Multiple ionization bursts in laser-driven hydrogen molecular ion

Theoretical study on H2(+) in an intense infrared laser field on the attosecond time scale reveals that the molecular ion shows multiple bursts of ionization within a half-cycle of the laser field oscillation, in contrast to the widely accepted tunnel ionization picture for an atom. These bursts are found to be induced by transient localization of the electron at one of the nuclei, and a relation between the time instants of the localization and the vector potential of the laser light is derived. A scheme is proposed to probe the localization dynamics by an extreme ultraviolet laser pulse.     

Electron tomography of Nafion ionomer coated on Pt/carbon black in high utilization electrode for PEFCs

To confirm the superiority of newly developed electrocatalyst layer (ECL) for polymer electrolyte fuel cells, three-dimensional dispersion states of Nafion ionomer in Pt/carbon black agglomerates were analyzed by electron tomography based on multiple TEM images taken at different tilt angles. Uniform distribution of the ionomer has been first observed, proving the high catalyst utilization in the new ECL distinctive from that of the conventional one.     

On-Line Coupling of a Micro Liquid Chromatograph to a Fourier Transform Infrared Spectrophotometer

A micro liquid chromatograph-interfaced Fourier transform infrared spectrophotometer system (LC/FTIR) for on line analysis of liquid chromatography effluents is described. About 2 μg of injected diethylphthalate can be detected using a 0.025 mm pathlength flow cell. Several examples of a micro LC/FTIR are demonstrated.     

Optimization of background electrolyte composition for simultaneous contactless conductivity and fluorescence detection in capillary electrophoresis of biological samples

In this article, optimization of BGE for simultaneous separation of inorganic ions, organic acids, and glutathione using dual C⁴D‐LIF detection in capillary electrophoresis is presented. The optimized BGE consisted of 30 mM 2‐[4‐(2‐hydroxyethyl)piperazin‐1‐yl]ethanesulfonic acid, 15 mM 2‐amino‐2‐hydroxymethyl‐propane‐1,3‐diol, and 2 mM 18‐crown‐6 at pH 7.2 and allowed simultaneous separation of ten inorganic anions and cations, three organic acids and glutathione in 20 min. The samples were injected hydrodynamically from both capillary ends using the double‐opposite end injection principle. Sensitive detection of anions, cations, and organic acids with micromolar LODs using C⁴D and simultaneously glutathione with nanomolar LODs using LIF was achieved in a single run. The developed BGE may be useful in analyses of biological samples containing analytes with differing concentrations of several orders of magnitude that is not possible with single detection mode.     

Microscopic Elucidation of Solid‐Electrolyte Interphase (SEI) Film Formation via Atomistic Reaction Simulations: Importance of Functional Groups of Electrolyte and Intact Additive Molecules

Secondary batteries such as Li‐ion battery are expected to be utilized as not only ubiquitous electric power sources such as mobile phones but also large‐scale electricity storage devices. Therefore, it is urgent to develop the higher performance secondary batteries. Their lifetime and stability are found to be strongly dependent on the nature of passivation film called solid electrolyte interphase (SEI) film formed on the anode surface in the initial charge‐discharge cycle. However, since it is difficult to directly observe the film formation processes in experiment, its microscopic mechanism is still not found. On the other hand, although the theoretical methods are useful complement to the experiment, some new methodologies are necessary to understand the long‐term processes of SEI film, which is produced as a result of that a lot of chemical reactions proceed simultaneously. Under the circumstances, we have developed Red Moon method that can simulate such complex chemical reaction systems, and were able to analyze for the first time the SEI film formation processes on the anode surface at the atomistic level. Then, we clarified theoretically the microscopic mechanism of the additive effect which is essential to improve the Na‐ion battery performance so as to enhance the SEI film formation. This new microscopic insight must provide an important guiding principle for use in designing the most suitable electrolytes for developing high‐performance secondary batteries.     

De-excitation process and hot luminescence in the FA(type I) center in KCl:Na

The de-excitation process of F_A(type I) centers in KCl:Na has been investigated by measuring the hot luminescence spectrum from optically excited F_A centers with time-resolved spectroscopy. The experimental results are analyzed by using a model that describes a time evolution of the phonon wave packet during the vibronic relaxation process from the Franck-Condon state to a relaxed excited state. From the analysis of the experimental data, information on the vibronic mixing between 2p and 2s states, whose magnitude varies during the relaxation process, and the adiabatic potential energy curves of 2s and 2p states are extracted. The present results are compared with the already known ones of the F_A(type II) centers.     

Zirconia-based planar NO2 sensor using ultrathin NiO or laminated NiO–Au sensing electrode

The nanostructured thin NiO films with the thicknesses of 30–180 nm were examined as a sensing electrode (SE) for the planar mixed-potential-type yttria-stabilized zirconia (YSZ)-based NO₂ sensor. The sensing characteristics were examined in the temperature range of 600–800 °C under the wet condition (5 vol.% water vapor). Among the NiO-SEs tested, the 60 nm-thick NiO-SE sintered at 1,000 °C was found to give the highest NO₂ sensitivity in the NO₂ concentration range of 50–400 ppm accompanying with fast response/recovery at the operating temperatures of 600–700 °C. The high NO₂ sensitivity was attributed to the high catalytic activity for both electrochemical reactions of O₂ and NO₂ at the interface of NiO-SE/YSZ. The ultrathin gold layer with the thickness of about 60 nm was additionally formed on the 60 nm-thick NiO-SE to fabricate the laminated-type (60 nm NiO/60 nm Au)-SE. It was demonstrated that the use of this laminated (NiO–Au)-SE improved both the sensitivity and the selectivity to NO₂.     

Photochemical reaction of silyl-substituted 1,4-disila(dewar-benzene) with isocyanide and phenylacetylene

The irradiation of silyl-substituted 1,4-disila(Dewar-benzene) 1 with light of wavelength λ > 320 nm in the presence of 2,6-dimethylphenyl-isocyanide or phenylacetylene produced 1,4-bis(di-tert-butylmethylsilyl)-2,3,5,6-tetraethyl-7-(2,6-dime-thylphenylimino)-1,4-disilabicyclo[2.2.1]hepta-2,5-diene 5 or 1,4-bis(di-tert-butylmethylsilyl)-2,3,5,6-tetraethyl-1-(2-phenylethynyl)-1,4-disilacyclohexa-2,5-diene 6 , respectively. The molecular structures of 5 and 6 were determined by spectroscopic data and X-ray crystallography. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:87–92, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20411     

Highly Enantioselective Reactions of Configurationally Labile Epimeric Diamine Complexes of Lithiated S‐Benzyl Thiocarbamates

Substitution reactions that employ primary‐carbamoyl‐protected arylmethanethiols are described. The enantiodetermining step was found to occur in the post‐deprotonation step as a dynamic thermodynamic resolution with a chiral bis(oxazoline) ligand. The configurationally labile lithium complexes were trapped with various electrophiles to yield different substitution products in good to excellent yields and enantiomeric excesses. The absolute configurations of the substitution products were determined, and the stereochemical pathway of the substitution reaction was elucidated for different classes of electrophiles. The temperature‐dependent epimerization process was monitored by ¹H and ⁶Li NMR spectroscopy.