Highly Reactive β-Dicalcium Silicate: I, Hydration Behavior at Room Temperature

The hydration behavior at 25°C of β-dicalcium silicate synthesized from hillebrandite (Ca₂,(SiO₃)(OH)₂) at 600°C was studied over a period of 224 d. The hydration rate of the β-dicalcium silicate having fibrous crystals with specific surface area of 7 m²/g is extremely rapid. For water/solids ratios of 0.5 and 1.0, the hydration reaction is completed in 28 and 14 d, respectively. The hydrate contains almost no Ca(OH)₂, and its Ca/Si ratio is close to 2. SEM observations indicate that the hydrate forms an outer shell on the surface of β-dicalcium silicate and grows inwards. The silicate anion structure is considered to consist of dimers and single-chain structures from ²⁹Si MAS NMR. Variations of physical properties of press-formed bodies have also been discussed.     

Measurement of space charge distribution in epoxy resin

Internal space charge behavior of insulating materials has recently attracted attention of many researchers, and a large number of experimental studies were carried out by using the materials for dc cables, such as XLPE, LDPE, and HDPE. Epoxy resins are used for insulation under strong electric fields in power apparatus and in electronic devices, and we investigated the behavior of internal space charge using the pulsed electroacoustic method. Two types of epoxy resins were studied: insulation-grade and craft-grade. When dc electric fields were applied to the craft resins treated by immersing them into room-temperature water for 8 and 24 h, positive and negative charges accumulated near the anode and the cathode, respectively, and the charge distribution changed with the immersion time. On the other hand, no charge was observed in the insulation-grade epoxy resin. Next, we treated the samples by immersing them into 100 °C water for 8 h. When the sample was treated for 8 h, hetero charge distribution, which means positive charges near the cathode and negative charges near the anode, was observed. This result is consistent with a previous paper reporting that by chemical analysis, secondary decomposition had occurred. These results show that water and temperature influence the internal space charge behavior of epoxy resins. © 1999 Scripta Technica, Electr Eng Jpn, 129(3): 9–16, 1999     

Methotrexate Alters the Expression of microRNA in Fibroblast-like Synovial Cells in Rheumatoid Arthritis

We aimed to investigate the effect of methotrexate (MTX) on microRNA modulation in rheumatoid arthritis fibroblast-like synovial cells (RA-FLS). RA-FLS were treated with MTX for 48 h. We then performed miRNA array analysis to investigate differentially expressed miRNAs. Transfection with miR-877-3p precursor and inhibitor were used to investigate the functional role of miR-877-3p in RA-FLS. Gene ontology analysis was used to investigate the cellular processes involving miR-877-3p. The production of cytokines/chemokines was screened by multiplex cytokine/chemokine bead assay and confirmed by ELISA and quantitative real-time PCR. The migratory and proliferative activities of RA-FLS were analyzed by wound healing assay and MKI-67 expression. MTX treatment altered the expression of 13 miRNAs (seven were upregulated and six were downregulated). Among them, quantitative real-time PCR confirmed that miR-877-3p was upregulated in response to MTX (1.79 ± 0.46-fold, p < 0.05). The possible target genes of miR-877-3p in RA-FLS revealed by the microarray analysis were correlated with biological processes. The overexpression of miR-877-3p decreased the production of GM-CSF and CCL3, and the overexpression of miR-877-3p inhibited migratory and proliferative activity. MTX altered the miR-877-3p expression on RA-FLS, and this alteration of miR-877-3p attenuated the abundant production of cytokines/chemokines and proliferative property of RA-FLS.     

Interlaboratory validation of quantitative duplex real-time PCR method for screening analysis of genetically modified maize

To reduce the cost and time required to routinely perform the genetically modified organism (GMO) test, we developed a duplex quantitative real-time PCR method for a screening analysis simultaneously targeting an event-specific segment for GA21 and Cauliflower Mosaic Virus 35S promoter (P35S) segment [Oguchi et al., J. Food Hyg. Soc. Japan, 50, 117-125 (2009)]. To confirm the validity of the method, an interlaboratory collaborative study was conducted. In the collaborative study, conversion factors (Cfs), which are required to calculate the GMO amount (%), were first determined for two real-time PCR instruments, the ABI PRISM 7900HT and the ABI PRISM 7500. A blind test was then conducted. The limit of quantitation for both GA21 and P35S was estimated to be 0.5% or less. The trueness and precision were evaluated as the bias and reproducibility of the relative standard deviation (RSD(R)). The determined bias and RSD(R) were each less than 25%. We believe the developed method would be useful for the practical screening analysis of GM maize.     

PEG Modification Effect of Silica on the Suzuki–Miyaura Coupling Reaction Using Silica-immobilized Palladium Catalysts

Abstract  

The Pd phosphine complex catalysts immobilized onto polyethylene glycol (PEG)-modified silica were prepared in order to clarify the effect of the PEG modification on the Suzuki–Miyaura coupling reaction in organic solvents. For the reaction of ethyl p-bromobenzoate and phenylboronic acid in the presence of potassium carbonate in toluene, the PEG-modified silica-immobilized Pd catalysts exhibited much higher activities than the catalysts without PEG modification.     

Biological Evaluation of Double Point Modified Analogues of 1,25-Dihydroxyvitamin D2 as Potential Anti-Leukemic Agents

Structurally similar double-point modified analogues of 1,25-dihydroxyvitamin D₂ (1,25D₂) were screened in vitro for their pro-differentiating activity against the promyeloid cell line HL60. Their affinities towards human full length vitamin D receptor (VDR) and metabolic stability against human vitamin D 24-hydroxylase (CYP24A1) were also tested. The analogues (PRI-1730, PRI-1731, PRI-1732, PRI-1733 and PRI-1734) contained 5,6-trans modification of the A-ring and of the triene system, additional hydroxyl or unsaturation at C-22 in the side chain and reversed absolute configuration (24-epi) at C-24 of 1,25D₂. As presented in this paper, introduction of selected structural modifications simultaneously in two distinct parts of the vitamin D molecule resulted in a divergent group of analogues. Analogues showed lower VDR affinity in comparison to that of the parent hormones, 1,25D₂ and 1,25D₃, and they caused effective HL60 cell differentiation only at high concentrations of 100 nM and above. Unexpectedly, introducing of a 5,6-trans modification combined with C-22 hydroxyl and 24-epi configuration switched off entirely the cell differentiation activity of the analogue (PRI-1734). However, this analogue remained a moderate substrate for CYP24A1, as it was metabolized at 22%, compared to 35% for 1,25D₂. Other analogues from this series were either less (12% for PRI-1731 and PRI-1733) or more (52% for PRI-1732) resistant to the enzymatic deactivation. Although the inactive analogue PRI-1734 failed to show VDR antagonism, when tested in HL60 cells, its structure might be a good starting point for our design of a vitamin D antagonist.     

Synthesis of Calcium Silicate Hydrate with Ca/Si = 2 by Mechanochemical Treatment

An amorphous, C-S-H-like phase with Ca/Si = 2 was synthesized from amorphous precipitated silica, calcium oxide, and water by mechanochemical treatment using a vibration mill at room temperature. The product was studied by XRD, ²⁹Si MASNMR, TEM, analytical TEM, and TGA-DTA. After 14 h of treatment, the starting materials react to form an amorphous phase (C-S-H-like phase). The XRD pattern of C-S-H-like phase resembles the C-S-H formed hydrothermally or by cement hydration except it has no reflection at 0.182 nm. The ²⁹Si NMR results revealed a silicate anion structure of C-S-H-like phase consisting mainly of a mixture of a monomer and a dimer. On heating, the C-S-H-like phase decomposed into β-dicalcium silicate below 1000°C.     

Crystal Phase and Orientation Control in Integrated Ferroelectric CaBi4Ti4O15 Using a Tailored Liquid of Alkoxides

We used a Ca–Bi–Ti complex alkoxide, in which metal–oxygen bonding was confirmed by spectroscopic analysis, to deposit CaBi₄Ti₄O₁₅ (CBTi144) thin films in various configurations. The phase transition of non-ferroelectric pyrochlore to ferroelectric perovskite in the complex-alkoxy-derived CBTi144 thin films was found to depend on the Pt bottom electrodes. Matching of the atomic arrangement to the Ca–Bi–Ti–O thin films was predominant rather than the strain and crystallinity of the bottom electrode. The thin films crystallized at 650°C on (111)-oriented Pt showed random orientation and ferroelectric P – V hysteresis loops. The endurance property was excellent against a number of switchings. For this reason, CBTi144 thin films would be expected to be excellent for application to ferroelectric random access memories (FeRAM). Polar-axis-oriented CBTi144 films were fabricated on Pt foils using the complex metal alkoxide solution. The 500-nm-thick film had a columnar structure comprising well-developed grains. The a / b -axis orientation of the ferroelectric films is considered to be associated with the preferred orientation of Pt foil. The film showed improved ferro- and piezoelectric properties. The P _r, E _c, and d ₃₃ values were enhanced to become twice those of CBTi144 thin films with random orientation. These polar-axis-oriented CBTi144 films are eminently useful in devices as Pb-free piezoelectric materials.