Kinetic study of proton-transfer reactions of phenylnitromethanes. Implication for the origin of nitroalkane anomaly

Measurements of rate constants and substituent effects for three important elementary steps of proton-transfer reactions of phenylnitromethane were reported. The Hammett ρ values for the deprotonation of ArCH(2)NO(2) with OH(-), protonation of ArCH═NO(2)(-) with H(2)O, and protonation of ArCH═NO(2)(-) with HCl were determined in aqueous MeOH at 25 °C. Comparison of these experimentally observed ρ values with those calculated at B3LYP/6-31G* revealed that aci-nitro species (ArCH═NO(2)H), which is formed on the O-protonation of ArCH═NO(2)(-), does not lie on the main route of the proton-transfer reaction. Analysis of the Br?nsted plot implies that the proton-transfer reaction of most XC(6)H(4)CH(2)NO(2) exhibits nitroalkane anomaly, but not for p-NO(2)C(6)H(4)CH(2)NO(2), and that the transition state charge imbalance is an origin of anomaly.     

Fluidic shear-assisted formation of actuating multilamellar lipid tubes using microfabricated nozzle array device

Molecular self-assemblies exhibiting automatic motions have received much attention as potential artificial models of living organisms. We have developed a microfluidic picolitre nozzle-array device to form multilamellar lipid tubes (MLTs) under fluidic shear stress, which transformed into different two patterns (yarn-balls and double-helixes) and also exhibited unique self-actuation behaviors.     

Millimeter-sized flat crystalline sheet architectures of fullerene assemblies with anisotropic photoconductivity

The coassembly of C(60) derivatives through arene-perfluoroarene interactions has been used for the first time to develop millimeter-sized flat crystalline sheets. Time-resolved microwave conductivity (TRMC) measurements exhibited anisotropic features with over double the charge carrier mobility in the direction parallel to the plane of the crystal than perpendicular to the plane. This study demonstrates a strategy to obtain large-sized 2-dimensional architectures of C(60) with anisotropic optoelectronic functions.     

Control-free air vent system for ultra-low volume sample injection on a microfabricated device.

An improved method of sample injection was demonstrated for introducing ultra-low volume liquid on a microfabricated device. In our previous study, a pressure-driven injection method has been introduced and was applied to on-chip electrophoresis. In this study, the need for control of the air vent, which was indispensable for sample injection in the previous study, was completely eliminated, facilitating sample injection with great simplicity and high accuracy. This was realized by altering the topology of the air vent channel, which is connected to a hydrophobic and narrow channel (called a passive valve). Several types of air vent channels were designed and their injection performances were tested. In addition, by modifying the shape and the position of air vent channel and passive valve, the residual liquid volume inside the passive valve after sample injection was decreased to approximately 0.5% of the injected volume, a value which showed high reproducibility.     

Core-exciton induced resonant photoemission in the covalent semiconductor black phosphorus

Valence band photoemission spectra of black phosphorus have shown anomalous behavior at the excitation of 2p core-excitons. The intensity of the 2.7 ev peak shows a clear Fano type interference due to a direct recombination of core-excitons leaving one hole in valence bands. Besides, strong enhancement of the 10.8 eV peak is interpreted as due to a core-exciton induced resonance with two-hole final states. The role of core-excitons as intermediate states for photoemission processes is newly revealed in the experiments.     

Ultraviolet photoemission and 4d core reflectance spectra of SmSe(100)

Ultraviolet photoemission (UPS) and inner core reflectance spectra have been measured on SmSe(100) surface with synchrotron radiation. Besides the multiplet structures observed in UPS spectra for the Sm 4f, 5p and 5s excitations, the reflectance spectrum has revealed a multiplet structure associated with the Sm 4d→4f excitation. Each band of the UPS spectra has shown remarkably different hν dependence and the resonant behavior of the cross section. Sm 4f- and Se 4p-derived valence band features are unambiguously identified by the angle resolved UPS.