Enantioselective addition Of diketene to aldehydes promoted by chiral schiff base—titanium alkoxide complex. Application to asymmetric synthesis of potential inhibitors of HMG coenzyme reductase

Highly enantioselective addition of diketene to aldehydes was achieved by using novel Schiff base—titanium alkoxide complexes. Up to 92% ee of 5-hydroxy-3-oxoesters was obtained. This procedure provides an efficient method for the asymmetric synthesis of potential inhibitors of HMG coenzyme reductase.     

Influence of the introduction of flexible alkyl chains on the thermal behavior and mechanical properties of mesogenic epoxy thermosets

A mesogenic epoxy resin (DGETAM) was cured with a series of curing agents having different lengths of long alkyl chain (nBAB, n = 4, 8, 12). Properties of the curings were compared with those of the DGEBA cured with the same curing agents revealing the achievement of a balance between certain levels of thermal properties and excellent mechanical properties. Moreover, some curing systems were prepared with twin mesogenic type epoxy resins (DGEnMA, n = 4, 6, 8, 10, 12) having different lengths of alkyl chain as a flexible spacer and the same curing agents (n′BABs). Combinations of the same concentrations of chemical structures in the basic units of the network structure were applied, and the thermal and mechanical properties of their curing systems were investigated. The fracture energy of each system increased considerably with the increase of the alkyl chain length that adjoins the two mesogenic groups in the epoxy resins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44244.     

Structure and mechanical properties of multi‐hollowed fibers produced by CO2 laser irradiated neck drawing

Multi‐hollowed fibers with a hollowness ratio of over 20% were successfully produced using a neck‐drawing technique accompanied by CO₂ laser irradiation on unoriented and amorphous polytrimethylene terephthalate (PTT) fibers with diameters of approximately 104 µm. The structure and mechanical properties of the multi‐hollowed fibers were characterized using scanning electron microscopy, wide angle X‐ray diffraction (WAXD), birefringence measurements, and tensile tests. Crystal orientation factors in the direction normal to the (010) and (002) planes, which were obtained from WAXD patterns, were lower in comparison to values obtained in previous studies on fibers that did not feature these hollows [9] because of the development of these internal hollows. The PTT fibers in this study also displayed high toughness, about 465 MPa (3.5 cN/dtex) strength and about 40% elongation, and had excellent elastic recovery (>95%) after 10 stretch cycles. POLYM. ENG. SCI., 56:609–616, 2016. © 2015 Society of Plastics Engineers     

On-off switching properties of one-dimensional photonic crystals consisting of azo-functionalized polymer liquid crystals having different methylene spacers and polyvinyl alcohol

In this paper, photoresponsive behavior of multi-bilayered films having precisely controlled layer thickness prepared by stacking an azo-functionalized polymer liquid crystal, PMAzXAc, and polyvinyl alcohol alternatively, PVA, is described. The multi-bilayered films were found to reflect a light of specific wavelength depending on the layer thickness and refractive index, and showed the reversible change in the reflection intensity by irradiation with visible and UV lights. The change in the reflection intensity was brought about by change in the molecular orientation of PMAzXAc between an out-of-plane orientation and a photo-induced isotropic state, and was strongly dependent on the number of methylene spacer of PMAzXAc linking the azobenzene side group with the acrylate polymer main chain. PMAz6Ac with hexa-methylene spacer showed the largest change in the reflection intensity, while smaller change in the reflection intensity was observed for PMAzXAc having shorter or longer methylene spacer than 6. The effect of the methylene spacers on the photochemical change in the molecular orientation of azobenzene chromophores in the multi-bilayered films will be discussed.     

Influence of swelling of noncrystalline regions in silk fibers on modification with methacrylamide

The degrees of swelling of noncrystalline regions of domestic and tussah silk fibers were investigated by measuring the small-angle X-ray scattering intensity of the fibers in wet conditions and analyzing the scattering intensity based on a two-phase model, i.e., crystalline regions and water-swollen noncrystalline regions. The influence of the degree of swelling of noncrystalline regions on the graft treatment of these fibers with methacrylamide was investigated. The changes in the structure caused by the graft treatment were also analyzed using the wide-angle X-ray diffraction measurements. As compared with the tussah silk fibers, the domestic silk fibers showed a larger degree of swelling of the noncrystalline regions, and gained a larger amount of resin by the graft treatment. The crystallites with smaller sizes in the tussah silk fibers were destroyed preferentially by the graft treatment. For the domestic silk fibers, the crystallites were destroyed more seriously and rather homogeneously independent of the crystallite sizes. © 1996 John Wiley & Sons, Inc.     

Interconnection reliability and interfacial structure between Au alloy bump and Al pad using ultrasonic bonding*

Flip chip technology with Au bumps on a substrace has been widely applied to electronic equipment such as smart phones. The purposes of this study are to examine the effect of Al pad thickness on the bondability of flip chip using ultrasonic bonding and to clarify interfacial structures between Au alloy bumps and Al pads by ultrasonic bonding compared before and after a thermal cycle test. Suitable Al thickness for excellent initial Au/Al bonding without chip cracking are 0.8 μm because a thin Al layer could not reduce stress to a chip under an Al pad during the ultrasonic bonding process. Intermetallic compounds between the Au alloy bump and chip after reflows consisted of five Au-Al layers, and a pure Al layer remained. On the other hand, after the temperature cycle test at 218/423 K, intermetallic compounds between the Au alloy bump and chip were changed into two kinds of Au-Al layers, so a pure Al layer did not exist. In addition, if thick intermetallic compound layers existed around the bonding region, bondability deteriorated easily by thermal stress due to a thermal cycle test, therefore the open failure rate was rising when the Au thickness was 1.2 μm.     

Degradation of cyanuric acid in soil by Pseudomonas sp. NRRL B-12227 using bioremediation with self-immobilization system

The rates of degradation of cyanuric acid, a key intermediate in a metabolic pathway of s-triazine herbicides, were measured for Pseudomonas sp. NRRL B-12227. The rate of degradation was affected by the rate of cyanuric acid transport through cell membranes and the activity of cyanuric acid amidohydrolase inside the cells. At low concentrations of cyanuric acid, the acclimation of cells to cyanuric acid and/or added nutrients effectively enhanced the degradation rate. The strain was also applied to bioremediation using a Bioremediation with Self-Immobilization System (BSIS), in which Pseudomonas sp. NRRL B-12227 cells were co-immobilized with Bacillus subtilis, the latter of which secretes a viscous polymer, in a shallow layer of soil packed in a column. More than 70% of the Pseudomonas sp. NRRL B-12227 cells were co-immobilized with the B. subtilis in a 7.5 cm layer of the packed soil by self-aggregation. More than 60% of the 1 mM cyanuric acid supplied to the packed soil was degraded in this layer during a 72 h period.     

Occurrence and sources of perfluorinated surfactants in rivers in Japan

We analyzed perfluorinated surfactants (PFSs) in 20 river samples and 5 wastewater secondary effluent samples in Japan to reveal their occurrence and sources. Nine PFS species were determined: perfluorooctanesulfonate (PFOS), perfluorooctane sulfonamide (FOSA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), perfluorododecanoate (PFDDA), and perfluorotridecanoate (PFTDA). PFSs were detected in all rivers, revealing nationwide contamination of rivers. In particular, 11 out of 20 river samples exceeded New Jersey guidance for PFOA in drinking water (40 ng/L). PFOS, PFHpA, PFOA, and PFNA were major species in Japan. Concentrations of PFOS, PFHpA, and PFNA in rivers were strongly correlated with population density, suggesting that the chemicals were derived from urban activities. PFOA showed a significant but weak correlation. We used crotamiton, a marker of sewage effluent, for further source analysis. Concentrations of PFOS, PFHpA, and PFNAwere strongly correlated with those of crotamiton, and plots of secondary effluents fell near the regression lines of rivers, indicating that the PFOS, PFHpA, and PFNA in rivers were derived from sewage effluent. On the other hand, PFOA was found at remarkably high levels (54-192 ng/L) in seven river samples containing low levels of crotamiton, suggesting that it was derived from nonsewage point sources, as well as sewage effluent. The total fluxes of sewage-derived PFOS, PFHpA, PFOA, and PFNA from Japan were estimated to be 3.6, 2.6, 5.6, and 2.6 t/year, respectively. This is the first report to identify PFOA in several rivers, derived from nonsewage point sources, by using a marker of sewage effluent.     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.