Reactive extraction of diols with phenyl boronic acid and trioctylmethylammonium chloride as coextractants and quantitative structure–property relationship of their extraction behaviors

BACKGROUND: Diols that can be produced biologically have attracted much attention because of the increased cost of producing them chemically. The cost of separating the diols from the broth forms a major part of the total cost of microbial production. Reactive extraction using organoboronate is one promising method for recovering diols from the dilute aqueous solution. RESULTS: A basic investigation of solvent extraction of diols was conducted at 303 K employing phenylboronic acid and trioctylmethylammonium chloride as coextractants in the mixed solvent. Both the tetrahedral boronate anion complex and trigonal boronate neutral complex were extracted. 1,3‐diols and vicinal diols were extracted, but 1,4‐diol was not extracted. Extraction equilibrium constants were correlated with the enthalpies of formation of the complexes, which were calculated by molecular modeling with semi‐empirical molecular orbital calculations considering the solvent effect. CONCLUSION: The complex extraction behaviour of diols with phenylboronic acid and quaternary ammonium salt can be predicted by using the quantitative structure–property relationship (QSPR). Copyright © 2009 Society of Chemical Industry     

Effect of soybean varieties on the content and composition of isoflavone in rice-koji miso

To clarify the effect of soybean varieties on isoflavone, a useful component for human health, in soybean products, we investigated changes in the isoflavone content and composition in rice-koji miso, after fermentation/aging for 6 or 12 months using varieties of soybeans (Tohoku-126, Tohoku-135, Tohoku-139, Suzuyutaka and Chinese soybeans), by high performance liquid chromatography. In soybeans, the total isoflavone content in Tohoku-126 was 444 mg/100 g, which was 1.2–2.0 times the content in the other soybean varieties. The malonyl glycosides and aglycones in soybeans accounted for more than 60% and only a few percent, respectively. As for rice-koji miso, the total isoflavone and aglycone contents were the highest in miso prepared from Tohoku-126. The ratios of glycosides to aglycones (80.1–92.6%) in miso were higher than those in the original soybeans. The time course of the isoflavone composition during the fermentation/aging process of rice-koji miso indicated that glycosides decreased from 86.4% to 44.9% after 6 months but aglycones increased from 9.6% to 53.3%.     

Effect of cleaving environment on the growth of ZnSe on the GaAs (1 1 0) surface by molecular beam epitaxy

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

Surface modification using polymer Langmuir-Blodgett films

We describe a simple and effective approach to introduce a functional group into polymer film on a solid surface using reactive polymer LB films. N-dodecylacrylamide copolymers containing terminal amino groups in the side chains as the reactive moiety form a stable monolayer, and the monolayer was transferred onto a solid support to modify the solid surface using the Langmuir-Blodgett method. The transferred coatings were characterized with fluorescence, IR spectroscopies, and X-ray diffraction. The reactivity of the terminal amino group incorporated in the LB films was investigated in detail using fluorescein isothiocyanate (FITC) as a fluorescent probe. The chemical reaction between amino groups in the LB films and FITC in the bulk solution was completed within approximately 30 minutes and the chemical bond formation was confirmed by infrared spectroscopy. Furthermore, the fluorescent image of the multilayers reacted with FITC were observed with fluorescent microscopy. This method is effective for tailoring functional organic ultrathin films on solid substrates.     

Radiation-induced graft copolymerization of mixtures of styrene and n-butyl acrylate onto cellulose and cellulose triacetate

Mixtures of styrene and n-butyl acrylate of various compositions were grafted onto cellulose and cellulose triacetate fibers preirradiated with γ-rays at 0°C in air. Monomer reactivity ratios of the grafted copolymers were found to be different from those of the nongrafted copolymers or those of AIBN-initiated copolymers. The active species initiating the graft copolymerization were trapped radicals for cellulose and peroxides for cellulose triacetate. Kinetic investigations of the graft copolymerization of styrene onto preirradiated cellulose triacetate fibers were also carried out, and it was found that the kinetic scheme for radical polymerization is also applicable to graft copolymerization in a heterogeneous system.     

High Capacity Li2S–Li2O–LiI Positive Electrodes with Nanoscale Ion-Conduction Pathways for All-Solid-State Li/S Batteries

All-solid-state lithium–sulfur (Li/S) batteries are promising next-generation energy-storage devices owing to their high capacities and long cycle lives. The Li₂S active material used in the positive electrode has a high theoretical capacity; consequently, nanocomposites composed of Li₂S, solid electrolytes, and conductive carbon can be used to fabricate high-energy-density batteries. Moreover, the active material should be constructed with both micro- and nanoscale ion-conduction pathways to ensure high power. Herein, a Li₂S–Li₂O–LiI positive electrode is developed in which the active material is dispersed in an amorphous matrix. Li₂S–Li₂O–LiI exhibits high charge–discharge capacities and a high specific capacity of 998 mAh g⁻¹ at a 2 C rate and 25 °C. X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy observation suggest that Li₂O–LiI provides nanoscale ion-conduction pathways during cycling that activate Li₂S and deliver large capacities; it also exhibits an appropriate onset oxidation voltage for high capacity. Furthermore, a cell with a high areal capacity of 10.6 mAh cm^–2 is demonstrated to successfully operate at 25 °C using a Li₂S–Li₂O–LiI positive electrode. This study represents a major step toward the commercialization of all-solid-state Li/S batteries.     

Heteroepitaxial growth of Zn1−xCdxSe on cleavage-induced GaAs (110) surface in ultra high vacuum

Zn_1−xCd_xSe epitaxial growth by molecular beam epitaxy (MBE) on the GaAs (110) surface cleaved in ultra high vacuum (UHV) was investigated. The growth mode of Zn_1−x Cd_xSe on GaAs (110) was not a simple Stranski–Krastanow type. At initial growth stage, growth mode was two-dimensional type. However, as the growth proceeds three-dimensional island growth and two-dimensional growth modes compete. As a result, two kinds of structures were spontaneously formed on the surface, pyramidal-shaped islands and ridge structures aligned to the [1 0] direction. Anisotropic in-plane strain relaxation on (110) is suggested as the formation mechanism of such structures.     

Advances in nature-guided materials processing

The center of excellence (COE) titled ‘The Creation of Nature-Guided Materials Processing’ has been established in Nagoya University as the 21st Century COE Program supported by Ministry of Education, Culture, Sports, Science and Technology. In the Nature COE, various activities on the education and research are being performed through learning the laws of nature, namely, methods of attaining ‘appearance of the maximum function under the minimum substance and energy consumption’, which the nature and living organisms have acquired through their evolution in long period. Together with such educational programs for PhD students as research incentive, oversea training, and external evaluation programs, an ‘Open-Cluster Program’ was originated for promoting researches proposed by research groups consisting of young researchers in and out of the university and also for fostering them.

The researches are being advanced on materials used for living bodies, mimicking structures which nature or living bodies are forming, and producing materials by mimicking processes to form the structures observed in the nature or the living bodies. In this COE, these researches are conducted by four groups to extend the processes observed in the natural world to a new type of processing, that is, thoroughly examined and rationalized by plunging a scalpel of engineering and to establish a new academic field of materials science and engineering.     

Hot-carrier-injected oxide region in front and back interfaces inultra-thin (50 nm), fully depleted, deep-submicron NMOS andPMOSFET's/SIMOX and their hot-carrier immunity

The hot-carrier-injected oxide region in the front and back interfaces is systematically clarified for fully depleted surface-channel nMOSFET's and surface-channel and buried-channel pMOSFET's fabricated on an ultra-thin (50 nm)-film SIMOX wafer. Based on these results, the influence of these injected carriers on front-channel properties is investigated. NMOSFET degradation is shown to be caused by hot-carriers injected into the drain side of the front oxide and pMOSFET degradation by hot-electrons injected into the drain side of both the front oxide and the back oxide. Additionally, it is shown experimentally that these fully depleted devices with effective channel lengths between 0.1-0.2 μm have fairly high hot-carrier immunity, even for single-drain structures     

Generation of single-walled carbon nanotubes from alcohol and generation mechanism by molecular dynamics simulations

Recent advances in high-purity and high-yield catalytic chemical vapor deposition (CVD) generation of single-walled carbon nanotubes (SWNTs) from alcohol are comprehensively presented and discussed on the basis of results obtained from both experimental and numerical investigations. We have uniquely adopted alcohol as a carbon feedstock, and this has resulted in high-quality, low-temperature synthesis of SWNTs. This technique can produce SWNTs even at a very low temperature of 550 degrees C, which is about 300 degrees C lower than the conventional CVD methods in which methane or acetylene is typically used. We demonstrate the excellence of the proposed alcohol catalytic CVD method for high-yield production of SWNTs when Fe-Co on USY-zeolite powder was used as a catalyst. At optimum CVD conditions, a SWNT yield of more than 40 wt % was achieved over the weight of the catalytic powder within the reaction time of 120 min. In addition to the advantages for mass production, this method is also suitable for the direct synthesis of high-quality SWNTs on Si and quartz substrates when combined with the newly developed liquid-based "dip-coat" technique to mount catalytic metals on the surface of substrates. This method allows easy and costless loading of catalytic metals without the need for any support or underlayer materials that were usually required in previous studies for the generation of a sufficient quantity of SWNTs on an Si surface. Finally, the result of molecular dynamics simulation for the SWNT growth process is presented to obtain a fundamental insight into the initial growth mechanism on the catalytic particles.