Host–Guest Complexation of Perethylated Pillar[5]arene with Alkanes in the Crystal State

Activated perethylated pillar[5]arene crystals show an unexpected alkane‐shape‐ and ‐length‐selective gate‐opening behavior. Activated crystals were obtained upon removing solvents from perethylated pillar[5]arene crystals by heating. The activated crystals could quantitatively take up n‐alkanes with carbon chains containing more than five carbon atoms as a consequence of their gate‐opening pressure. As the chain length of the n‐alkanes increased, the gate pressure decreased. A transformation into a herringbone structure was induced when n‐hexane was used as a guest. By contrast, cyclic and branched alkanes were not taken up and could not induce a crystal transformation because they were too large to fit in the cavities of the pillar[5]arene. Alkane‐shape‐selective molecular recognition of pillar[5]arenes in the solution state was translated into the vapor/crystal state.     

An LC method for quantifying bepridil in human plasma using 1-naphthol as the internal standard

A modified method for the quantitative determination of bepridil hydrochloride in human plasma is described. This method is unrelated to chemical methods currently in use. The mobile phase is 50 mM phosphate buffer (pH3.0)-methanol-acetonitrile-triethylamine (57:3:40:1, v/v), and the samples are fractionated on a C8-3 column (150 × 4.6 mm, 5 μm) using a flow rate of 0.9 mL/min. Bepridil was detected by UV spectroscopy at 254 nm. The retention times of bepridil and 1-naphthol were 12.6 min and 7.5 min, respectively; there was no interference originating from human plasma. We confirmed that the bepridil and 1-naphthol peaks were not influenced by the presence of 32 commercial medicines frequently co-administered with bepridil. Additionally, the concentration of bepridil in the plasma of five patients treated with bepridil for atrial fibrillation was measured. These samples were collected just before each dosage of bepridil. Their rhythm and rate control were well maintained. Trough concentrations ranged from 233.9 to 347.4 ng/mL, similar to previously reported values.     

Domino allylation and cyclization of ortho-alkynylbenzaldehydes with allyltrimethylsilane catalyzed by Pd(II)-Cu(II) bimetallic systems

The reaction of ortho-alkynylated benzaldehydes 1 with allyltrimethylsilane under the Pd(OAc)₂-CuCl₂ catalyst system gave the isochromene derivatives 2 together with the chlorinated products 3. When the reaction was conducted in the presence of half equiv of H₂O, the formation of 3 was suppressed and 2 was obtained in good to high yields. When the reaction of 1a was carried out with trimethylsilylcyanide instead of allylsilane, the cyano group-substituted isochromene 9 was obtained in 94% yield.     

Effects of organic modifiers on the chiral recognition by different types of silica-immobilized bovine serum albumin

We prepared three columns containing bovine serum albumin immobilized on silica by different means and the effects of organic modifiers in the eluent on chiral separation were studied using N-substituted amino acids. Adsorption on silica, covalent immobilization to diol-silica with carbonyldiimidazole (CSP-II) and covalent immobilization to amino-silica with glutaraldehyde were studied. CSP-II had the highest stereoselectivity and was the most affected by organic modifiers in the eluent. The hydrophobicity of amino acid moiety affected the chiral recognition of N-benzoylamino acids and the aromaticity of the N-substituted group was important.     

Beryllium double K X-ray emission by proton and helium ion bombardment

X-ray spectra from beryllium by proton and helium ion bombardment are studied. A clear peak due to double K-shell ionization is observed at 146.1 eV by helium ion bombardment. For proton bombardment, a peak of double K-shell ionization is not observable.     

Concise synthesis of dl-febrifugine

Racemic compound (1) of the antimalarial agents febrifugine (d-1) was synthesized using an stereoselective Michael reaction of an omega-amidoenone (5) which was prepared by the Wittig reaction of piperidinediol (7).     

Photoinduced cycloadditions of electron deficient nitrones to alkenes

Oxaziridines are proposed as intermediates in the photoinduced cycloadditions of electron deficient nitrones to dipolarophiles.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

Control of hole opening in single-wall carbon nanotubes and single-wall carbon nanohorns using oxygen

Due to the simplicity of the process, holes in the graphene walls of single-wall carbon nanotubes (SWNTs) and single-wall carbon nanohorns (SWNHs) have often been opened using O2 gas at high temperatures, even though this contaminates the nanotubes with carbonaceous dust (C-dust). To open holes with less C-dust contamination, we found that a slow temperature increase of 1 degrees C/min or less, in air, was effective. We also found that SWNHs having little C-dust could store a large quantity of materials inside the tubes. We infer that the local temperature increase due to the exothermic reaction of combustion may have been suppressed in the slow combustion process, which was effective in reducing the C-dust.