Theoretical fine spectroscopy with symmetry adapted cluster-configuration interaction general-R method: first-row K-shell ionizations and their satellites

Molecular core ionization spectra and their satellites were studied by the symmetry adapted cluster-configuration interaction (SAC-CI) general-R method. The core-electron binding energies of C, N, O, and F atoms of 22 molecules were calculated with an average deviation of 0.11 eV from the experimental values. The energy splittings between K-shell gerade and ungerade states were calculated and discussed in relation to the bond length. The satellite spectra of the C 1s and N 1s core ionizations of methane and ammonia were investigated. The SAC-CI general-R method gave many shake-up states with moderate intensities, reproducing the general feature of the experimental spectra, and thus enabling the detailed understanding and assignments of the core-electron ionization spectra.     

Synthesis of optically active β-alkyl aspartate via [3,3] sigmatropic rearrangement of α-acyloxytrialkylsilane

The synthesis of four types of optically active β-carbon-substituted analogs of threo-β-hydroxy aspartate (THA) and a β-carbon-substituted analog of threo-β-benzyloxy aspartate (TBOA), which are potent blockers of excitatory amino acid transporters in the mammalian central nervous system, via the chirality-transferring ester-enolate Claisen rearrangement of α-acyloxytrialkylsilane is described.     

Sensitive determination of ambenonium chloride in serum from patients with myasthenia gravis using ion-exchange resin extraction and reversed-phase ion-pair chromatography

An effective and selective procedure for the extraction of ambenonium chloride (AMBC) from serum using a weak cation-exchange extraction cartridge has been developed. The solid-phase extraction procedure permitted the extraction of AMBC from serum without adhesion to materials such as the containers. A 200-microliter volume of the eluate could be directly injected on to a reversed-phase ion-pair high-performance liquid chromatographic column. The recovery was in the range 97-100%. The limit of detection for AMBC was 0.5 ng/ml in serum (signal-to-noise ratio = 3). The method was used to determine the serum concentration of AMBC in patients with myasthenia gravis. The method would be useful for monitoring AMBC in serum in order to study its pharmacokinetic behaviour in patients under oral administration therapy.     

Synthesis and photovoltaic properties of thieno[3,4‐b]pyrazine or dithieno[3′,2′:3,4;2″,3″:5,6]benzo[1,2‐d]imidazole‐containing conjugated polymers

Novel conjugated polymers composed of benzo[1,2‐b:4,5‐b′]dithiophene and thieno[3,4‐b]pyrazine or dithieno[3′,2′:3,4;2″,3″:5,6]benzo[1,2‐d]imidazole units are synthesized by Stille polycondensation. The resulting polymers display a longer wavelength absorption and well‐defined redox activities. The effective intramolecular charge‐transfer and energy levels of all polymers are elucidated by computational calculations. Bulk‐heterojunction solar cells based on these polymers as p‐type semiconductors and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as an n‐type semiconductor are fabricated, and their photovoltaic performances are for the first time evaluated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1067–1075     

Base‐amplifying silicone resins with photobase‐generating side chains and their application to negative‐working photoresists

To accomplish high photosensitivity of resist systems including photobase generators, we have proposed the concept of base‐proliferation reactions that generate base molecules in a nonlinear manner by the action of a catalytic amount of base; however, excessive diffusion of generated base molecules is still a problem. We have designed novel functional silicone resins bearing both base‐amplifying units and photobase‐generating units, and synthesized resins with various composition ratios. The synthesized resins are decomposed autocatalytically after UV irradiation and subsequent heating at 100 °C, which indicates progression of base‐proliferation reactions. High photosensitivity (8.1 mJ cm^?2) was recorded, and it was found that the photosensitivity is about 490 times enhanced by replacing a base‐catalytic reaction system with the base‐proliferation reaction system. Furthermore, a 4 × 10 µm line‐and‐space pattern has been successfully fabricated using the silicone resin. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1205–1212     

Development of Calcium Phosphate Glass-Ceramics for Surgical and Dental Use

Abstract

Two types of glass-ceramics have been developed in the system of calcium phosphate without silica. The preparation conditions, crystallization processes, and some of physical properties are briefly reported. These glass-ceramics have high potential use for bone substitutes and dental materials such as dental crown, root and tooth.     

Simultaneous manifestation of metallic conductivity and single-molecule magnetism in a layered molecule-based compound

Single-molecule magnets (SMMs) show superparamagnetic behaviour below blocking temperature at the molecular scale, so they exhibit large magnetic density compared to the conventional magnets. Combining SMMs and molecular conductors in one compound will bring about new physical phenomena, however, the synergetic effects between them still remain unexplored. Here we present a layered molecule-based compound, β′′-(BEDO-TTF)₄ [Co(pdms)₂]·3H₂O (BO4), (BEDO-TTF (BO) and H₂pdms are bis(ethylenedioxy)tetrathiafulvalene and 1,2-bis(methanesulfonamido)benzene, respectively), which was synthesized by using an electrochemical approach and studied by using crystal X-ray diffraction. This compound simultaneously exhibited metallic conductivity and SMM behaviour up to 11 K for the first time. The highest electrical conductivity was 400–650 S cm⁻¹ at 6.5 K, which is the highest among those reported so far for conducting SMM materials. Furthermore, antiferromagnetic ordering occurred below 6.5 K, along with a decrease in conductivity, and the angle-independent negative magnetoresistance suggested an effective electron correlation between the conducting BO and Co(pdms)₂ SMM layers (d–π interactions). The strong magnetic anisotropy and two-dimensional conducting plane play key roles in the low-temperature antiferromagnetic semiconducting state. BO4 is the first compound exhibiting antiferromagnetic ordering among SMMs mediated by π-electrons, demonstrating the synergetic effects between SMMs and molecular conductors.

A metallic single-molecule magnet was synthesised demonstrating simultaneous metallic conduction and excellent SMM properties at the same temperature range for the first time, with potential applications in molecule-based quantum spintronics.