Kenji Yasunaga

A Multiple Shock Tube and Chemical Kinetic Modeling Study of Diethyl Ether Pyrolysis and Oxidation

The pyrolysis and oxidation of diethyl ether (DEE) has been studied at pressures from 1 to 4 atm and temperatures of 900-1900 K behind reflected shock waves. A variety of spectroscopic diagnostics have been used, including time-resolved infrared absorption at 3.39 mum and time-resolved ultraviolet emission at 431 nm and absorption at 306.7 nm. In addition, a single-pulse shock tube was used to measure reactant, intermediate, and product species profiles by GC samplings at different reaction times varying from 1.2 to 1.8 ms. A detailed chemical kinetic model comprising 751 reactions involving 148 species was assembled and tested against the experiments with generally good agreement. In the early stages of reaction the unimolecular decomposition and hydrogen atom abstraction of DEE and the decomposition of the ethoxy radical have the largest influence. In separate experiments at 1.9 atm and 1340 K, it is shown that DEE inhibits the reactivity of an equimolar mixture of hydrogen and oxygen (1% of each).

Fabrication and Characterization of a K+-Selective Nanoelectrode and Simultaneous Imaging of Topography and Local K+ Flux Using Scanning Electrochemical Microscopy

A nanopipette containing a solution of bis(benzo-15-crown-5) dissolved in 1,6-dichlorohexane was used as an ion-selective electrode (ISE) to probe K(+) for shear force-based constant-distance scanning electrochemical microscopy (SECM). In a previous study, the ISE responded only at low K(+) concentrations ([K(+)] < 1 mM), due to the depletion of the bis(benzo-15-crown-5) at the oil/water interface at high K(+) concentrations and the unstable response of the tip at the oil/water interface for shear force and current detection. In the present study, a nanopipette reshaped by heating and with the hydrophobic layer removed was used as the ISE. This modified ISE enabled a rapid response to changes in K(+) flux at a physiological concentration of K(+) and allowed SECM imaging on a nanometer scale. The fabricated nano-ISE was used as a probe for shear force-based SECM. Topography and K(+) flux images were obtained simultaneously at a polycarbonate membrane filter with 5 μm pores and human embryonic kidney 293 cells (HEK293). Several areas containing a K(+) flux larger than the surrounding areas were found in the SECM images of the HEK293 cells, which indicated the existence of K(+) channels.