Testing hypotheses by using optimal statistical criteria. I

We propose a method for constructing statistical criteria. It can be used for testing an arbitrary finite set of simple alternative hypotheses. A concept of an optimal statistical criterion is introduced, special cases of which are the Bayesian criterion and the minimax criterion. It is proved that any optimal statistical criterion can be constructed on the basis of the likelihood ratio.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 46, No. 4, pp. 378–388, April, 1994.     

Study of the mobility,surface area,and sintering behavior of agglomerates in the transition regime by tandem differential mobility analysis

The surface area of nanosized agglomerates is of great importance as the reactivity and health effects of such particles are highly dependent on surface area. Changes in surface area through sintering during nanoparticle synthesis processes are also of interest for precision control of synthesised particles. Unfortunately, information on particle surface area and surface area dynamics is not readily obtainable through traditional particle mobility sizing techniques. In this study, we have experimentally determined the mobility diameter of transition regime agglomerates with 3, 4, and 5 primary particles. Agglomerates were produced by spray drying well-characterised polystyrene latex particles with diameters of 55, 67, 76, and 99 nm. Tandem differential mobility analysis was used to determine agglomerate mobility diameter by selecting monodisperse agglomerates with the same number of primary particles in the first DMA, and subsequently completely sintering the agglomerates in a furnace aerosol reactor. The size distribution of the completely sintered particles was measured by an SMPS system, which allowed for the determination of the number of primary particles in the agglomerates. A simple power law regression was used to express mobility diameter as a function of primary particle size and the number of primary particles, and had an excellent correlation (R² = 0.9971) with the experimental data. A scaling exponent was determined from the experimental data to relate measured mobility diameter to surface area for agglomerates. Using this relationship, the sintering characteristics of agglomerates were also examined for varying furnace temperatures and residence times. The sintering data agreed well with the geometric sintering model (GSM) model proposed by Cho & Biswas (2006a) as well as with the model proposed Koch & Friedlander (1990) for sintering by viscous flow.     

Modified gap states in Fe/MgO/SrTiO3 interfaces studied with scanning tunneling microscopy

The geometric and electronic structures of Fe islands on MgO film layers were studied with scanning tunneling microscopy and spectroscopy. The MgO layers were grown on a Nb-doped single crystal SrTiO₃ (100) surface. Deposited Fe atoms aggregate into islands, the height and diameter of which are about 2.5 and 9.4 nm respectively. Fe islands modify the electronic structure of MgO surface; a ring type depression in the scanning tunneling microscope topography appears by lowered local electron density of states around Fe islands. We find that adsorbed Fe atoms reduce the gap states of MgO layers around Fe islands, which is attributed to the reason for the depletion of the electronic density of states.     

Monte Carlo approximation through Gibbs output in generalized linear mixed models

Geyer (J. Roy. Statist. Soc. 56 (1994) 291) proposed Monte Carlo method to approximate the whole likelihood function. His method is limited to choosing a proper reference point. We attempt to improve the method by assigning some prior information to the parameters and using the Gibbs output to evaluate the marginal likelihood and its derivatives through a Monte Carlo approximation. Vague priors are assigned to the parameters as well as the random effects within the Bayesian framework to represent a non-informative setting. Then the maximum likelihood estimates are obtained through the Newton Raphson method. Thus, out method serves as a bridge between Bayesian and classical approaches. The method is illustrated by analyzing the famous salamander mating data by generalized linear mixed models.     

Oligoether-strapped calix[4]pyrrole: an ion-pair receptor displaying cation-dependent chloride anion transport

A ditopic ion-pair receptor (1), which has tunable cation- and anion-binding sites, has been synthesized and characterized. Spectroscopic analyses provide support for the conclusion that receptor 1 binds fluoride and chloride anions strongly and forms stable 1:1 complexes ([1·F](-) and [1·Cl](-)) with appropriately chosen salts of these anions in acetonitrile. When the anion complexes of 1 were treated with alkali metal ions (Li(+), Na(+), K(+), Cs(+), as their perchlorate salts), ion-dependent interactions were observed that were found to depend on both the choice of added cation and the initially complexed anion. In the case of [1·F](-), no appreciable interaction with the K(+) ion was seen. On the other hand, when this complex was treated with Li(+) or Na(+) ions, decomplexation of the bound fluoride anion was observed. In contrast to what was seen with Li(+), Na(+), K(+), treating [1·F](-) with Cs(+) ions gave rise to a stable, host-separated ion-pair complex, [F·1·Cs], which contains the Cs(+) ion bound in the cup-like portion of the calix[4]pyrrole. Different complexation behavior was seen in the case of the chloride complex, [1·Cl](-). Here, no appreciable interaction was observed with Na(+) or K(+). In contrast, treating with Li(+) produces a tight ion-pair complex, [1·Li·Cl], in which the cation is bound to the crown moiety. In analogy to what was seen for [1·F](-), treatment of [1·Cl](-) with Cs(+) ions gives rise to a host-separated ion-pair complex, [Cl·1·Cs], in which the cation is bound to the cup of the calix[4]pyrrole. As inferred from liposomal model membrane transport studies, system 1 can act as an effective carrier for several chloride anion salts of Group 1 cations, operating through both symport (chloride+cation co-transport) and antiport (nitrate-for-chloride exchange) mechanisms. This transport behavior stands in contrast to what is seen for simple octamethylcalix[4]pyrrole, which acts as an effective carrier for cesium chloride but does not operates through a nitrate-for-chloride anion exchange mechanism.     

Determination and pharmacokinetics of [6]-gingerol in mouse plasma by liquid chromatography-tandem mass spectrometry

This study describes the development of a rapid and sensitive high‐performance liquid chromatography–electrospray ionization tandem mass spectrometry (LC‐MS/MS) assay for the quantification of [6]‐gingerol in mouse plasma and application to a pharmacokinetic study after dose ranging in mice. The assay involved a protein precipitation step with acetonitrile and an isocratic elution using a mobile phase consisting of acetonitrile and water containing 0.1% formic acid (80:20 v/v). The multiple reaction monitoring was based on the transition of m/z = 277.2 → 177.1 for [6]‐gingerol and 294.2 → 137.1 for nonivamide (internal standard). The assay was validated to demonstrate the specificity, linearity, recovery, accuracy, precision and stability. The calibration curves were linear over the wide concentration range of 10–10,000 ng/mL (r ≥ 0.9988). The lower limit of quantification was 10 ng/mL using a small volume of mouse plasma (20 μL). The method was successfully applied to a pharmacokinetic study in mice after intravenous injection of [6]‐gingerol at 1.5, 3 and 6 mg/kg doses. The pharmacokinetics of [6]‐gingerol were linear over the dose range studied as demonstrated by the linear increase in area under the concentration‐time curve (AUC_inf) with no significant change in the systemic clearance (Cl_s), volume of distribution (V_ss) and elimination half‐life (t_1/2) as a function of dose. Copyright © 2011 John Wiley & Sons, Ltd.     

A calix[2]phenol[2]pyrrole and a fused pyrrolidine-containing derivative

The hybrid calix[2]phenol[2]pyrrole 4 and the fused pyrrolidine-containing macrocycle 9 were synthesized from two different isomeric starting materials, namely dimethyl 2-hydroxyisophthalate and 5-hydroxyisophthalate, respectively. The fused species 9 is devoid of obvious substrate binding properties. In contrast, the heterocalix system 4 displays the fluoride-induced conformational changes characteristic of the parent system.     

A benzothiazole-based receptor-immobilised silica nanoparticle as chemosensor for Hg2+

Fluorogenic benzothiazole-based receptor has been easily immobilised onto filter paper and silica nanoparticle by sol-gel reaction. The sensing ability of the benzothiazole-immobilised thin layer filter paper chromatography (TLC-1) was evaluated on the basis of fluorescent changes caused by metal ions that were dropped onto the TLC plate. The TLC-1 exhibited a high affinity and selectivity for Hg²⁺ over other competing metal ions. Therefore, the TLC-1 holds promise as a portable sensor for the detection of Hg²⁺ in aqueous solution. Furthermore, the adsorption capacity of a column packed with SiO₂-1 was evaluated by the application of metal ions under various experimental conditions, such as pH, flow rate and concentration. The SiO2-1 column removed 98% of Hg²⁺ from drinking water containing 10 ppb of Hg²⁺. The adsorption capacity of the SiO₂-1 column was not strongly affected by pH and flow rates.