The effect of solvents on the extraction of lanthanoids with 18-crown-6 and trichloroacetate

The effect of solvents on the extraction of lanthanoids with 18-crown-6 and trichloroacetic acid was investigated for the solvents, 1,1,-dichloroethane, 1,2-dichloroethane, 1,1, 2,2-tetrachloroethane, chloroform, di-2-chloroethyl ether, and methylene chloride. Distribution coefficients (25 °C) normalized to the water solubility (wt./vol.) in the solvents correlated to the polarizability index (^*) for La³⁺, Ce³⁺, Pr³⁺, and Nd³⁺ with r values=0.93,0.93,0.95, and 0.98, respectively. The distribution coefficients for Nd³⁺ also correlated with the Hildebrand solubility parameter () (r=0.98). These correlations agree with the literature that for large ions, the extraction thermodynamic properties correlate with the polarizability index and Hildebrand solubility parameter.     

The development and application of capillary electrophoresis methods for food analysis

Capillary electrophoresis (CE) offers the analyst a number of key advantages for the analysis of the components of foods. CE offers better resolution than, say, high-performance liquid chromatography (HPLC), and is more adept at the simultaneous separation of a number of components of different chemistries within a single matrix. In addition, CE requires less rigorous sample cleanup procedures than HPLC, while offering the same degree of automation. However, despite these advantages, CE remains under-utilized by food analysts. Therefore, this review consolidates and discusses the currently reported applications of CE that are relevant to the analysis of foods. Some discussion is also devoted to the development of these reported methods and to the advantages/disadvantages compared with the more usual methods for each particular analysis. It is the aim of this review to give practicing food analysts an overview of the current scope of CE.     

Acoustic imaging of objects buried in soil

In this study, we demonstrate an acoustic system for high-resolution imaging of objects buried in soil. Our goal is to image cultural artifacts in order to assess in a rapid manner the historical significance of a potential construction site. We describe the imaging system and present preliminary images produced from data collected from a soil phantom. A mathematical model and associated computer software are developed in order to simulate the signals acquired by the system. We have built the imaging system, which incorporates a single element source transducer and a receiver array. The source and receiver array are moved together along a linear path to collect data. Using this system, we have obtained B-mode images of several targets by using delay-and-sum beamforming, and we have also applied synthetic aperture theory to this problem.     

Parity violation in elastic electron-proton scattering and the Proton's strange magnetic form factor

We report a new measurement of the parity-violating asymmetry in elastic electron scattering from the proton at backward scattering angles. This asymmetry is sensitive to the strange magnetic form factor of the proton as well as electroweak axial radiative corrections. The new measurement of A = -4.92+/-0.61+/-0.73 ppm provides a significant constraint on these quantities. The implications for the strange magnetic form factor are discussed in the context of theoretical estimates for the axial corrections.     

Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl)

A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.     

Puroindoline-a, a lipid binding protein from common wheat, spontaneously forms prolate protein micelles in solution

The self-assembly in solution of puroindoline-a (Pin-a), an amphiphilic lipid binding protein from common wheat, was investigated by small angle neutron scattering, dynamic light scattering and size exclusion chromatography. Pin-a was found to form monodisperse prolate ellipsoidal micelles with a major axial radius of 112 ± 4.5 ? and minor axial radius of 40.4 ± 0.18 ?. These protein micelles were formed by the spontaneous self-assembly of 38 Pin-a molecules in solution and were stable over a wide pH range (3.5-11) and at elevated temperatures (20-65 °C). Pin-a micelles could be disrupted upon addition of the non-ionic surfactant dodecyl-β-maltoside, suggesting that the protein self-assembly is driven by hydrophobic forces, consisting of intermolecular interactions between Trp residues located within a well-defined Trp-rich domain of Pin-a.     

The Infrared Spectrum of Solid Chlorotrifluoromethane

The Infrared spectrum of solid chlorotrifluoromethane (CF₃Cl) has been studied and compared with that of matrix-isolated CF₃Cl. Crystal field splitting patterns of the strongest modes ν₁ and ν₄ suggest the crystal structure to be orthorhombic with a C_2v factor group and two molecules per unit cell located on C_s sites.     

Compositional dependence of the electrical conductivity of vanadium phosphate glass

The bulk resistivities of vanadium phosphate glasses in the compositional range from 65 to 85 mole % V₂O₅ were measured and fitted as a function of composition to the equation for conductivity as proposed by Mott and later modified by Sayer and Mansingh for n, the number of unoccupied mearest sites surrounding the final hopping site of the small polaron. The fit to the experimental data was found to be best if the number n is chosen to be proportional to the total number of V⁵⁺ sites in the glass. Also n is found to be non-integer and can be regarded as the effective number of unoccupied sites surrounding the final site in the sense of eqn (24) developed in this paper. Values for n ranged from 0.2 to 5 for different compositions of the glass. A model for the structure of vanadium phosphate glass is proposed to explain the data.     

A multielectrode microcompartment culture platform for studying signal transduction in the nervous system

This paper describes the design, fabrication, and characterization of a microfabricated compartmented culture system (micro-CCS) useful for electrophysiological signaling studies in cultured neurons. The focus of the paper is the process of interfacing the micro-CCS with cultured neurons and to demonstrate the applicability of the system for biochemical-mediated electrophysiological studies. Moreover, we show that we can record action potentials from cultured neurons through the extracellular compartmented application of elevated levels of K(+) ions. Finally, we show that we can isolate the electrophysiological effects of the sodium channel blocker tetrodotoxin in one of the compartments of a two compartment culture while recording electrophysiological data from both compartments.     

Auxiliary Likelihood-Based Approximate Bayesian Computation in State Space Models

A computationally simple approach to inference in state space models is proposed, using approximate Bayesian computation (ABC). ABC avoids evaluation of an intractable likelihood by matching summary statistics for the observed data with statistics computed from data simulated from the true process, based on parameter draws from the prior. Draws that produce a “match” between observed and simulated summaries are retained, and used to estimate the inaccessible posterior. With no reduction to a low-dimensional set ofsufficient statistics being possible in the state space setting, we define the summaries as the maximum of an auxiliary likelihood function, and thereby exploit the asymptotic sufficiency of this estimator for the auxiliary parameter vector. We derive conditions under which this approach—including a computationally efficient version based on the auxiliary score—achieves Bayesian consistency. To reduce the well-documented inaccuracy of ABC in multiparameter settings, we propose the separate treatment of each parameter dimension using an integrated likelihood technique. Three stochastic volatility models for which exact Bayesian inference is either computationally challenging, or infeasible, are used for illustration. We demonstrate that our approach compares favorably against an extensive set of approximate and exact comparators. An empirical illustration completes the article. Supplementary materials for this article are available online.