Synthesis and gas permeability of ABA‐type triblock copolymers derived from fluorine‐containing polyimide with polyhedral oligomeric silsesquioxane

ABA‐type triblock copolymers derived from 4,4'‐(hexafluoroisopropylidene)diphthalicanhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) and methacryl phenyl polyhedral oligomeric silsesquioxane (MPPOSS) were synthesized by atom transfer radical polymerization. The chemical structure of the synthesized ABA‐type triblock copolymer was confirmed by ¹H NMR, ¹³C NMR, ²⁹Si NMR and Fourier transform infrared analyses. The ratios of 6FDA‐TeMPD and MPPOSS determined by TGA were 94/6, 85/15, 77/23, 68/32, 57/43 and 31/69. The film density of the ABA‐type triblock copolymer films did not conform to the mixing rule because of polyimide (PI) chain aggregation. Based on contact angle and water uptake analyses, the hydrophobicity of the ABA‐type triblock copolymer film was determined to be higher than the theoretical value because of POSS cage effects and PI chain aggregation. The gas permeability coefficient of the ABA‐type triblock copolymer decreased compared with that of PI because of aggregation of PI chains and inhibition of solubility decreases by substitutes with high affinity. ABA‐type triblock copolymer CO₂/H₂ separation performance increased compared with that of PI. The ABA‐type triblock copolymer derived from PI and MPPOSS can be described as a polymer material with higher hydrophobicity and higher CO₂/H₂ selectivity than PI. © 2015 Society of Chemical Industry     

Shrinkage Behavior of Knoop Indentations in Silica and Soda–Lime–Silica Glasses

The annealing characteristics of Knoop-indented silica and soda–lime–silica glasses were investigated. These glasses were indented using a Knoop indenter in water, and they were annealed at various temperatures below the glass transition temperature. The major diagonal length of the Knoop indentation was measured before and after annealing, and the change of the diagonal length was determined. The change of diagonal length in silica glass was much larger than that in soda–lime–silica glass. This was attributed to the occurrence of more densification around the Knoop indentation in the silica glass. The activation energy of the shrinkage of the Knoop indentation in the silica glass, estimated from the temperature dependence of the relaxation time, was 46 kJ/mol, which was much less than that of viscous flow in silica glass. This suggested that the shrinkage of the Knoop indentation was caused by the structural relaxation of densified glass around the Knoop indentation.     

Isomerization and anti-Markovnikov arylation of olefin catalyzed by an iridium complex

An iridium acetylacetonato complex, a catalyst for anti-Markovnikov arylation of olefins, was found to work as a catalyst for olefin isomerization. 2-butene was obtained with 0.55 cis/trans ratio in isomerization of 1-butene. Moreover, in 1-hexene/benzene solution, isomerization and arylation of 1-hexene were simultaneously catalyzed by the iridium complex.     

Effect of Amount of Boron Doping on Compression Deformation of Fine-Grained Silicon Carbide at Elevated Temperature

The effect of the amount of boron doping in the range of 0 to 1.0 wt% on the high-temperature deformation of fine-grained β-silicon carbide (SiC) was investigated by compression testing. Flow stress at the same grain size increased as the amount of boron doping decreased. The stress exponent increased from 1.3 to 3.4 as the amount of boron doping decreased. The strain rates of undoped SiC were ∼2 orders of magnitude lower than those of 1.0-wt%-boron-doped SiC of the same grain size. The apparent activation energies of SiC doped with 1.0 wt% boron and of undoped SiC were 771 ± 12 and 884 ± 80 kJ/mol, respectively. These results suggest that the actual contribution of grain-boundary diffusion to the accommodation process of grain-boundary sliding decreased as the amount of boron doping decreased. Consequently, the apparent contribution of the dislocation glide increased.     

Photophysical properties and photostability of novel symmetric polycyclicphenazine-type fluorescent dyes and the dye-doped films

Novel symmetric polycyclicphenazine-type fluorescent dyes have been synthesized and characterized in solution and in polymer films. The dyes exhibited two strong absorption bands at around 365-428 nm and 519-567 nm and an intense fluorescence band at around 560-600 nm (Ф = 0.70-0.87) in 1,4-dioxane. The dye-doped polymer films showed excellent wavelength conversion function that efficiently convert ultraviolet and yellow lights into red light (Ф = 0.61-0.92). Moreover, the photostability of the dye-doped PS, PMMA, and PLA films has been investigated.     

Estimation of nitrogen flow within a village-farm model in Fakara region in Niger,Sahelian zone of West Africa

To determine the efficiency of utilization of organic matter in agricultural production, nitrogen flow was estimated within a village-farm model in the west of Niger, West Africa. Nitrogen was focused on in this study as it is known to be a major nutrient component of organic matter and one of the limiting nutrients in Sahelian soil. Local practices regarding the use of organic matter and pertinent information on traditional practices for soil fertility management were determined by interviews with local farmers. To estimate nitrogen flow in farmlands and consumption in the village through various activities, quantitative measurements of crop yield and organic amendment were carried out. Data on human and livestock excreta were taken from published reports. The size and classification of farmlands were as follows: 0.5 ha adjacent farmland, 1.6 ha threshing farmland, 6.0 ha transported-manure farmland, 5.5 ha corralling farmland, and 86.5 ha extensively managed farmland (EMF). Levels of nitrogen flow from these farmlands to the studied villages were 0.9, 2.9, 9.6, 15.2, and 94.2 Mg, while the flows to these farmlands were 14.6, 6.3, 13.7, 17.5, and 26.3 Mg, respectively. Upon calculation of nitrogen balance −8 kg ha⁻¹ year⁻¹ was estimated in EMF, but there was a positive balance in other types of farmland, which ranged from 4 to 262 kg ha⁻¹ year⁻¹, indicating inefficient use of nitrogen in the study area for crop production. The results indicated that nutrient flow in the study site was unequally distributed and nitrogen was not recycled. Therefore, efforts should be made to establish efficient utilization of available nutrients by reducing the loss from livestock feed and human consumption. At the same time, more research is needed to improve the management of EMF.     

Microwave roasting and positional distribution of fatty acids of phospholipids in soybeans (Glycine max L.)

Whole soybeans were exposed to microwave roasting for 6, 12, and 20 min at a frequency of 2,450 MHz and were studied not only for phospholipid composition but also for positional distribution of the fatty acids. During microwave roasting, the greatest rate of phospholipid losses (P<0.05) was observed in phosphatidylethanolamine (PE), followed by phosphatidylcholine (PC) and phosphatidylinositol (PI), respectively. Therefore, the effects of microwave roasting on the composition and positional distribution of the fatty acids are likely clearer in PE than in PC or PI. However, the principal characteristics for the positional distribution of fatty acids are still retained during microwave roasting: unsaturated fatty acids, especially linoleic, are predominantly concentrated in the 2-position, and saturated fatty acids, especially palmitic, primarily occupy the 1-position after 12 or 20 min of roasting. The results suggest that unsaturated fatty acids located in the 2-position are significantly protected from microwave roasting.     

Size and surface modification of amorphous silica particles determine their effects on the activity of human CYP3A4 in vitro

Because of their useful chemical and physical properties, nanomaterials are widely used around the world - for example, as additives in food and medicines - and such uses are expected to become more prevalent in the future. Therefore, collecting information about the effects of nanomaterials on metabolic enzymes is important. Here, we examined the effects of amorphous silica particles with various sizes and surface modifications on cytochrome P450 3A4 (CYP3A4) activity by means of two different in vitro assays. Silica nanoparticles with diameters of 30 and 70 nm (nSP30 and nSP70, respectively) tended to inhibit CYP3A4 activity in human liver microsomes (HLMs), but the inhibitory activity of both types of nanoparticles was decreased by carboxyl modification. In contrast, amine-modified nSP70 activated CYP3A4 activity. In HepG2 cells, nSP30 inhibited CYP3A4 activity more strongly than the larger silica particles did. Taken together, these results suggest that the size and surface characteristics of the silica particles determined their effects on CYP3A4 activity and that it may be possible to develop silica particles that do not have undesirable effects on metabolic enzymes by altering their size and surface characteristics.