An in-syringe La-coprecipitation Method for the Preconcentration of Oxo-anion Forming Elements in Seawater Prior to an ICP-MS Measurement

A lanthanum (La) coprecipitation method with low sample consumption was explored for the preconcentration of oxo-anion forming elements prior to a measurement by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration procedure was composed of two main steps: (1) the formation of a coprecipitate with the lowest possible La and (2) the redissolution of target analytes with minimal use of nitric acid, and the elimination of high concentration La from the analysis sample. Each step was performed in a 25 mL-volume syringe to reduce the sample consumption and to avoid contamination from the experimental environment. Various parameters, such as the concentration and volume of La added into the sample solution, the precipitation pH, the aging time, and the volume of HNO(3) were optimized to obtain good recoveries and high detection sensitivities for V, As, Sb, and W, which could be hardly recovered by solid-phase extraction using a chelating resin. The obtained method was evaluated through the analysis of seawater reference materials (CASS-4 and NASS-5). The recoveries exceeded 80%, and the observed values were in good agreement with the certified values.     

Orbital restriction on the functional form of the Lagrangian

The fact that a non-relativistic particle describes an orbit imposes a restriction on the functional form of the Lagrangian. For a classical particle subjected to an arbitrary local ‘generalized force,’ the (local) Lagrangian is shown to involve, at highest, first, second and third time-derivatives of the position respectively, in one, two and three dimensions. The generalization in the quantum régime is indicated with the aid of Feynman's path integrals.     

Theory of the Half-integer Quantum Hall Effect in Graphene

The unusual quantum Hall effect (QHE) in graphene is described in terms of the composite (c-) bosons, which move with a linear dispersion relation. The “electron” (wave packet) moves easier in the direction [1 1 0 c-axis] ≡ [1 1 0] of the honeycomb lattice than perpendicular to it, while the “hole” moves easier in [0 0 1]. Since “electrons” and “holes” move in different channels, the particle densities can be high especially when the Fermi surface has “necks”. The strong QHE arises from the phonon exchange attraction in the neighborhood of the “neck” surfaces. The plateau observed for the Hall conductivity and the accompanied resistivity drop is due to the superconducting energy gap caused by the Bose-Einstein condensation of the c-bosons, each forming from a pair of one-electron–two-fluxons c-fermions by phonon-exchange attraction. The half-integer quantization rule for the Hall conductivity: (1/2)(2P?1)(4e²/h), P=1,2,..., is derived.     

A sensitive and selective method for the quantitative analysis of miglitol in rat plasma using unique solid‐phase extraction coupled with liquid chromatography–tandem mass spectrometry

A sensitive, selective and robust liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method was developed for the quantification of miglitol in rat plasma. The sample preparation procedures involved protein precipitation and unique solid‐phase extraction, which efficiently removed sources of ion suppression and column degradation interference present in the plasma. Chromatographic separation was achieved on an amide column using 10 mmol/L CH₃COONH₄ and CH₃CN:CH₃OH (90:10, v/v) as the mobile phase under gradient conditions. Detection was performed using tandem mass spectrometry equipped with an electrospray ionization interface in positive ion mode.The selected reaction monitoring transitions for miglitol and a stable isotope‐labeled internal standard were m/z 208 → m/z 146 and m/z 212 → m/z 176, respectively. The correlation coefficients of the calibration curves ranged from 0.9984 to 0.9993 over a concentration range of 0.5–100 ng/mL plasma. The quantification limit of the proposed method was more than 10 times lower than those of previously reported LC‐MS/MS methods. The novel method was successfully validated and applied to a pharmacokinetic study in rats. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurement of particle distribution in microchannel flow using a 3D-TIRFM technique

The presence of bio-substances in the near-wall region in micro bio-chemical analysis chips is an important topic but one which is difficult to investigate directly. In this paper we developed an accurate 3D-TIRFM technique, which was used to investigate the three-dimensional positions of nano-particles. The depth was calibrated using a piezo stage. As an example of an application of this technique, the concentration profile of nano-particles near a wall surface was investigated. The results showed that the concentration profile was non-uniform and lower than that in the bulk. In addition the ionic strength of the solvent strongly influenced the concentration profile. It was concluded that the non-uniform concentration profile is due to the influence of the electric double layer around the particles and the surface. This demonstrates the importance of selecting suitable electric characteristics, since a non-uniform and low concentration profile near the wall will affect the reaction efficiency and the sensitivity in micro bio-chemical analysis.     

Modeling of fiber-reinforced cement composites: Discrete representation of fiber pullout

The discrete modeling of individual fibers in cement-based materials provides several advantages, including the ability to simulate the effects of fiber dispersion on pre- and post-cracking composite performance. Recent efforts in this direction have sought a balance between accurate representation of fiber behavior and computational expense. This paper describes a computationally efficient approach to representing individual fibers, and their composite behavior, within lattice models of cement-based materials. Distinguishing features of this semi-discrete approach include: (1) fibers can be positioned freely in the computational domain, irrespective of the background lattice representing the matrix phase; (2) the pre- and post-cracking actions of the fibers are simulated with little computational expense, since the number of system degrees of freedom is independent of fiber count. Simulated pullouts of single fibers are compared with theory and test results for the cases of perfectly-plastic and slip-hardening behavior of the fiber–matrix interface. To achieve objective results with respect to discretization of the matrix, pullout forces are distributed along the embedded lengths of fibers that bridge a developing crack. This is in contrast to models that lump the pullout force at the crack surfaces, which can lead to spurious break-off of matrix particles as the discretization of the matrix is refined. With respect to fracture in multi-fiber composites, the proposed model matches theoretical predictions of post-cracking strength and pullout displacement corresponding to the load-free condition. The work presented herein is a significant step toward the modeling of strain-hardening composites that exhibit multiple cracking.     

Spatial structure,regression to steady states based on a coupled random walk process

Based on a simple model of coupled random walks, coupled Fokker-Planck equations are derived. It is shown that their steady state solutions exhibit spatial structures. The condition for regressive solutions, the stability condition are expressed in terms of jumping probabilities.On leave of absence from Tohoku University, Department of Applied Science, Faculty of Engineering, Sendai 980 Japan     

Differentiation between isomeric oxidative metabolites of a piperidine-containing drug by liquid chromatography-tandem mass spectrometry with stable-isotope tracer technique

This report describes the application of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to differentiation of hydroxylations and N-oxidations and of two different aliphatic hydroxylations in the investigation of the metabolism of pibutidine hydrochloride, a novel H2 antagonist, the structure of which includes a piperidine ring. Pibutidine metabolites in urine samples from adult male volunteers after oral administration of pibutidine hydrochloride were separated by reversed-phase LC and ionized using an electrospray ionization (ESI) interface. A hydroxylated form of pibutidine was distinguished from the N-oxide by comparison of their product ion spectra, although their mass-to-charge ratios of protonated molecules were identical. Further, two hydroxylated compounds were present in rat microsomal incubation mixtures with pibutidine. The distinction between their positions of hydroxylation (beta- and gamma-carbon hydroxylation) on the piperidine ring was studied using [piperidine-2H10] pibutidine as incubation substrate. The production of the beta-hydroxylated form was accompanied by the elimination of three 2H, resulting from a mechanism including the formation of iminium/enamine. The participation of the iminium ion intermediate in the beta-hydroxylation was confirmed by the observation that a cyanide adduct of pibutidine was formed instead of the beta-hydroxylated form when another incubation was performed in the presence of cyanide.     

3 + 2] Cycloreversion of bicyclo[m.3.0]alkan-3-on-2-yl-1-oxonium ylides to alkenyloxyketenes. Stereospecific aspect

Rhodium(II)-catalyzed intramolecular reaction of diazoketones 1 bearing a cyclic ethereal moiety transiently formed bicyclo[m.3.0]octan-3-one-1-oxonium-2-ylides (2), which underwent sigmatropic and stereospecific [3 + 2] cycloreversion reaction to form alkenyloxyketenes 3. The ketenes were efficiently trapped by methanol to form the corresponding esters 4. Mechanistic studies revealed that the size of ethereal ring can be variable at least from THF to the THP, oxepane, and oxocane moiety, i.e., m = 3-6. On the other hand, the size of the ylide ring containing the carbonyl unit is limited to a five-membered ring. The cycloreversion was found to be stereospecific as was proven by the reactions of diastereoisomeric pairs bearing a methyl group at the bond-cleaving position. From threo isomers 7, (E)-alkenyloxyacetates 15 were exclusively formed (77-84%), whereas from erythro isomers 8, (Z)-isomers 16 were formed (80-88%). Mechanism of the cleavage from diazoacetonyl-substituted cyclic ethers to alkenyloxyketenes via bicyclic oxonium ylides was analyzed on the basis of calculations employing the hybrid density functional B3LYP and the highly correlated quadratic configuration interaction QCISD method to reveal that the concerted [3 + 2] cycloreversion is the key step of this reaction.     

On the metal–insulator transition in vanadium dioxide

The conductivity σ of vanadium dioxide (VO₂) drops at a metal–insulator transition by four orders of magnitude due to the structural change between tetragonal and monoclinic crystals. In order to elucidate this conductivity drop, we introduce the semiclassical equation of motion to describe the dynamics of the conduction electron (wave packet), where the existence of a k-vector k is prerequisite for the conduction. We showed that the periodicity using the non-orthogonal bases does not legitimize the electron dynamics in solids. The theory suggests that the decrease in the dimensionality of the k-vectors due to the structural change is the cause of the conductivity drop.