SOLUBILITY IN ORGANIC DILUENTS AND EXTRACTION BEHAVIOR OF CALIX[4]ARENE CARBOXYLATES WITH DIFFERENT ALKYL CHAINS

ABSTRACT

Two types of alkylcalix[4]arene carboxylates with different alkyl chains, together with three types with the same alkyl chains were synthesized to investigate their solubility in four different organic diluents. The solubility was found to be enhanced by using the calixarene compounds with longer alkyl chains and by using mixtures of compounds with different alkyl chains. The order of solubility in the different organic diluents was found to be:

chloroform > toluene ? EXXSOL D80 ≈ hexane.

The stoichiometry of the copper complex with the compounds having the same alkyl chains was also determined and the maximum loading capacity of copper with each extractant was estimated.     

Application of finite fourier transformation for the solution of the diffusion equation

Application of the finite Fourier transformation is discussed for the solution of the diffusion equation in one dimension, two dimensional x-y and triangular geometries. It can be shown that the equation by the Nodal Green's function method in Cartesian coordinate can be derived as a special case of the finite Fourier transformation method.     

Effect of microstructures on dielectric breakdown strength of sintered reaction-bonded silicon nitride ceramics

Silicon nitride (Si₃N₄) was prepared from silicon by a sintered reaction-bonded silicon nitride method using yttria and magnesia as sintering additives. Post-sintering (PS) of nitrided compacts was carried out at 1850°C under a nitrogen pressure of 1 MPa. Effect of PS time on microstructure and dielectric breakdown strength (DBS) of the prepared Si₃N₄ ceramics was evaluated. The DBS was measured using specimens with four different thicknesses (0.30, 0.20, 0.10, and 0.05 mm) in order to examine the thickness dependence. The porosity of the sintered Si₃N₄ decreased by prolonging the PS time, and the full density could be achieved at the PS time of over 6 h. After full densification, rod-like β-Si₃N₄ grains grew up, and their maximum grain size increased from 45.1 to 154.7 μm by prolonging the PS time from 6 to 48 h. The DBS of the thick Si₃N₄ substrates (0.30 mm) showed little variation from 35.4 to 47.0 kV/mm, regardless of the PS time. On the other hand, that of the thin ones (0.05 mm) dramatically decreased from 99.5 to 9.8 kV/mm with increased the PS time from 6 to 48 h. Because the DBS sharply decreased at the thin substrate sintered for longer time in which some large-elongated grains might span the substrate thickness-wise throughout, it was inferred that the interface between β-Si₃N₄ grains and grain boundary phase/intergranular glassy films might be a path of the dielectric breakdown.     

Development of a strain for efficient degradation of polychlorinated biphenyls by patchwork assembly of degradation pathways

Rhodococcus jostii RHA1 accumulates chlorobenzoates (CBA) during the degradation of polychlorinated biphenyls (PCBs). CBA degradation is considered one of the rate-limiting steps in the complete degradation of PCBs. To reduce the accumulation of CBAs, the upper pathway enzyme genes for PCB degradation of RHA1 were introduced into a CBA-degrading bacterium, Burkholderia sp. NK8. The resulting recombinant strain exhibited no biphenyl 2,3-dioxygenase (BphA) activity encoded by bphAaAbAcAd genes, which encode the large and small subunits of the terminal oxygenase component and the ferredoxin and reductase subunits responsible for electron transfer from NADH to the large subunit. The remaining enzyme genes involved in the transformation of biphenyl to benzoate, bphB2C1D1, which encode dehydrogenase, ring-cleavage dioxygenase and hydrolase, conferred activities to NK8. To obtain the BphA activity of RHA1 in NK8, sets of BphA genes were constructed by combining the bphAaAbAcAd genes of RHA1 and bphA3A4 of Pseudomonas pseudoalcaligenes KF707, encoding the ferredoxin and reductase subunits. Hybrid derivatives of BphA containing the KF707 bphA3 conferred BphA activity to NK8, and a derivative containing the RHA1 bphAaAb and KF707 bphA3A4 genes exhibited the highest BphA activity. A plasmid containing the RHA1 bphAaAb and KF707 bphA3A4 genes plus the RHA1 bphB2C1D1 genes was constructed and introduced into NK8. The resulting recombinant strain efficiently degraded 2-, 3- and 4-chlorobiphenyls with an apparent reduction in CBA accumulation in comparison to the recombinant mutant strain, which had an insertion in the cbeA gene to inactivate CBA dioxygenase.     

Changes in the amounts of water-soluble umami-related substances in porcine longissimus and biceps femoris muscles during moist heat cooking

Time course changes in amounts of glutamic acid, total free amino acid, inosine monophosphate (IMP), and 2%-trichloroacetic acid-soluble oligopeptides in whole, muscle only, and cooking juice during wet-heat cooking in pork longissimus and biceps femoris muscles were investigated because the movements of umami-relevant substances during cooking treatment had not previously been clarified in detail. The amounts of glutamic acid, total free amino acid, and IMP significantly (P<.05) decreased and increased in muscle and cooking juice during 180min of cooking, respectively. The whole amounts of glutamic acid and total free amino acid remained unchanged during cooking treatment. The whole amount of IMP, however, increased significantly at 10min of cooking (P<.05) and was maintained after the 10-min period. The extramuscular oligopeptides amount increased significantly in response to the cooking treatment (P<.05). The intramuscular amount of oligopeptides decreased at 30min of cooking but increased significantly (P<.05) after 60min. The whole meat oligopeptides amount increased significantly during a 180-min cooking treatment (P<.05). These results indicate that glutamate, total free amino acid, and IMP were released from the muscle during cooking, and that IMP levels increased in the initial phase of cooking. In addition, oligopeptides increased during wet-heat cooking of pork muscles.     

Base metal Co-fired (Na,K)NbO3 structures with enhanced piezoelectric performance

A NaF-Nb₂O₅ flux doped (Na,K)NbO₃ (NKN) based lead-free ceramic was successfully co-fired with nickel inner electrodes in reduced atmospheres. No chemical reactions and/or inter-diffusion were detected at the interface between the nickel (Ni) electrodes and the NKN-based piezoelectrics. Dielectric, resistivity, and electromechanical performance were measured with processing under different firing conditions and flux additions to obtain high densities. Ceramics are obtained with submicron grain structures with the NaF-Nb₂O₅ sintering aids (2 and 4 wt%) fluxes, and high densities when firing at low pO₂ (10^?10 atms) atmospheres at sintering temperatures ~1150 °C for 2 hours. High resistivities and low losses can be obtained through a second annealing condition at 850 °C and 10^?7 atms at 8 hours. High d ₃₃ values (over 350 pm/V) determined under unipolar converse electromechanical measurements were obtained in the simple prototyped co-fired structures to show feasibility towards base metal electrodes in multilayer actuators.     

Effects of species and moisture content on penetration of liquid in laser incised lumber by the passive impregnation method

Penetration of liquid by passive impregnation method for Douglas-fir (Pseudotsuga menziesii Franco), sugi (Cryptomeria japonica D. Don) and Japanese larch (Larix leptolepis Gordon) was studied. Effects of initial moisture content of sugi (16, 43 and 70% moisture content) on liquid penetration were also studied. Dried Douglas-fir (mc=14%) and sugi (mc=16%), and green Japanese larch (mc=45%) and sugi (mc=70%) were treated by passive impregnation method for penetration analysis. It was observed that dried sugi had the highest level of liquid penetration both in length (170 mm) and width (8 mm) for all measured sections followed by green sugi, green Japanese larch and dried Douglas-fir. In case of different initial moisture content, the highest absorption (624 kg/m³) and penetration (maximum 87 and 96% at cross and longitudinal surfaces, respectively) was observed for sugi having the lowest initial moisture content under the same passive impregnation conditions. Absorption and penetration decreased with the increase of initial moisture content for sugi. These results could help in designing incising pattern and density, as well as solving the problems related to high initial moisture content of wood for passive impregnation.     

High-performance polymer photovoltaic devices with inverted structure prepared by thermal lamination

Use of a lamination process for the introduction of Au electrode, instead of conventional metal evaporation, improved the power conversion efficiency (PCE) of inverted-structure photovoltaic devices from 1.6% to 2.6% based on a bulk heterojunction of poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C₆₁ butyric acid methyl ester (PCBM). X-ray photoelectron spectroscopy indicated that a thin layer of P3HT is spontaneously formed at the air/polymer blend layer interface during the spin-coating process. It is suggested that the vacuum-evaporated gold could destroy the surface-segregated thin layer of P3HT, while the lamination process preserves the surface structure working as an electron-blocking layer. The insertion of a PEDOT:PSS layer, between the metal electrode and polymer layer, in the lamination process further improved the PCE to 3.3% with a short-circuit current density of 9.94 mA cm⁻², an open-circuit voltage of 0.60 V, and a fill factor of 55% under AM1.5 100 mW cm⁻² irradiation.