A naphtho-tri-t-butyltrisdehydro[16]annulene and related compounds

Synthesis of naphtho-tri-t-butyltrisdehydro[16]annulene containing a hexapentaene and an acetylene units has been described. It was found that the [16]annulene is less stable and the paratropicity is much stronger as compared with previously reported isomeric naphtho[16]-annulene containing a diacetylene and a butatriene linkage.     

Dendron-grafted sulfur-terminated phenyleneethynylene molecular rods and blue luminescence self-assembly with Au nanoparticles

Dendron-grafted phenyleneethynylenes with alpha,omega-disulfur containing groups were newly synthesized and characterized for self-assembly with Au nanoparticles; an intense blue photoluminescence of the composite film was observed.     

Development of New Modifiers for Titanium Alkoxide-Based Sol-Gel Process

The effects of several hydroxyketones such as acetol, actoin, -ketobutanol themselves and their combinations with monoethanolamine (MEA) or ethylenediamine (ED) on the stabilization of titanium tetraisopropoxide (TTIP) in isopropanol solution are examined. Acetoin itself and the imine derivatives of acetol and acetoin were found to show extraordinarily strong stabilizing effect for the alkoxide. The properties including the crystal modifications and refractive index of TiO₂ films that were dip-coated using each stabilized solution are examined and discussed in comparison with those of the films obtained from the diethanolamine (DEA) systems. The effect of UV-light irradiation to the gel films on the crystallization of TiO₂ is also examined and discussed.     

Discovery of Hexagonal Structured Pd–B Nanocrystals

We report on hexagonal close-packed (hcp) palladium (Pd)–boron (B) nanocrystals (NCs) by heavy B doping into face-centered cubic (fcc) Pd NCs. Scanning transmission electron microscopy–electron energy loss spectroscopy and synchrotron powder X-ray diffraction measurements demonstrated that the B atoms are homogeneously distributed inside the hcp Pd lattice. The large paramagnetic susceptibility of Pd is significantly suppressed in Pd–B NCs in good agreement with the reduction of density of states at Fermi energy suggested by X-ray absorption near-edge structure and theoretical calculations.     

Electrochemical detection of endotoxin using recombinant factor C zymogen

We have developed a zymogen-based electrochemical sensor. Zymogen is an inactive enzyme precursor (proenzyme) and it is necessary to transform it biochemically (e.g., by hydrolysis and conformational change) to make it an active enzyme. In this study, we demonstrated the detection of endotoxin by using recombinant Factor C (rFC), which is a protease zymogen activated by endotoxin binding. The activated rFC hydrolyzes a synthetic substrate of Boc-Val-Pro-Arg-p-nitroanilnide to generate an electrochemical active compound, p-nitroaniline (pNA). The liberated pNA was detected by differential pulse voltammetry at –0.75 V. By using this electrochemical process, 5000 endotoxin units (EU) L^?1 and 1000 EU L^?1 were detected in a Tris-Ac buffer with a pH of 7.5 at 37 °C for reaction times of 1 h and 3 h, respectively. The concept of zymogen-based electrochemical sensors is expected to lead to the development of new biosensors.     

Biradical character of linear π-conjugated oligomer dications composed of thiophene, pyrrole, and methylthio end-capping units

Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.     

Highly selective photoinduced perfluoroalkylation of vinylsilanes and its application to synthesis of water-shedding polysilanes

The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (R_fI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI₂) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and R_fI (about 1.0 mM CHCl₃ solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate.