Preparation and lithium doping of gallium oxynitride by ammonia nitridation via a citrate precursor route

Gallium oxynitride, isostructural to hexagonal gallium nitride (h-GaN), was obtained by ammonia nitridation of a precursor prepared from the addition of citric acid to an aqueous solution of gallium nitrate. Gallium oxynitride produced at 750 °C had a small amount of gallium vacancies, and was formulated as (Ga_0.89□_0.11) (N_0.66O_0.34) where the symbol □ stands for gallium vacancy. Both the gallium vacancies and oxygen substituted for nitrogen were randomly distributed within the structure. The amount of vacancies decreased with nitridation temperatures in the range of 750-850 °C. Approximately, 10 at% Li⁺ was doped into the gallium oxynitride, using a similar preparation with the additional presence of lithium nitrate, resulted in the random substitution of Ga³⁺ in an atomic ratio of Li/Ga<1 at 750 °C. Oxygen was codoped with lithium and substituted nitrogen in the wurtzite-type crystal lattice. These substitutions reduced the electrical conductivity in the gallium oxynitride semiconductor. A new oxynitride, Li₂Ga₃NO₄, was also obtained with Li₂CN₂ impurity using similar preparations from a mixture of Li/Ga?1. The crystal structure was isostructural with h-GaN, and was refined as P6₃mc with a=0.31674(1) nm, and c=0.50854(2) nm. The Ga and Li occupancies at the 2b site were refined to be 0.6085 and 0.3915, respectively, assuming that the other 2b site was randomly occupied with 1/5O and 4/5N. When the new compound was washed for over 1 min for the removal of Li₂CN₂ impurities, it was decomposed to a mixture of α-GaOOH and α-LiGaO₂. The as-prepared product with Li/Ga=1 showed the highest intensity in yellow luminescence among the products under excitation at 254 nm.     

Determination of sulfates of androsterone and epiandrosterone in human serum using isotope diluted liquid chromatography-electrospray ionization-mass spectrometry

A promising liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for analysis of the sulfates of 5alpha-androgen, androsterone and epiandrosterone (A-S and EpiA-S) in human serum was developed. The method was used to assess one of the markers of 5alpha-reductase activity of males including patients with prostate cancer (PC). After deproteinization with acetonitrile, the androgen sulfates and the internal standard, [7,7,16,16-2H4]dehydroepiandrosterone-S, were extracted from human serum using a solid-phase extraction cartridge and washed with hexane. The extract was reconstituted and applied to the LC/ESI-MS system operated in the selected ion monitoring mode. The method was validated over the range 0.02-5 microg/mL (A-S) and 0.005-1.5 microg/mL (EpiA-S) using 10 microL of human serum. The method was a concise procedure without chemical or enzymatic hydrolysis of the conjugates, purification by high-performance liquid chromatography and/or derivatization, and proved to be satisfactory in its reproducibility and accuracy. The levels of these androgen sulfates tended to decrease during aging, and the A-S levels in the sera obtained from both healthy males and patients with PC were correlated with their EpiA-S levels.     

Performance of throughout in-capillary derivatization capillary electrophoresis employing an on-line sample and run buffer loading device

We report on the effect on performance of varying the length of the capillary during throughout in-capillary derivatization (TICD) capillary electrophoresis (CE). Performance was evaluated by on-line coupling with a sample and CE runbuffer loading device that was newly introduced for this study. The device was assembled with a low cost using two 5 mm inner diameter (ID) disposable polyethylene syringes. First, a sequence was manually formed consisting of a 200 microL run buffer solution plug, a 100 microL sample plug and another 200 microL run buffer solution plug. Each plug was separated from its neighbor by a 100 microL air plug. When each plug reached the injection point where both a platinum-wire anode and the end of the separation capillary tube were located, 340 V/cm separation voltage (electrophoresis voltage) and 34 V/cm injection voltage were applied to the capillary for 3 s. Then the analytes were derivatized during migration in 50 microm ID capillaries filled with 2 mM o-phthalaldehyde (OPA)/N-acetylcysteine (NAC) in a 20 mM phosphate-borate buffer (pH 10), followed by separating and detecting of OPA derivatives by absorbance of 340 nm. Derivatization, separation, and detection were performed systematically using capillaries which varied in length from 5 to 80 cm. In the case of TICD-CE of a mixture containing 1 mM aspartic acid (Asp) and 20 mM m-nitorophenol (MNP) as a test solution, it was determined that peak area and peak width ratios of Asp to MNP did not depend on capillary length. Enantiomeric separations of DL-alanine (Ala) and Asp were examined using a run buffer consisting of a 45 microM beta-cyclodextrin (CD)-2 mM OPA/NAC-20 mM phosphate-borate buffer (pH 10). Even though the resolution of these enantiomeric pairs decreased with decreasing capillary length, as expected, the peaks corresponding to both enantiomeric amino acids were identified even when a 5 cm capillary was used. An 8-component amino acid mixture was also tested with 5 cm and 10 cm capillaries.     

Statistical properties of aggregation with injection

We study a generalized aggregation process in which charged particles diffuse and coalesce randomly on a lattice. For one-dimensional and mean-field models, we show that there exists a statistically-invariant steady state when randomly charged particles are continuously injected. The steady-state charge distribution obeys a power law with the exponent depending both on the type of the injection and on the spatial dimension. The response of the system to a perturbation (i.e., relaxation) is characterized by either a power law decay (t ^– ,1) or a compressed exponential decay [exp(–t ),>1].     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Assembly of Na3V2(PO4)3 Nanoparticles Confined in a One‐Dimensional Carbon Sheath for Enhanced Sodium‐Ion Cathode Properties

Structural and morphological control is an effective approach for improvement of electrochemical properties in rechargeable batteries. One‐dimensionally assembled structure composed of NASICON‐type Na₃V₂(PO₄)₃ nanoparticles were fabricated through an electrospinning method to meet the requirements for the development of efficient electrode materials in Na‐ion batteries. High‐temperature treatment of electrospun precursor fibers under an argon flow provides a nonwoven fabric of nanowires comprising crystallographically oriented nanoparticles of NASICON‐type Na₃V₂(PO₄)₃ within a carbon sheath. The mesostructure comprising NASICON‐type Na₃V₂(PO₄)₃ and carbon give a short sodium‐ion transport pass and an efficient electron conduction pass. Electrochemical properties of NASICON‐type Na₃V₂(PO₄)₃ are improved on the basis of one‐dimensional nanostructures designed in the present study.     

A new approach of direct sample-digestion before vaporization for determination of a metal in rocks by inductively coupled plasma atomic emission spectrometry.

A new approach to sample digestion, subsequent vaporization and introduction to an inductively coupled plasma (ICP) atomic emission spectrometer was developed for the direct determination of magnesium. To each small sample cuvette made of tungsten, a ground rock sample was precisely weighed. The cuvette was situated on a tungsten boat furnace. Ammonium fluoride solution was added to the cuvette as a chemical modifier. After the on-furnace digestion has been completed, the analyte, magnesium, in the cuvette was vaporized and introduced into the ICP atomic emission spectrometer. Since the powdered samples were wet-digested in the sample cuvettes prior to vaporization, they could be analyzed by using a calibration curve prepared from aqueous standard solutions. This method was applied to the determination of magnesium in several standard reference materials with satisfactory results.     

Photoelectric pulse interval distribution of gaussian-lorentzian light

The time interval distribution of two successive photoelectric pulses depends not only upon the spectral linewidth but also on the correlation factor. The distribution is derived in the case of gaussian-lorentzian light under the condition of a markovian process and is also applied to the analysis of the counting loss of a circuit with dead time, from which information on the spectral linewidth is obtained. The theoretical counting loss is compared with the experimental one.     

Thermodynamic properties in the approach to the quantum critical point of the spin-ladder material Na2Co2(C2O4)3(H2O)2

Magnetic susceptibility and heat capacity measurements as a function of temperature on a single-crystal sample of a spin-ladder material, Na2Co2(C2O4)3(H2O)2, are reported. Principal susceptibilities, parallel and perpendicular to the ladder direction, respectively, show broad maxima around 22 and 17 K. Both susceptibilities decay exponentially down to about 5 K and thereafter they are essentially independent of temperature. These findings amount to a signature of a quantum phase transition from a spin-liquid to Néel ordered state previously predicted theoretically. No anomaly is found in the heat capacity around the transition temperature.