Anisotropic Thermal Expansion of β-Ca2SiO4 Monoclinic Crystal

Crystals of β-Ca₂SiO₄ (space group P 12₁/ n 1) were examined by high-temperature powder X-ray diffractometry to determine the change in unit-cell dimensions with temperature up to 645°C. The temperature dependence of the principal expansion coefficients (α_i) found from the matrix algebra analysis was as follows: α₁= 20.492 × 10⁻⁶+ 16.490 × 10⁻⁹ ( T - 25)°C⁻¹, α₂= 7.494 × 10⁻⁶+ 5.168 × 10⁻⁹( T - 25)°C⁻¹, α₃=−0.842 × 10⁻⁶− 1.497 × 10⁻⁹( T - 25)°C⁻¹. The expansion coefficient α₁, nearly along [302] was approximately 3 times α₂ along the b -axis. Very small contraction (α₃) occurred nearly along [     01]. The volume changes upon martensitic transformations of β↔α_L' were very small, and the strain accommodation would be almost complete. This is consistent with the thermoelasticity.     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel iron oxide–silica coreshell powders compacted by using pulsed electric current sintering: Optical and magnetic properties

The properties of the bulk materials consolidated of silica coreshell powders with iron oxide core have been studied. Iron oxide nanoparticles smaller than 20 nm in size were synthesized by a reverse co-precipitation process in ambient atmosphere. Coreshell structures with various amounts of iron oxide were prepared via a modified Stöber method. The powders were compacted by using pulsed electric current sintering (PECS) at 1373 K. The morphologies, microstructures, phases, optical, and magnetic properties of the samples were studied by using transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), UV–visible spectroscopy (UV–Vis), and vibrating sample magnetometer (VSM). Transmittance values in the 250–800 nm range varied with the amount of iron oxide. Sample with the lower content was transparent while the sample with the highest content was opaque with microporosity. The compact with the highest iron oxide content showed the ferromagnetic behaviour at 300 K. The phase transformations in the coreshell powders during the sintering process are discussed.     

Prediction of a New Ligand-Binding Site for Type 2 Motif based on the Crystal Structure of ALG-2 by Dry and Wet Approaches

ALG-2 is a penta-EF-hand Ca(2+)-binding protein and interacts with a variety of intracellular proteins. Two types of ALG-2-binding motifs have been determined: type 1, PXYPXnYP (X, variable; n = 4), in ALIX and PLSCR3; type 2, PXPGF, in Sec31A and PLSCR3. The previously solved X-ray crystal structure of the complex between ALG-2 and an ALIX peptide containing type 1 motif showed that the peptide binds to Pocket 1 and Pocket 2. Co-crystallization of ALG-2 and type 2 motif-containing peptides has not been successful. To gain insights into the molecular basis of type 2 motif recognition, we searched for a new hydrophobic cavity by computational algorithms using MetaPocket 2.0 based on 3D structures of ALG-2. The predicted hydrophobic pocket designated Pocket 3 fits with N-acetyl-ProAlaProGlyPhe-amide, a virtual penta-peptide derived from one of the two types of ALG-2-binding sites in PLSCR3 (type 2 motif), using the molecular docking software AutoDock Vina. We investigated effects of amino acid substitutions of the predicted binding sites on binding abilities by pulldown assays using glutathione-S-transferase -fused ALG-2 of wild-type and mutant proteins and lysates of cells expressing green fluorescent protein -fused PLSCR3 of wild-type and mutants. Substitution of either L52 with Ala or F148 with Ser of ALG-2 caused loss of binding abilities to PLSCR3 lacking type 1 motif but retained those to PLSCR3 lacking type 2 motif, strongly supporting the hypothesis that Pocket 3 is the binding site for type 2 motif.     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Studies on phase separation rate in porous polyimide membrane formation by immersion precipitation

Phase separation rate during porous membrane formation by immersion precipitation was investigated by light scattering in a polyimide/N‐Methylpyrrolidone (NMP)/water system. In the light scattering measurement, plots of scattered intensity against scattered angle showed maxima in all cases, which indicated that phase separation occurred by a spinodal decomposition (SD). Characteristic properties of the early stage of SD, such as an apparent diffusion coefficient D_app and an interphase periodic distance Λ, were obtained. The growth process of Λ was also followed by light scattering. The growth rate had the same tendency as D_app when water content in the nonsolvent bath and the polymer concentration in the cast solution were changed. The pore size of the final membrane increased with decreasing water content, which was opposite to the tendency of Λ growth rate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 292–296, 2003     

Porous cellulose acetate membrane prepared by thermally induced phase separation

Microporous cellulose acetate membranes were prepared by a thermally induced phase separation (TIPS) process. Two kinds of cellulose acetate with acetyl content of 51 and 55 mol % and two kinds of diluents, such as 2‐methyl‐2,4‐pentandiol and 2‐ethyl‐1,3‐hexanediol, were used. In all polymer‐diluent systems, cloud points were observed, which indicated that liquid–liquid phase separation occurred during the TIPS process. The growth of droplets formed after the phase separation was followed using three cooling conditions. The obtained pore structure was isotropic, that is, the pore size did not vary across the membrane. In addition, no macrovoids were formed. These pore structures were in contrast with those usually obtained by the immersion precipitation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3951–3955, 2003     

Evaluation of mixing profiles for a new micromixer design strategy

The relationship between mixing history and reaction performance in microreactors using computational fluid dynamics (CFD) simulations is identified. In the idealized, simplified mixing model, mixing proceeds linearly and only the mixing time determined the reaction performance. However, in the case of realistic models where mixing proceeds unequally, the partial rapid progression of mixing, more than the mixing time, significantly impacts the reaction. The use of the fluid segment size distribution to capture this effect is proposed. The effective Damköhler number derived from the fluid segment size distribution predicted the reaction yield well. To demonstrate the utility of the mixing profile design strategy, we fabricated a novel micromixer with multiple partial rapid mixing zones. This micromixer achieved excellent results both in a CFD simulation and an experiment. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1154–1161, 2016     

One-Step Generation of Multiple Gene-Edited Pigs by Electroporation of the CRISPR/Cas9 System into Zygotes to Reduce Xenoantigen Biosynthesis

Xenoantigens cause hyperacute rejection and limit the success of interspecific xenografts. Therefore, genes involved in xenoantigen biosynthesis, such as GGTA1, CMAH, and B4GALNT2, are key targets to improve the outcomes of xenotransplantation. In this study, we introduced a CRISPR/Cas9 system simultaneously targeting GGTA1, CMAH, and B4GALNT2 into in vitro-fertilized zygotes using electroporation for the one-step generation of multiple gene-edited pigs without xenoantigens. First, we optimized the combination of guide RNAs (gRNAs) targeting GGTA1 and CMAH with respect to gene editing efficiency in zygotes, and transferred electroporated embryos with the optimized gRNAs and Cas9 into recipient gilts. Next, we optimized the Cas9 protein concentration with respect to the gene editing efficiency when GGTA1, CMAH, and B4GALNT2 were targeted simultaneously, and generated gene-edited pigs using the optimized conditions. We achieved the one-step generation of GGTA1/CMAH double-edited pigs and GGTA1/CMAH/B4GALNT2 triple-edited pigs. Immunohistological analyses demonstrated the downregulation of xenoantigens; however, these multiple gene-edited pigs were genetic mosaics that failed to knock out some xenoantigens. Although mosaicism should be resolved, the electroporation technique could become a primary method for the one-step generation of multiple gene modifications in pigs aimed at improving pig-to-human xenotransplantation.     

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.