Efficient transformation of 7,14-dihydroxy-ent-kaurenes to novel ent-abietanes having cis-fused α-methylene γ-lactones under Mitsunobu reaction conditions and their cytotoxicities

Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed.     

Development of Plasma Window for gas charge stripper at RIKEN RIBF

A differential pumping system with a Plasma Window (PW) has been developed for an application to a window-less He gas charge stripper. A PW with Southern Methodist University design was newly fabricated and tested off-line for evaluation of differential pumping efficiency. Switching gases for plasma seed from Ar to He was tested. It was found that the PW reduced the pressure at the first differential pumping section to 1/13 for Ar and to 1/17 for He, comparing with differential pumping without PW. At the second pumping section, the pressures were drastically reduced to 1/160 and to 1/4,520 for Ar and He, respectively. These pressure reduction factors indicate that one differentially pumped stage could be removed from a conventional differential pumping system.     

Synthesis,Crystal Packing,and Ambipolar Carrier Transport Property of Twisted Dibenzo[g,p]chrysenes

A versatile method for the synthesis of dibenzo[g,p]chrysene (DBC) derivatives based on regio‐ and stereoselective stannyllithiation to diarylacetylenes is described. This method affords a variety of DBCs possessing both electron‐donating and electron‐withdrawing functional groups. These twisted molecules take brickwork packing structures in single crystals. Thus, ambipolar carrier transport properties with mobility values of up to 10^?3 cm² V^?1 s^?1 in the amorphous state were achieved. Functional groups on DBC frameworks are considered to increase carrier mobility through the enhancement of intermolecular interactions in the brickwork packing structures.     

Mineral Composition of Seawater Bittern Nigari Products and Their Effects on Changing of Browning and Antioxidant Activity in the Glucose/Lysine Maillard Reaction

Seawater bittern (nigari) is a concentrated solution remaining after the crystallization process of salt that has been used as a coagulant for tofu. Recently, various nigari products are distributed in the East Asia. To clarify the properties of nigari products, major mineral composition of six nigari products was determined. Then, effects of the nigari on the browning and antioxidant activity during the glucose/lysine Maillard reaction were investigated. Though the predominant cation was Mg²⁺, the content was varied by each product (0.88–6.49 mol/L). The other major ion contents were also varied. Each 0.5 mol/L of d-glucose and l-lysine were incubated with the nigari (5–50 % (v/v)) or nigari-related salts (1 or 2 mol/L). The browning (OD at 465 nm) and antioxidant activity (1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging capacity and ferrous-reducing power) were increased remarkably by the nigari containing high Mg²⁺ content. The browning tended to be high with sulfates (Na₂SO₄, (NH₄)₂SO₄). On the other hand, high content of MgCl₂ decreased slightly the browning and antioxidant activity. These results suggest that the reaction and antioxidant activities were affected not only by salinity and cations but also by anions and other elements in the nigari.     

Optimization of SIMS analytical parameters for water content measurement of olivine

Secondary ion mass spectrometry (SIMS) has a wide range of applications in Earth Science research, thanks to its high precision and sensitivity, and its capacity in direct insitu micromeasurement. The technique is operated in ultra-high vacuum (UHV) conditions, especially for the measurement of volatiles such as hydrogen, or the water content in nominally anhydrous minerals (NAMs). To minimize the water background and obtain accurate and precise water contents in NAMs (eg, olivine) critical parameters such as presputtering time, field aperture (FA), dynamic transfer on/off, and primary beam current intensity were investigated for a CAMECA IMS 1280-HR system. When the chamber vacuum reaches approximately 2 × 10⁻⁹ mbar, we set the DTOS OFF, raster size to 50 μm and primary beam current to 5 nA, and used 2000 μm FA and 170-second presputtering time. Consequently, an approximately 1.2 ppmw water background and 3.6 ppmw limit of detection (LOD) were yielded, from analyzing the San Carlos olivine. Meanwhile, the water content and homogeneity of a range of olivine minerals were characterized for potential use as reference materials for SIMS water content measurement. Olivine water content calibration curve was also established by comparing the Fourier transform infrared (FTIR) results with the SIMS-measured ¹⁶O¹H⁻/¹⁶O⁻ ratios. Accuracy and precision of water content measurement were estimated to be better than approximately 10% in this study.     

Photopolyaddition of dithiols to bis(alkoxyallene)s

Polyadditions of 1,4-benzenedithiol (BDT) to bis(alkoxyallene)s, such as 1,4-bis(allenyloxy)xylene (3) and 1,4-bis(allenyloxy) benzene (4) , were carried out in benzene at 25°C by irradiation with a high pressure mercury lamp. Thiol groups were added to the terminal double bonds of the allenyloxy groups selectively to afford polymers containing reactive carbon–carbon double bonds in the main chain, similar to the radical polyadditions using azobis(isobutyronitrile) (AIBN). The molecular weight of the polymer obtained from BDT and 3 was 10 times higher than that of the polymer produced in the radical polyaddition with AIBN; whereas the molecular weight of the polymer from BDT and 4 was similar to that in the radical polyaddition, probably because of poor solubility of 4 and the polymer toward benzene. The geometrical structure of carbon–carbon double bonds in the polymer isomerized from an E to Z structure with reaction time by virtue of both the addition elimination of thiyl radical to the double bonds and the UV irradiation. © 1996 John Wiley & Sons, Inc.     

A hydrogel with rubber elasticity transition

Reaction between dimethyldivinylsilane and 3,6-diazaoctane in the presence of 3-lithio-3,6-diazaoctane yields a new telechelic oligomer, poly(silamine), which consists of alternating 3,3-dimethyl-3-silapentane and N,N′-diethylethylenediamine units in the main chain. Poly(silamine) shows unique phase transition properties in response to the degree of protonation of amino groups in the polymer. Poly(silamine) also shows a strong interaction with several anions. Due to the interaction between poly(silamine) and anions along with the protonation of amino groups in the poly(silamine), the rubber elasticity of poly(silamine) is drastically changed. A discrete volume change can be observed when the environmental pH of the poly(silamine) gels is varied. This can be explained not only by a change in ionic osmotic pressure but also by a change in the rubber elasticity of the networks in the gel.