Size Controlled Synthesis of Gold Nanoparticles by Porphyrin with Four Sulfur Atoms

Tetradentate thioacetyl porphyrin ligand (1) was synthesized to protect gold nanoparticles. 1-protected gold nanoparticles were characterized by UV-vis spectroscopy and XPS. Analysis by XPS showed that all of four thioacetyl groups of 1 were dissociated and bound to the surface of gold nanoparticles in thiolate form. The size of 1-protected gold nanoparticles (GN:1) was controlled by thioacetyl group/HAuCl₄ molar ratio and approached to 2 nm. Compared with a protecting ligand without porphyrin plane (2) or dodecanethiol, 1 can control the size of gold nanoparticles efficiently probably due to the tetradentate ligation effect.     

Temperature- and pH-responsive photosensitization activity of polymeric sensitizers based on poly-N-isopropylacrylamide

We previously reported that a copolymer consisting of N-isopropylacrylamide (NIPAM) and benzophenone (BP) units, behaves as a photosensitizer showing temperature-controlled oxygenation activity in water (J. Am. Chem. Soc.2006, 128, 8751). This polymer shows a heat-induced oxygenation enhancement at low temperature region (5-20 °C), while showing a heat-induced oxygenation suppression at high temperature region (20-60 °C), resulting in an off-on-off activity profile against the temperature window. This is driven by a heat-induced phase transition of the polymer from coil to micelle and then to globule states. In the present work, effects of adding an amine component (N-[3-(dimethylamino)propyl]acrylamide: DMAPAM) to the polymer on the sensitization activity were studied, where the relationship between the phase transition behavior and the activity was clarified by several spectroscopic analyses. The polymers, poly(NIPAM_x-co-BP_y-co-DMAPAM_z), show activity controlled by temperature and pH. The off-on-off activity profile shifts to higher temperature with a pH decrease. This is because protonation of the DMAPAM units leads to an increase in the polymer polarity and, hence, the polymer aggregates at higher temperature. In addition, increase in the DMAPAM content of the polymer leads to further shift of the activity profile. In contrast, at pH < 8, no activity enhancement is observed because complete protonation of the DMAPAM units suppresses polymer aggregation.     

Aerobic Alcohol Oxidation by Ruthenium Species Stabilized on Nanocrystalline Magnesium Oxide by Basic Ionic Liquids

The selective oxidation of various alcohols into their corresponding aldehydes and ketones was achieved by ruthenium species stabilized on the nanocrystalline magnesium oxide (NAP‐MgO) by the incorporation of choline hydroxide, a basic ionic liquid, in excellent yields. The procedure is simple, efficient and environmentally benign. The catalyst can be used for four cycles with almost consistent activity.     

To Journal of Phase Equilibria and Diffusion Phase Relationship of the BaO-ZrO<Subscript>2</Subscript>-YO<Subscript>1.5</Subscript> System at 1500 and 1600 °C

Phase relationship of a BaO-ZrO₂-YO_1.5 system at 1500 and 1600 °C was examined in order to determine whether a phase separation at the composition of 15% yttrium-doped barium zirconate exists. According to a pseudoternary phase diagram of the BaO-ZrO₂-YO_1.5 system established by this work, the solubility of yttria into cubic barium zirconate at 1600 °C is 0.25 in a mole fraction of yttria (X_textYO1.5 ) (X_{{{text{YO}}_{1.5} }} ) . Thus, we confirmed that there is no phase separation at the composition of 15% yttrium-doped barium zirconate at 1600 °C. On the other hand, at 1500 °C, there might be a phase separation at the composition of 15% yttrium-doped barium zirconate into yttrium-doped barium zirconate where quite small amount of yttrium is doped and a new phase whose composition is close to reported BZ(II) phase.     

Fracture Strength and Microstructure of β-SiAlON with Hafnia Addition

The influence of HfO₂ addition on the fracture strength and microstructure of ß-SiAlON ceramics sintered from Si₃N₄ and Al₂O₃ powders was investigated. The strength was increased by the addition of HfO₂, from ∼500 MPa to 700 MPa, and was almost constant from ambient temperature to 1300°C. Monoclinic HfO₂ grains that were distributed in the SiAlON grain boundaries had a flat shape (∼20 nm thick) and were surrounded by an amorphous phase. The aluminum concentration in ß-SiAlON in the samples with an Al₂O₃ starting composition of 15 wt% was decreased by the addition of HfO₂. The amount of secondary phases was very small at grain boundaries between the SiAlON grains; amorphous phases were observed infrequently at the triple points but were very small (∼20 nm). The effects of HfO₂ addition on the mechanism of the microstructure development and fracture strength are discussed.     

MiR-10a in Pancreatic Juice as a Biomarker for Invasive Intraductal Papillary Mucinous Neoplasm by miRNA Sequencing

New biomarkers are needed to further stratify the risk of malignancy in intraductal papillary mucinous neoplasm (IPMN). Although microRNAs (miRNAs) are expected to be stable biomarkers, they can vary owing to a lack of definite internal controls. To identify universal biomarkers for invasive IPMN, we performed miRNA sequencing using tumor-normal paired samples. A total of 19 resected tissues and 13 pancreatic juice samples from 32 IPMN patients were analyzed for miRNA expression by next-generation sequencing with a two-step normalization of miRNA sequence data. The miRNAs involved in IPMN associated with invasive carcinoma were identified from this tissue analysis and further verified with the pancreatic juice samples. From the tumor-normal paired tissue analysis of the expression levels of 2792 miRNAs, 20 upregulated and 17 downregulated miRNAs were identified. In IPMN associated with invasive carcinoma (INV), miR-10a-5p and miR-221-3p were upregulated and miR-148a-3p was downregulated when compared with noninvasive IPMN. When these findings were further validated with pancreatic juice samples, miR-10a-5p was found to be elevated in INV (p = 0.002). Therefore, three differentially expressed miRNAs were identified in tissues with INV, and the expression of miR-10a-5p was also elevated in pancreatic juice samples with INV. MiR-10a-5p is a promising additional biomarker for invasive IPMN.     

Relation between crystal structure and lattice oxygen content of sintered reaction-bonded silicon nitride

When reaction-bonded silicon nitride containing MgO/Y₂O₃ additives is sintered at three different temperatures to form sintered reaction-bonded silicon nitride (SRBSN), the thermal conductivity increases with sintering temperature. The β-Si₃N₄ (silicon nitride) crystals of SRBSN ceramics were synthesized and characterized to investigate the relation between the crystal structure and the lattice oxygen content. The hot-gas extraction measurement result and the crystal structure obtained using Rietveld analysis suggested that the unit cell size of the β-Si₃N₄ crystal increases with the decrease in the lattice oxygen content. This result is reasonable considering that the lattice oxygen with the smaller covalent radius substitutes nitrogen with the larger one in the β-Si₃N₄ crystals. The lattice oxygen content decreased with increasing sintering temperature which also correlated with increase in thermal conductivity. Moreover, it is noteworthy from the viewpoint that it may be possible to apply the lattice constant analysis for the nondestructive and simple measurement of the lattice oxygen content that deteriorates the thermal conductivity of the β-Si₃N₄ ceramics.     

Negative ion etching of Al−Si−Cu by employing a magnetic filter in halogen plasmas

Al etching was studied employing negative ions generated in downstream Cl₂ plasma. The Al etch rate by the alternate irradiation of positive and negative ions was two times higher than that by usual positive ions. In order to etch the Al film practically on an insulator covered electrode coupled with RF power, reduction of the negative self bias voltage (Vdc) was examined using a magnetic filter which traps electrons. The reason for the high etching reactivity is that the dominant negative ions F in SF₆ and Cl⁻ in Cl₂ plasmas are atomically very similar to the radicals. Addition of SF₆ and H₂ to a Cl₂/BCl₃ mixture reduced Vdc significantly. However, fluorine and hydrogen atoms inhibited Al etching in spite of sufficient ion energy.     

Re-evaluation of Radiation-Energy Transfer to an Extraction Solvent in a Minor-Actinide-Separation Process Based on Consideration of Radiation Permeability

ABSTRACT

Absorbed-dose estimation is essential for evaluation of the radiation tolerance of minor-actinide-separation processes. We propose a dose-evaluation method based on radiation permeability, with comparisons of heterogeneous structures seen in the solvent-extraction process, such as emulsions forming in the mixture of the organic and aqueous phases. A demonstration of radiation-energy-transfer simulation is performed with a focus on the minor-actinide-recovery process from high-level liquid waste with the aid of the Monte Carlo radiation-transport code PHITS. The simulation results indicate that the dose absorbed by the extraction solvent from alpha radiation depends upon the emulsion structure, and that from beta and gamma radiation depends upon the mixer-settler-apparatus size. Non-negligible contributions of well-permeable gamma rays were indicated in terms of the plant operation of the minor-actinide-separation process.