Superconductivity in entirely end-bonded multiwalled carbon nanotubes

We report that entirely end-bonded multiwalled carbon nanotubes (MWNTs) can exhibit superconductivity with a transition temperature (T(c)) as high as 12 K, which is approximately 30 times greater than T(c) reported for ropes of single-walled nanotubes. We find that the emergence of this superconductivity is highly sensitive to the junction structures of the Au electrode/MWNTs. This reveals that only MWNTs with optimal numbers of electrically activated shells, which are realized by end bonding, can allow superconductivity due to intershell effects.     

Determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell

A method is described for determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell (ID–ICP–ORCMS). Sediment samples were digested with HNO₃, HClO₄, and HF, and the digestion included an elaborate evaporation process to remove bromine from the digested solution. Simple strong cation-exchange disk filtration was used to remove rare earth elements (REE) from the digested solution, because REE²⁺ seriously interfere with Se isotopes (i.e. ¹⁵⁶Gd²⁺ with ⁷⁸Se⁺, ¹⁶⁰Gd²⁺ with ⁸⁰Se⁺). Addition of acetic acid to the filtrate was examined to improve the sensitivity of ICP–ORCMS measurement of Se⁺ by means of a carbon-enhancement effect. The interfering for selenium isotopes were almost eliminated by use of H₂ as reaction gas. Interference from BrH⁺ formed in the reaction cell was negligible because the Br was removed in the evaporation process. Approximately 99.5% of REE were removed by cation-exchange disk filtration yet more than 99% of Se remained in the filtrate solution. The intensity for Se⁺ was enhanced approximately fourfold by addition of 5% (v/v) of acetic acid whereas that for was barely enhanced. Measured ⁸⁰Se/⁷⁸Se ratios in unspiked digested solutions of the sample were in good agreement with that for an Se standard solution. The analytical results for Se in the certified reference materials MESS-3 and PACS-1 were in good agreement with their certified values, with small uncertainties.      

Electrospray deposition, model, and experiment: toward general control of film morphology

Poly(vinylidene fluoride) film formation with electrospray deposition has been studied with support of a droplet evaporation model. The input parameters of the model consist basically of the solvent, the solute concentration, the flow rate, and the solution conductivity. The model provides the droplet size, the solute concentration, the droplet velocity, and the shear stress of the droplet at impact as a function of the distance between the nozzle and the substrate. With some additional experimental information such as the size change of the film with spray distance and the viscosity of the solution, the growth rate of the film and the shear rate of the droplet at impact can be determined. Growth rate is shown to define distinct regimes of film formation. In those regimes, only a single factor or a limited number of factors controls the film morphology. The most important factors include the shear rate and the surface energy. It is found that at a specific range of growth rates only the shear rate determines the morphology of the polymer film. Growth rate, as the defining quantity of film morphology, is not limited to polymer solutions. Therefore, the growth rate, in combination with the control factors mentioned above, functions as a general framework through which understanding and control of film formation with electrospray deposition can be improved.     

Perturbation Formula for Phase Velocity of Rayleigh Waves in Prestressed Anisotropic Media

Herein we consider Rayleigh waves propagating along the free surface of a macroscopically homogeneous, anisotropic, prestressed half-space. We adopt the formulation of linear elasticity with initial stress and assume that the deviation of the prestressed anisotropic medium from a comparative ‘unperturbed’, unstressed and isotropic state, as formally caused by the initial stress and by the anisotropic part of the incremental elasticity tensor, be small. No assumption, however, is made on the material anisotropy of the incremental elasticity tensor. With the help of the Stroh formalism, we derive a first-order perturbation formula for the shift of phase velocity of Rayleigh waves from its comparative isotropic value. Our perturbation formula does not agree totally with that which was derived some years ago by Delsanto and Clark, and we provide another argument as further support for our version of the formula. According to our first-order formula, the anisotropy-induced velocity shifts of Rayleigh waves, taken in totality of all propagation directions on the free surface, carry information only on 13 elastic constants of the anisotropic part of the incremental elasticity tensor. The remaining eight elastic constants are those which would become zero if were monoclinic with the two-fold symmetry axis normal to the free surface of the material half-space in question.     

Electron-boson coupling and oxygen-isotope effect in the optical conductivity of high-Tc superconductors

We have investigated electron-boson coupling in the optical conductivity of high-T_c superconductors through the optical self-energy. The real part of the self-energy (ReΣ^op(ω)) of YBa₂Cu₃O_y (YBCO) shows a characteristic doping dependence. In the optimally doped YBCO, ReΣ^op(ω) has a single peak around 65 meV, which corresponds to the kink structure of the band dispersion. On the other hand, in the under-doped YBCO, the peak structure of ReΣ^op(ω) splits into two parts. To evaluate contribution from the phonons in electron-boson coupling, we have measured oxygen-isotope effects by substituting ¹⁶O→¹⁸O for the optimally doped and under-doped YBCO.     

Stereoselective synthesis of scyphostatin hydrophilic moiety

A stereoselective synthesis of scyphostatin hydrophilic moiety was accomplished. Substrate- and reagent-controlled dihydroxylation of tri- and monosubstituted alkenes afforded desired diols, respectively. Chemo- and stereoselective allylation of α-(methoxycarbonyl)cyclohexanone provided allylcyclohexanol. Oxidative cleavage of glycol and subsequent β-elimination of siloxycyclohexanone furnished the desired epoxycyclohexenone.     

Recent examples of the use of biocatalysts with high accessibility and availability in natural product synthesis

Utilization of biocatalysts with high accessibility and availability, which have recently been applied in the preparation of enantiomerically enriched starting materials and synthetic intermediates for natural product syntheses (mainly 2013–2017) are summarized in this review. The main contents are as follows: 1) recruitment of biocatalysts for the transformation of organic compounds; 2) special precautions for preparative-scale biocatalytic synthetic experiments; 3) asymmetric reduction of carbonyl substrates; 4) kinetic resolution of alcohol and carboxylate enantiomers; 5) desymmetrization of multifunctional alcohol and carboxylate substrates; and 6) recognition of remote and non-central chirality.     

Helicity Induction and Memory of the Macromolecular Helicity in a Polyacetylene Bearing a Biphenyl Pendant

A novel, cis‐transoidal poly‐(phenylacetylene) bearing a carboxybiphenyl group as the pendant (poly‐ 1 ) was prepared by polymerization of (4′‐ethoxycarbonyl‐4‐biphenylyl)acetylene with a rhodium catalyst followed by hydrolysis of the ester groups. Upon complexation with various chiral amines and amino alcohols in dimethyl sulfoxide (DMSO), the polymer exhibited characteristic induced circular dichroism (ICD) in the UV/Vis region due to the predominantly one‐handed helix formation of the polymer backbone as well as an excess of a single‐handed, axially twisted conformation of the pendant biphenyl group. Poly‐ 1 complexed with (R)‐2‐amino‐1‐propanol showed unique time‐dependent inversion of the macromolecular helicity. Furthermore, the preferred‐handed helical conformation of poly‐ 1 induced by a chiral amine was further “memorized” after the chiral amine was replaced with achiral 2‐aminoethanol or n‐butylamine in DMSO. In sharp contrast to the previously reported memory in poly((4‐carboxyphenyl)acetylene), the present helicity memory of poly‐ 1 was accompanied by memory of the twisted biphenyl chirality in the pendants. Unprecedentedly, the helicity memory of poly‐ 1 with achiral 2‐aminoethanol was found to occur simultaneously with inversion of the axial chirality of the biphenyl groups followed by memory of the inverted biphenyl chirality, thus showing a significant change in the CD spectral pattern.