Changes in the melting temperature and crystal structure of poly(vinylidene fluoride) by knotting

A significant increase in the melting temperature of knotted fibers of poly(vinylidene fluoride) (PVDF) was detected by differential scanning calorimetry. The melting peak partially returned to the original peak after the fibers were unknotted. Knotted PVDF fibers were observed with an optical microscope at crossed‐nicol conditions. The knotted portions of the fibers showed birefringence even above the melting temperature of the fibers before knotting. The dependence of the physical properties of PVDF under applied stress was estimated in order to investigate the influence of knotting. The fracture temperature of PVDF fibers increased with applied stress below 1 MPa and decreased above 10 MPa because the applied stress increased the melting temperature of PVDF crystals, but strong stress mechanically broke the fibers. The X‐ray diffraction patterns of the PVDF fibers under different stress were divided into the peaks of α‐ and β‐phase crystals and amorphous. The peak area of the β‐phase crystal increased and that of the amorphous decreased with applied stress. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Generation of disk-like domains with nanometer scale thickness in merocyanine dye LB film induced by hydrothermal treatment

We have characterized the binary LB films of merocyanine dye (MS) and arachidic acid (C₂₀) before and after hydrothermal treatment (HTT), which is defined as a heat treatment under relative humidity of 100%, focusing on the morphology studied by bright field (BF) microscopy and fluorescence (FL) microscopy. BF microscopy observation has revealed that the as-deposited MS-C₂₀ binary LB film is found to emit intense red fluorescence over the whole film area by 540-nm excitation. Since the surface image is almost featureless, it is considered that the crystallite sizes of J-aggregate are less than 10 μm. Interestingly, after HTT, round-shaped domains are observed in the LB systems, and the sizes are reaching 100 μm in diameter. Crystallites of J-aggregate, which are bluish in color and emit intense red fluorescence, tend to be in the round domains. We have observed two different types of domains, i.e., blue-rimmed domains and white-rimmed domains, which are postulated to be confined in the inner layers and located at the outermost layer, respectively. The thickness of the domains is equal to or less than that of the double layer of the MS-C₂₀ mixed LB film, which is ca. 5.52 nm. The molecular order of MS in the J-aggregate is improved by the HTT process leading to the significant sharpening of the band shape together with the further red shift of the band (from 590 to 594 nm up to 597 to 599 nm). The reorganized J-band is considered to be ‘apparently’ isotropic owing to the random growth of the J-aggregate in the film plane. We consider that the lubrication effect by the presence of water molecules predominates in the HTT process.     

Structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics for a-IGZO thin-film transistors

In this letter, we investigated the structural and electrical characteristics of high-κ Er₂O₃ and Er₂TiO₅ gate dielectrics on the amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) devices. Compared with the Er₂O₃ dielectric, the a-IGZO TFT device incorporating an Er₂TiO₅ gate dielectric exhibited a low threshold voltage of 0.39 V, a high field-effect mobility of 8.8 cm²/Vs, a small subthreshold swing of 143 mV/decade, and a high I_on/I_off current ratio of 4.23 × 10⁷, presumably because of the reduction in the oxygen vacancies and the formation of the smooth surface roughness as a result of the incorporation of Ti into the Er₂TiO₅ film. Furthermore, the reliability of voltage stress can be improved using an Er₂TiO₅ gate dielectric.     

Comparison of Cellular Uptake and Inflammatory Response via Toll-Like Receptor 4 to Lipopolysaccharide and Titanium Dioxide Nanoparticles

The innate immune response is the earliest cellular response to infectious agents and mediates the interactions between microbes and cells. Toll-like receptors (TLRs) play an important role in these interactions. We have already shown that TLRs are involved with the uptake of titanium dioxide nanoparticles (TiO₂ NPs) and promote inflammatory responses. In this paper, we compared role of cellular uptake and inflammatory response via TLR 4 to lipopolysaccharide (LPS) and TiO₂ NPs. In the case of LPS, LPS binds to LPS binding protein (LBP) and CD 14, and then this complex binds to TLR 4. In the case of TiO₂ NPs, the necessity of LBP and CD 14 to induce the inflammatory response and for uptake by cells was investigated using over-expression, antibody blocking, and siRNA knockdown experiments. Our results suggested that for cellular uptake of TiO₂ NPs, TLR 4 did not form a complex with LBP and CD 14. In the TiO₂ NP-mediated inflammatory response, TLR 4 acted as the signaling receptor without protein complex of LPS, LBP and CD 14. The results suggested that character of TiO₂ NPs might be similar to the complex of LPS, LBP and CD 14. These results are important for development of safer nanomaterials.     

Serial Changes of Serum Growth Factor Levels and Liver Regeneration after Partial Hepatectomy in Healthy Humans

This study aimed to investigate the associations of the serial changes of serum levels of various growth factors with liver regeneration after hepatectomy in healthy liver donors. Sixteen healthy liver donors who underwent conventional liver resection were included. Serum levels of various growth factors before hepatectomy and on postoperative day (POD) 1, 3, 5 and 7 were measured. Liver volume data calculated by multi-detector computed tomography using workstation. The ratio of remnant liver volume on POD 0 to liver volume before the operation was 51% ± 20%. The ratio of liver volume on POD 14 to liver volume on POD 0 were inversely correlated with remnant liver volume on POD 0 (r = −0.91). The ratio of liver volume on POD 14 to liver volume on POD 0 were significantly correlated with serum hepatocyte growth factor (HGF) levels on POD 1 (r = 0.54), serum leptin levels on POD 1 (r = 0.54), and serum macrophage colony-stimulating factor (M-CSF) levels on POD 5 (r = 0.76) and POD 7 (r = 0.80). These results suggest that early-phase elevation of serum levels of HGF, leptin and M-CSF may be associated with the acceleration of liver regeneration after hepatectomy in humans.     

Time-resolved DXAFS study on the reduction processes of Cu cations in ZSM-5

The time-resolved reduction process of copper cations in/on ZSM-5 during temperature-programmed reduction (300–700 K) was studied by energy-dispersive X-ray absorption fine structure (DXAFS) as well as transmission electron microscopy (TEM). Two Cu-ZSM-5 samples with different Cu loadings were prepared by an ion-exchange method. The Cu K-edge DXAFS spectra for isolated Cu₂₊ species in the channels of ZSM-5 and CuO particles on the outer surfaces of ZSM-5 were recorded at an interval of 1 s during the reduction. The curve fitting analysis of the EXAFS data and the XANES analysis revealed that the isolated Cu₂₊ species in the channels were reduced stepwise. They were reduced to isolated Cu₊ species at 400–450 K and the Cu₊ species to Cu₀ metallic clusters at 550–650 K. Small clusters like Cu₄ were initially formed, followed by particle growth. A small part of them went out to the outer surfaces of ZSM-5 during the reduction. In contrast, CuO particles on the outer surfaces were reduced directly to Cu₀ metallic particles around 450 K.     

Fracture Energy of an Aligned Porous Silicon Nitride

The fracture energy of a porous silicon nitride with aligned fibrous grains was investigated, using a chevron-notched-beam technique. A crack was constrained to propagate normal to the grain alignment. The obtained fracture energy was ∼500 J/m², which was ∼7 times larger than that of a dense silicon nitride with randomly oriented fibrous grains. The large fracture energy was attributable primarily to the sliding resistance associated with interlocking grains.     

Catalytic dehydration of 1,2-propanediol into propanal

Vapor-phase catalytic dehydration of 1,2-propanediol was investigated over several catalysts, such as acidic oxides and supported heteropoly acids. These acids catalyze the dehydration of 1,2-propanediol to produce propanal. In particular, silica-supported silicotungstic acid showed the highest catalytic activity in the formation of propanal. At low conversions, however, propanal reacted with another 1,2-propanediol to produce a cyclic acetal (2-ethyl-4-methyl-1,3-dioxolane). Such acetal formation reduced the selectivity to propanal. Under optimum reaction conditions, 100% conversion was attained with propanal selectivity higher than 93 mol% at 200 °C.     

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.