Calcite and fluorite as catalyst for the Knövenagel condensation of malononitrile and methyl cyanoacetate under solvent-free conditions

When milled together with calcite or fluorite, malononitrile and methyl cyanoacetate readily underwent Knövenagel condensation with aromatic aldehydes, giving the corresponding arylidenemalononitriles and (E)-α-cyanocinnamic esters in good to excellent yield.     

Measurement of temporal changes in vocal tract area function from 3D cine-MRI data

A 3D cine-MRI technique was developed based on a synchronized sampling method [Masaki et al., J. Acoust. Soc. Jpn. E 20, 375-379 (1999)] to measure the temporal changes in the vocal tract area function during a short utterance /aiueo/ in Japanese. A time series of head-neck volumes was obtained after 640 repetitions of the utterance produced by a male speaker, from which area functions were extracted frame-by-frame. A region-based analysis showed that the volumes of the front and back cavities tend to change reciprocally and that the areas near the larynx and posterior edge of the hard palate were almost constant throughout the utterance. The lower four formants were calculated from all the area functions and compared with those of natural speech sounds. The mean absolute percent error between calculated and measured formants among all the frames was 4.5%. The comparison of vocal tract shapes for the five vowels with those from the static MRI method suggested a problem of MRI observation of the vocal tract: data from static MRI tend to result in a deviation from natural vocal tract geometry because of the gravity effect.     

Structure and O2-reactivity of copper(I) complexes supported by pyridylalkylamine ligands

The structure and O2-reactivity of a series of copper(I) complexes supported by the pyridylalkylamine ligands are summarized, and the ligand effects such as the chelate ring size effect (five- vs. six-membered ring), the denticity effect (tetradentate vs. tridentate vs. didentate), the steric effect of 6-methylpyridine and the steric and/or electronic effects of N-alkyl substituents are discussed in detail.     

Design and synthesis of novel chiral spiro ionic liquids

[reaction: see text] Novel chiral imidazolium salts have been synthesized as examples of chiral ionic liquids with a spiro skeleton. Effects of N-substituents and counteranions on the melting point of spiro imidazolium salts and their chiral discrimination abilities are described.     

Electrical breakdown of microwave plasma in water

The electrical breakdown of microwave plasma in water was investigated between 1 and 30 kPa. The dependency of the ignition power for generating plasma on the size of coaxial electrode was measured. The ignition power decreases with a decrease of the diameter of the inner electrode. The behavior of microwave plasma in water was observed using a high-speed camera. The plasma ignites in a bubble generated by microwave heating. The model for calculating the electric field was created on the basis of the captured images of the bubble just before plasma ignition. The method presented can be used to visualize the electrical field distribution in the bubble. The electric field breakdown was calculated using the measured ignition power. The electric field breakdown of plasma in water is of the same order as gas phase plasma.     

Key Factors for Simultaneous Improvements of Performance and Durability of Core‐Shell Pt3Ni/Carbon Electrocatalysts Toward Superior Polymer Electrolyte Fuel Cell

It remains a big challenge to remarkably improve both oxygen reduction reaction (ORR) activity and long‐term durability of Pt?M bimetal electrocatalysts simultaneously in the harsh cathode environment toward widespread commercialization of polymer electrolyte fuel cells (PEFC). In this account we found double‐promotional effects of carbon micro coil (CMC) support on ORR performance and durability of octahedral Pt₃Ni nanoparticles (Oh Pt₃Ni/CMC). The Oh Pt₃Ni/CMC displayed remarkable improvements of mass activity (MA; 13.6 and 34.1 times) and surface specific activity (SA; 31.3 and 37.0 times) compared to those of benchmark Pt/C (TEC10E20E) and Pt/C (TEC10E50E‐HT), respectively. Notably, the Oh Pt₃Ni/CMC revealed a negligible MA loss after 50,000 triangular‐wave 1.0–1.5 V_RHE (startup/shutdown) load cycles, contrasted to MA losses of 40 % (TEC10E20E) and 21.5 % (TEC10E50E‐HT) by only 10,000 load cycles. It was also found that the SA increased exponentially with the decrease in the CO stripping peak potential in a series of Pt?M/carbon (M: Ni and Co), which predicts a maximum SA at the curve asymptote. Key factors for simultaneous improvements of performance and durability of core‐shell Pt₃Ni/carbon electrocatalysts toward superior PEFC is also discussed.