Intramolecular Pauson-Khand reaction of optically active aza-Baylis-Hillman adducts

The intramolecular Pauson-Khand reaction of aza-Baylis-Hillman adducts, which were prepared through the thio-Michael/imino-aldol domino reaction of optically active sulfinimines, was examined and gave optically active cis- and trans-pyrrolidine-fused cyclopentenones in a stereoselective manner.     

Top-down analysis of basic proteins by microchip capillary electrophoresis mass spectrometry

A system of microchip capillary electrophoresis/electrospray ionization mass spectrometry (microchip-CE/ESI-MS) for rapid characterization of proteins has been developed. Capillary electrophoresis (CE) enables rapid analysis of a sample present in very small quantity, such as at femtomole levels, at high resolution. Faster CE/MS analysis is expected by downsizing the normal capillary to the microchip (microchip) capillary. Although rapidity and high resolution are advantages of CE separation, electroosmotic flow (EOF) instability caused by the interaction between proteins and the microchannel surface results in low reproducibility in the analysis of basic proteins under neutral pH conditions. By coating the microchannel surface with a basic polymer, polyE-323, basic proteins, which have pI values of over 7.5, could be separated and detected by microchip-CE/MS on quadrupole (Q) and time-of-flight (TOF) hybrid instruments. By increasing the cone and collision voltages during the analysis by microchip-CE/ESI-MS of a small protein, some product ions, which contain the sequence information, could also be obtained, i.e., 'top-down' analysis of the protein could be accomplished with this microchip-CE/MS system. To our knowledge, this is the first report of 'top-down' analysis of a protein by microchip-CE/MS. Since it requires a much shorter time and a smaller sample amount for analysis than the conventional liquid chromatography (LC)/ESI-MS method, microchip-CE/MS promises to be suitable for the high-throughput characterization of proteins.     

Acoustic pulse echoes probed with time-resolved X-ray triple-crystal diffractometry

Acoustic pulse echoes generated by femtosecond laser irradiation were detected using time-resolved x-ray triple-crystal diffractometry. The determined time-dependent longitudinal strain component for pulse echoes in silicon and gallium arsenide plates showed that the polarity of the strain pulse was dependent on the optically induced initial stress, and that the bipolar pulse waveform was gradually deformed and broadened in the course of propagation. The three-dimensional wave front distortion of pulse echoes was shown simply as the pulse duration broadening, which was consistent with a boundary roughness for an unpolished plate.     

Ultrasonic speed microscopy for imaging of coronary artery

We have been developing a scanning acoustic microscope (SAM) system for medicine and biology featuring quantitative measurement of ultrasonic speed and attenuation of soft tissues. In the present study, we will propose a new concept ultrasonic speed microscopy that can measure the thickness and ultrasonic speed using fast Fourier transform of a single pulsed wave instead of continuous waves used in conventional SAM systems. Six coronary arteries were frozen and sectioned approximately 10 microm in thickness. They were mounted on glass slides without cover slips. The scanning time of a frame with 300 x 300 pixels was 121 s and two-dimensional distribution of ultrasonic speed was obtained. The ultrasonic speed was 1720 m/s in the thickened intima with collagen fiber, 1520 m/s in lipid deposition underlying fibrous cap and 1830 m/s in calcified lesion in the intima. These basic measurements will help understanding echogenecity in intravascular ultrasound (IVUS) images. Imaging of coronary artery with the ultrasonic speed microscopy provides important information for study of IVUS coronary imaging.     

Surface relaxation of polarized Xe atoms dissolved in deuterated ethanol

We measured the spin relaxation of polarized xenon atoms dissolved in deuterated ethanol. Surface relaxation was suppressed by coating the cell walls with deuterated eicosane. From the dependence of the decay rate on temperature and static magnetic field, we obtained the correlation time of random fluctuations of the local field at the liquid-solid interface. By varying the cell volume, the wall coating, and the surface area of the eicosane, we measured the contribution of the spin-rotation interaction to the relaxation. The use of both deuterated molecules enables us to distinguish surface relaxation from the magnetic dipole-dipole and spin-rotation interactions in solution.     

Evidence of the purely leptonic decay B- --> tau- nu(tau)

We present the first evidence of the decay B- --> tau- nu(tau), using 414 fb(-1) of data collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e+ e- collider. Events are tagged by fully reconstructing one of the B mesons in hadronic modes. We detect the signal with a significance of 3.5 standard deviations including systematics and measure the branching fraction to be B(B- --> tau- nu(tau)) = (1.79(-0.49) +0.56(stat)(-0.51) +0.46(syst)) x 10(-4). This implies that fB = 0.229(-0.031) +0.036(stat)(-0.037) +0.034(syst) GeV and is the first direct measurement of this quantity.     

Evidence for B-->eta'pi and improved measurements for B-->eta'K

We report evidence for the exclusive two-body charmless hadronic B meson decay B-->eta'pi, and improved measurements of B-->eta'K. The results are obtained from a data sample of 386x10(6) BB pairs collected at the Upsilon(4S) resonance, with the Belle detector at the KEKB asymmetric-energy e+e- collider. We measure B(B+-->eta'pi+)=[1.76(-0.62)(+0.67)(stat)(-0.14)(+0.15)(syst)]x10(-6) and B(B0-->eta'pi0)=[2.79(-0.96)(+1.02)(stat)(-0.34)(+0.25)(syst)]x10(-6). We also find the ratio of B(B+-->eta'K+)/B(B0-->eta'K0)=1.17+/-0.08(stat)+/-0.03(syst) and measure the direct CP asymmetries for the charged modes.     

Sodium‐ and Potassium‐Hydrate Melts Containing Asymmetric Imide Anions for High‐Voltage Aqueous Batteries

Aqueous Na‐ or K‐ion batteries could virtually eliminate the safety and cost concerns raised from Li‐ion batteries, but their widespread applications have generally suffered from narrow electrochemical potential window (ca. 1.23 V) of aqueous electrolytes that leads to low energy density. Herein, by exploring optimized eutectic systems of Na and K salts with asymmetric imide anions, we discovered, for the first time, room‐temperature hydrate melts for Na and K systems, which are the second and third alkali metal hydrate melts reported since the first discovery of Li hydrate melt by our group in 2016. The newly discovered Na‐ and K‐ hydrate melts could significantly extend the potential window up to 2.7 and 2.5 V (at Pt electrode), respectively, owing to the merit that almost all water molecules participate in the Na⁺ or K⁺ hydration shells. As a proof‐of‐concept, a prototype Na₃V₂(PO₄)₂F₃|NaTi₂(PO₄)₃ aqueous Na‐ion full‐cell with the Na‐hydrate‐melt electrolyte delivers an average discharge voltage of 1.75 V, that is among the highest value ever reported for all aqueous Na‐ion batteries.     

Reaction energy benchmarks of hydrocarbon combustion by Gaussian basis and plane wave basis approaches

The reaction energies of 275 elementary reactions from the hydrocarbon combustion model GRI-Mech 3.0 were evaluated by electronic structure calculations using both localized Gaussian basis and plane wave basis sets. In the Gaussian basis calculations, the d-polarization function on C, N, and O elements reduces the mean absolute deviation (MAD) from the experimental value by 53%, a significant improvement in computational accuracy. In the plane wave basis calculation using different exchange-correlation (XC) functionals, the MAD values were 0.316–0.426 eV when non-hybrid type XC functionals such as RPBE, PBE, PW91, revPBE, and PBEsol were used. On the other hand, hybrid functionals like B3LYP and HSE06 reduced the MAD values significantly down to 0.182 and 0.233 eV, respectively. The B3LYP results have 49% less MAD compared to the PBE results. These demonstrated the strong advantage of the hybrid functional for calculating gas-phase reaction energies. The present comprehensive benchmarks will be crucial for future microkinetics as well as machine learning studies on the catalytic reactions. © 2019 Wiley Periodicals, Inc.     

Mössbauer and photocatalytic studies of CaFe2O4 nanoparticle-containing aluminosilicate prepared from domestic waste simulated slag

The relationship between local structure and visible-light activated photocatalytic effect of simulated domestic waste slag glass–ceramics (R-NaWSFe) was investigated. The largest pseudo-first-order rate constant of 9.75?×?10^?3 min^?1 was estimated for methylene blue decomposition test under the visible-light irradiation using R-NaWSFe with additional 30 mass% of Fe₂O₃ heat-treated at 900 °C for 100 min. The reason for the high photoactivity of this sample was mainly due to nanoparticles of CaFe₂O₄ and α-Fe₂O₃ confirmed by the Mössbauer spectrum measured at 77 K. It is concluded that the nanoparticles of magnetic components in silica are essential for exhibiting visible-light activated catalytic effect.