of condensation is reused to vaporize the DME in the heat exchanger. Multistage compression and multistage flash distillation are employed. After compression, the temperature of DME is less than 50?°C. Because specific heat ratio of DME is only 1.11, the energy consumption of the compressor is reduced. Considering the adiabatic efficiency of the compressor and the net thermal efficiency, the total energy for dewatering is about 1100 kJ per 1-kg-water-content of the material being dewatered This process has significant potential and is compact than the existing dewatering processes.     

Characterization of atenolol transformation products on light-activated TiO2 surface by high-performance liquid chromatography/high-resolution mass spectrometry

We have studied the photocatalytic transformation of atenolol, 4-[2-hydroxy-3-[(1-methyl)amino]propoxyl]benzeneacetamide, a cardioselective beta-blocking agent used to treat cardiac arrhythmias and hypertension, under simulated solar irradiation using titanium dioxide as photocatalyst. The investigation involved monitoring drug decomposition, identifying intermediate compounds, assessing mineralization, and evaluating toxicity. High-performance liquid chromatography (HPLC) coupled to high-resolution mass spectrometry (HRMS) via an electrospray ionization (ESI) interface was a powerful tool for the identification and measurement of the degradation products; 23 main species were identified. Intermediates were characterized through their chromatographic behavior and evolution kinetics, coupled with accurate mass information. Through the full analysis of MS and MS(n) spectra and a comparison with parent drug fragmentation pathways, the diverse isomers were characterized. Neither atenolol nor the intermediates formed exhibit acute toxicity. All intermediates are easily degraded and no compound identified could withstand 2 h irradiation. Photomineralization of the substrate in terms of carbon mineralization and nitrogen release was rapid and, within 4 h of irradiation, organic nitrogen and carbon were completely mineralized.     

Layer-engineering of high-Tc superconductors: (Cu,Mo)Sr2(Ce,Y)4Cu2O13+delta with a quadruple-fluorite-layer block between CuO2 planes

Among high-Tc superconductive copper oxides, there have been known phases that contain fluorite-structured layers as an additional "blocking block" between adjacent CuO2 planes. Here, we report that even a phase with the CuO2 planes separated by a 12-A thick quadruple-fluorite-layer block can be synthesized in a single phase and strongly oxygenated form to exhibit superconductivity with a Tc value as high as 55 K. The new phase is the fourth member of the (Cu,Mo)Sr2(Ce,Y)sCu2O(5+2s+delta) or (Cu,Mo)-12s2 homologous series. Comparison with the previously known s = 1, 2, and 3 members of the series reveals the amazing conclusion that Tc remains essentially unaffected upon inserting additional fluorite-structured layers between the two CuO2 planes as long as the hole-doping level of the planes is kept constant.     

Temperature-controlled changeable oxygenation selectivity by singlet oxygen with a polymeric photosensitizer

A polymeric photosensitizer, poly(NIPAM-co-RB), consisting of N-isopropylacrylamide and rose bengal units, demonstrates a temperature-controlled changeable oxygenation selectivity by singlet oxygen in water.     

Highly emissive pi-conjugated alkynylpyrene oligomers: their synthesis and photophysical properties

We newly prepared para- and meta-linked alkynylpyrene oligomers and examined their photophysical properties. Oligomerization of monomeric building blocks was performed by CuI-promoted oxidative coupling reaction. The resulting oligomers mainly consist of 2-mer to 6-mer that were assigned on the basis of MALDI-TOF mass spectra, and the 2-mer, 3-mer, and 4-mer were isolated and fully characterized. From their absorption and fluorescence spectra, the para-linked oligomers were found to be somewhat pi-conjugated compared with meta-linked ones, and the fluorescence quantum yields decreased with increasing oligomer length (Phif = 0.79-0.55).     

Highly specific affinities of short peptides against synthetic polymers

We investigated polymer-binding 7-mer peptides that recognize differences in the polymer stereoregularity of all-purpose poly(methyl methacrylate)s (PMMAs) with simple chemical structures. Quantitative surface plasmon resonance measurements detected association/dissociation processes of the peptides against PMMA film surfaces, followed by an estimation of kinetic parameters such as association/dissociation rate constants and affinity constants. Greater association and smaller dissociation constants of the peptides were observed against a target isotactic PMMA than the structurally similar reference syndiotactic PMMA, followed by greater affinity constants against the target. A c02 peptide composed of the Glu-Leu-Trp-Arg-Pro-Thr-Arg sequence showed the greatest affinity constant (2.8x10(5) M(-1)) for the target, which was 41-fold greater than that for the reference, thus demonstrating extremely high peptide specificities. The substitution of each amino acid of the c02 peptide to Ala (Ala scanning) clearly revealed the essential amino acids for the affinity constants; the essential order was Pro5>Thr6>Arg7>Glu1>Arg4. In fact, the shorter 4-mer peptide composed of the C-terminal Arg-Pro-Thr-Arg sequence of the c02 peptide still demonstrated strong target specificity, although the N-terminal 4-mer peptide Glu-Leu-Trp-Arg completely lost its specificity. The possible conformations modeled with Molecular Mechanics supported the significance of the Arg-Pro-Thr-Arg sequence. The thermodynamic parameters of the c02 peptide suggested an induced fit mechanism for the specific affinity. The present affinity analyses of polymer-recognizing peptides revealed significant and general information that was essential for potential applications in peptidyl nanomaterials.     

A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

Synthesis of nickel nanoparticles supported on hollow samaria-doped ceria particles via the solution-spray plasma technique: Anode catalysts for SOFCs

Aiming at SOFC anode applications, we have synthesized nanometer-sized nickel catalysts supported on hollow spherical particles of samaria-doped ceria (Ni/SDC) by spraying a mixed solution of nickel, samarium, and cerium nitrates into an atmospheric pressure plasma. The as-prepared particles consisted of SDC (average diameter d_SDC = ca. 0.8 µm) and uniformly dispersed nanometer-sized NiO particles. When reduced in H₂ at 800 °C or 1000 °C, Ni nanoparticles (average diameter d_Ni = 34 nm) were found to be embedded uniformly into the SDC surface.