Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo‐Ring Formation with 8π‐6π Electrocyclization

Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo‐ring formation reactions proceed non‐enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo‐ring formation and 8π‐6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non‐enzymatic conversion to shimalactones in the dark.     

High-throughput solid-phase extraction of metal ions using an iminodiacetate chelating porous disk prepared by graft polymerization

A chelating porous sheet for use in solid-phase extraction was prepared by radiation-induced graft polymerization and subsequent chemical modifications. An epoxy-group-containing vinyl monomer was graft-polymerized onto a porous sheet made of polyethylene. The produced epoxy group of the graft chain was converted into an iminodiacetate group. The chelating porous sheet with a density of the iminodiacetate group of 2.1 mol/kg was cut into disks 13 mm in diameter to fit an empty cylindrical cartridge with a capacity of 6 mL. Breakthrough curves using the chelating-porous-disk-packed cartridge overlapped irrespective of the flow rate of the solution ranging up to 1500 mL/h because of negligible diffusional mass-transfer resistance of the copper ions to the iminodiacetate group of the graft chain.     

Influence of inserting AlN between AlSiON and 4H-SiC interface for the MIS structure

A control of interface between gate insulating film and semiconductor is required to achieve high-power field effect transistors (FET) using SiC. To improve the interface between the high-k layer and SiC, we propose inserting an AlN layer as an interfacial layer. The reason for selecting AlN film is that it has a wide bandgap, as well as almost the same lattice constant as that of 4H-SiC. The insertion of AlN film between 4H-SiC and the insulating film effectively reduces the interfacial roughness. The roughness of the interface between AlN and SiC can be suppressed compared with that of the thermal oxidized SiC. Moreover, the AlSiON film was deposited on the AlN layer as a high dielectric gate insulating film with low leakage current at high temperature and low space charge. The C-V characteristics of the AlSiON/AlN/SiC MIS structure with an AlN buffer layer are improved by increasing the deposition temperature of the AlN film. This demonstrates that AlSiON/AlN/SiC is one of attractive MIS structures for SiC devices.     

Fusion of phosphole and 1,1'-biacenaphthene: phosphorus(V)-containing extended π-systems with high electron affinity and electron mobility

A profusion of phospholes: Diacenaphtho[1,2-b:1',2'-d]phospholes, a new class of arene-fused phosphole π-systems, were synthesized and their structural and electrochemical properties studied. The P-sulfide derivative has a high electron-transporting ability (μ(E) =2.4×10(-3) cm(2) V(-1) s(-1)) in a vacuum-deposited film.     

Synthesis, structures and inclusion properties of tetranaphthalides: new macrocyclic clathrate hosts

Novel tetranaphthalide host compounds 3 and 4 bearing isomeric naphthalene moieties have been synthesized and their inclusion properties were investigated. These host compounds enclathrated several kinds of ketones, cyclic ethers, amides, sulfoxides and aromatic compounds. The structures of two representative inclusion compounds containing different host molecules and a common guest (dimethyl sulfoxide) were investigated by X-ray diffraction to determine the nature of guest inclusion and to rationalize their distinctly different thermal decomposition profiles.     

Vibrational properties of CaAlH5 and α-AlH3 with different AlH6 networks studied by inelastic neutron scattering

We performed a combined study using inelastic neutron scattering (INS) and first-principles calculations of the vibrational properties of CaAlH(5) and α-AlH(3) with different AlH(6) networks, a zigzag one-dimensional AlH(6) network for CaAlH(5), and a three-dimensional AlH(6) network for α-AlH(3). Both materials showed qualitatively similar INS spectra, in which CaAlH(5)/α-AlH(3) was mainly divided into three regions: (i) the translational modes (318/316 cm(-1)), (ii) the librational modes of the octahedral AlH(6) units (external molecular motion) in the lower frequency range and H-Al-H bond-bending modes (intra molecular motion) at a higher frequency (420-1157/513-1038 cm(-1)), and (iii) the Al-H bond-stretching modes (1238-1750/1486-1942 cm(-1)). In region ii, the appearance of both librational and bond-bending modes was determined by the networked nature of the octahedral AlH(6) units. In addition, the librational modes of AlH(6) on α-AlH(3) exhibit higher frequencies than CaAlH(5) due to the tighter bonding between the octahedral AlH(6) units. With regard to average frequencies for the Al-H, ω(S), bond-stretching modes, and average Al-H bond distances on the aluminum-based hydrides including CaAlH(5) and α-AlH(3), ω(S) showed lower frequencies that correlate with lengthening of the Al-H bond distances.     

Formation of a charge distribution within ionic gels by immobilized enzyme reaction: experimental observations and mathematical simulations

Thermally responsive cationic gels with immobilized urease, in the shape of a small cylinder with diameter 290 - 640 μm, were prepared via gelation of an aqueous monomer solution containing the enzyme. We used N-isopropylacrylamide and N-vinylimidazole as a thermo-sensitive and a pH-sensitive monomer, respectively. Diameters at different positions of the cylinder were microscopically measured in a cell through which substrate solution (pH 4; 35°C) was passed at a constant flow rate; thus, both substrate concentration and pH at the gel surface were maintained at a constant level. It was found that the gel undergoes a shrinking change due to an enzymatically induced increase in pH within the gel phase. There was a marked position dependence of the shrinking degree; the diameter at the center of the cylinder was smaller than those at the top and at the bottom, but the diameters at the top and bottom were identical with each other. This trend was observed at immobilized enzyme concentrations < 1 mg/mL, even after the establishment of swelling equilibrium. By mathematical simulations with a reaction-diffusion model, these results were understood in connection with a charge distribution which is formed as a result of an enzymatically generated pH gradient within the gel phase.