Structurally Diverse Polyamines: Solid‐Phase Synthesis and Interaction with DNA

A versatile solid‐phase approach based on peptide chemistry was used to construct four classes of structurally diverse polyamines with modified backbones: linear, partially constrained, branched, and cyclic. Their effects on DNA duplex stability and structure were examined. The polyamines showed distinct activities, thus highlighting the importance of polyamine backbone structure. Interestingly, the rank order of polyamine ability for DNA compaction was different to that for their effects on circular dichroism and melting temperature, thus indicating that these polyamines have distinct effects on secondary and higher‐order structures of DNA.     

Kinetically Stable Bicelles with Dilution Tolerance,Size Tunability,and Thermoresponsiveness for Drug Delivery Applications

Mixtures of a phospholipid (1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphatidylcholine, DPPC) and a sodium‐cholate‐derived surfactant (SC‐C₅) at room temperature formed phospholipid bilayer fragments that were edge‐stabilized by SC‐C₅: so‐called “bicelles”. Because the bilayer melting point of DPPC (41 °C) is above room temperature and because SC‐C₅ has an exceptionally low critical micelle concentration (<0.5 mm ), the bicelles are kinetically frozen at room temperature. Consequently, they exist even when the mixture is diluted to a concentration of 0.04 wt %. In addition, the lateral size of the bicelles can be fine‐tuned by altering the molar ratio of DPPC to SC‐C₅. On heating to ≈37 °C, the bicelles transformed into micelles composed of DPPC and SC‐C₅. By taking advantage of the dilution tolerance, size tunability, and thermoresponsiveness, we demonstrated in vitro drug delivery based on use of the bicelles as carriers, which suggests their potential utility in transdermal drug delivery.     

Development of Novel Inhibitors for Histone Methyltransferase SET7/9 based on Cyproheptadine

The histone methyltransferase SET7/9 methylates not only histone but also non‐histone proteins as substrates, and therefore, SET7/9 inhibitors are considered candidates for the treatment of diseases. Previously, our group identified cyproheptadine, used clinically as a serotonin receptor antagonist and histamine receptor (H1) antagonist, as a novel scaffold of the SET7/9 inhibitor. In this work, we focused on dibenzosuberene as a substructure of cyproheptadine and synthesized derivatives with various functional groups. Among them, the compound bearing a 2‐hydroxy group showed the most potent activity. On the other hand, a 3‐hydroxy group or another hydrophilic functional group such as acetamide decreased the activity. Structural analysis clarified a rationale for the improved potency only by tightly restricted location and type of the hydrophilic group. In addition, a SET7/9 loop, which was only partially visible in the complex with cyproheptadine, became more clearly visible in the complex with 2‐hydroxycyproheptadine. These results are expected to be helpful for further structure‐based development of SET7/9 inhibitors.     

Improvement of lysozyme recovery method from the precipitate of protein-anionic surfactant complexes

A new protein separation process using a surfactant and a polar organic solvent consists of a precipitation step and a recovery step. In the precipitation step, a protein-surfactant complex is precipitated from an aqueous solution, when an ionic surfactant, sodium di(2-ethylhexyl) sulfosuccinate (AOT), is added to an aqueous solution, including protein (lysozyme). In the recovery step, the precipitate is dissolved in a polar organic solvent, such as acetone, and the protein is recovered as precipitates when a very small amount of salt solution was added to remove surfactants from the protein-surfactant complex. However, the details of the protein recovery step from precipitate have not been studied yet. In this study, the improvement of the protein recovery step was examined from the viewpoint of a recovery ratio of protein and a remaining ratio of surfactant. The optimum NaCl concentration in the feed for the protein recovery was in the range of 0.05–0.2 kmol/m³. As the NaCl concentration in the feed increased to more than 0.2 kmol/m³, the precipitation ratio decreased due to the electrostatic screening effect of NaCl. It was found that the addition of a very small amount of NaCl solution to acetone was unnecessary when NaCl was included in the feed lysozyme solution. On the other hand, as the NaCl concentration decreased to less than 0.05 kmol/m³, the precipitation ratio was decreased due to the low re-precipitation of protein by the addition of a small amount of NaCl solution in acetone. In the case of the feed containing no salt, the desired NaCl concentration added to acetone was in the range above 0.2 kmol/m³. In addition, the most suitable volume ratio of acetone to feed was found to be 0.2.     

Characteristics and Reactivity of Lignin in Acacia and Eucalyptus Woods

The chemical characteristics of lignin, including the Klason lignin content, acid-soluble lignin content, proportion of the aromatic ring types [syringyl ratio = syringyl/(syringyl + guaiacyl)], and proportion of the diastereomeric forms for the β-O-4 structure [erythro ratio = erythro/(erythro + threo)], and pulpability were investigated for 28 wood samples belonging to the genera Acacia and Eucalyptus. Although the lignin characteristics of these 28 woods varied widely, the chemical characteristics of the two genera could be categorized in two clearly distinguished groups on the basis of the syringyl ratio. Clear negative correlations were observed between both the syringyl and erythro ratios and the total lignin content (sum of the Klason and acid-soluble lignin contents) within each genus. In addition, the syringyl ratio correlated positively with the erythro ratio and acid-soluble lignin content, regardless of the genus. The existence of a clear, high correlation between the syringyl and erythro ratios supports the hypothesis that the aromatic ring type (syringyl ratio) is a decisive factor for controlling the diastereomeric forms of the β-O-4 structure (erythro ratio). Each of the wood samples was also subjected to Kraft pulping, and it was demonstrated that the woods with higher syringyl ratios were easier to delignify. This tendency is reasonably attributed to the high reactivity of the erythro-rich and syringyl-rich β-O-4 structures, and the low lignin content of these syringyl-rich woods.     

Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

The role of aluminum in automotive weight reduction—part III

This series of articles provides, from an international perspective, an analysis of the future of the automotive industry and aluminum’s role in automobile weight reduction. Part I briefly described technological, environmental, and societal issues that are mandating vehicular weight reduction for, among other reasons, purposes of fuel economy. Part II described the status of the weight-reduction technologies that are currently available and projects how they may evolve in the coming years. Part III, the final installment, examines some of the specific strengths and weaknesses of aluminum alloys with regard to their long-term attractiveness to automakers.     

Transparent Hydroxyapatite Prepared by Hot Isostatic Pressing of Filter Cake

Hydroxyapatite powder was synthesized and formed into a compact in an aqueous medium using a filter-cake method. The compact was hot isostatically pressed at 700° to 1000°C and 100 MPa for 2 h. Fully dense, transparent materials were obtained above 800°C. Both forming and densification methods were found to be important in obtaining transparent materials.     

Measurement of longitudinal distribution of solids holdup in a three-phase fluidized bed by ultrasonic technique

A method of measurement of solids holdup in a three-phase reactor by analyzing the shape and the phase lag or lead of an ultrasonic wave has been proposed. The solids holdup in a solids-dilute three-phase fluidized bed could be measured without being affected by the presence of gas bubbles. The experimental values of solids axial dispersivity measured by the ultrasonic technique are in reasonable agreement with an empirical correlation of previous data obtained by other methods. The possibility of the application of the ultrasonic technique to the measurement of solids holdup in a three-phase fluidized bed has been suggested.