Fundamental properties of a touchable high‐power pulsed microplasma jet and its application as a desorption/ionization source for ambient mass spectrometry

Plasma‐based ambient desorption/ionization mass spectrometry (ADI–MS) has attracted considerable attention in many fields because of its capacity for direct sample analyses. In this study, a high‐power pulsed microplasma jet (HPPMJ) was developed and investigated as a new plasma desorption/ionization source. In an HPPMJ, a microhollow cathode discharge is generated in a small hole (500 µm in diameter) using a pulsed high‐power supply. This system can realize a maximum power density of 5 × 10⁸ W/cm³. The measured electron number density, excitation temperature and afterglow gas temperature of the HPPMJ were 3.7 × 10¹⁵ cm^‐3, 7000 K at maximum and less than 60 °C, respectively, which demonstrate that the HPPMJ is a high‐energy, high‐density plasma source that is comparable with an argon inductively coupled plasma while maintaining a low gas temperature. The HPPMJ causes no observable damage to the target because of its low gas temperature and electrode configuration; thus, we can apply it directly to human skin. To demonstrate the analytical capacity of ADI–MS using an HPPMJ, the plasma was applied to direct solid sample analysis of the active ingredients in pharmaceutical tablets. Caffeine, acetaminophen, ethenzamide, isopropylantipyrine and ibuprofen were successfully detected. Application to living tissue was also demonstrated, and isopropylantipyrine on a finger was successfully analyzed without damaging the skin. The limits of detection (LODs) for caffeine, isopropylantipyrine and ethenzamide were calculated, and LODs at the picogram level were achieved. These results indicate the applicability of the HPPMJ for high‐sensitivity analysis of materials on a heat‐sensitive surface. Copyright © 2014 John Wiley & Sons, Ltd.     

Origin of semiconductng behavior in rare-earth-doped barium titanate

New explanations of the origin of semiconduction and a peculiar characteristics of resistivity vs dopant concentration in rare-earth-doped barium titanate are presented on a basis of the combined data of cation vacancy concentration, resistivity, and oxygen diffusion coefficient of the material. A limited amount of rare-earth doping into barium titanate results in the introduction of Ba-site vacancies as well as Ti-site vacancies in the lattice. The existence of Ba-site vacancies profoundly alters the chemical bonding nature of the host lattice and thereby causes some loss of oxygen as well as the formation of oxygen vacancies with captured electrons in the lattice on firing the material at elevated temperatures, the latter giving rise to n-type semiconduction. A sudden fall in conductivity for a higher rare-earth concentration occurs in accordance with the number of Ba-site vacancies being zero.     

Effective luminescence quenching of tris(2,2-bipyridine)ruthenium(II) by methylviologen on clay by the aid of poly(vinylpyrrolidone)

Electron-transfer quenching of tris(2,2-bipyridine)ruthenium(II) by methylviologen in an aqueous suspension of clay in the presence of poly(vinylpyrrolidone) was investigated. The quenching behavior of the excited tris(2,2-bipyridine)ruthenium(II) on clay by the coadsorbed methylviologen indicated the homogeneous distribution of the adsorbed dyes. The quenching rate was high when the clay with larger particle size was used as the host. The adsorption of poly(vinylpyrrolidone) on clay resulted in the coadsorption of the tris(2,2-bipyridine)ruthenium(II) and methylviologen without segregation.     

A compositional fluctuation and properties of Pb(Zr,Ti)O3

Structure and properties of piezoelectric materials of composition Pb(Zr_xTi_1?x)O₃ near the morphotropic phase boundary between tetragonal and rhombohedral phases are studied. When these materials were prepared by a new “wet-dry combination technique”, no coexistence of these two phases was found in any range of compositions. This fact is in contrast with the case of Pb(Zr_xTi_1?x)O₃ prepared by an ordinary dry method. The coexistence behavior is interpreted in terms of compositional fluctuation, on the basis of which various properties of the materials are explained.     

Magnetic properties of lanthanum orthoferrites containing lattice defects

Polycrystalline lanthanum orthoferrites were prepared by firing coprecipitated hydroxides of La³⁺ and Fe³⁺ at elevated temperatures. The materials fired at temperatures below 1100°C were characterized by the coexistence of such lattice vacancies that the concentration ratio of V_La:V_Fe:V_o is always equal to that of the constituent atoms of LaFeO₃. They exhibited a large magnetic susceptibility, a low Néel temperature, and a small spontaneous magnetization, in comparison with lanthanum orthoferrite without these vacancies. These characteristics originated essentially from a local reduction in anisotropic superexchange interaction at vacant sites. The lowering of Néel temperature characteristic of these materials was interpreted in terms of a decrease in the number of Fe³⁺OFe³⁺ linkages due to the existence of oxygen and iron vacancies.     

Development of a High-Efficiency Decomposition Technology for Volatile Chemical Warfare Agent Sarin Using Dielectric Barrier Discharge

Plasma Chemistry and Plasma Processing - High-efficiency decomposition technology for volatile chemical warfare agent sarin was developed using a dielectric-barrier discharge (DBD). The power...     

A linear 5-coloring algorithm of planar graphs

A simple linear algorithm is presented for coloring planar graphs with at most five colors. The algorithm employs a recursive reduction of a graph involving the deletion of a vertex of degree 6 or less possibly together with the identification of its several neighbors.     

A theorem on paths in planar graphs

C. Thomassen extended Tutte's theorem on cycles in planar graphs in the paper “A Theorem on Paths in Planar Graphs”. This note corrects a flaw in his proof.     

Evaporite Borate‐Containing Mineral Ensembles Make Phosphate Available and Regiospecifically Phosphorylate Ribonucleosides: Borate as a Multifaceted Problem Solver in Prebiotic Chemistry

RNA is currently thought to have been the first biopolymer to support Darwinian natural selection on Earth. However, the phosphate esters in RNA and its precursors, and the many sites at which phosphorylation might occur in ribonucleosides under conditions that make it possible, challenge prebiotic chemists. Moreover, free inorganic phosphate may have been scarce on early Earth owing to its sequestration by calcium in the unreactive mineral hydroxyapatite. Herein, it is shown that these problems can be mitigated by a particular geological environment that contains borate, magnesium, sulfate, calcium, and phosphate in evaporite deposits. Actual geological environments, reproduced here, show that Mg²⁺ and borate sequester phosphate from calcium to form the mineral lüneburgite. Ribonucleosides stabilized by borate mobilize borate and phosphate from lüneburgite, and are then regiospecifically phosphorylated by the mineral. Thus, in addition to guiding carbohydrate pre‐metabolism, borate minerals in evaporite geoorganic contexts offer a solution to the phosphate problem in the “RNA first” model for the origins of life.