Complexation of Am(III) and Nd(III) by 1,10-Phenanthroline-2,9-Dicarboxylic Acid

The complexant 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) is a planar tetradentate ligand that is more preorganized for metal complexation than its unconstrained analogue ethylendiiminodiacetic acid (EDDA). Furthermore, the backbone nitrogen atoms of PDA are aromatic, hence are softer than the aliphatic amines of EDDA. It has been hypothesized that PDA will selectively bond to trivalent actinides over lanthanides. In this report, the results of spectrophotometric studies of the complexation of Nd(III) and Am(III) by PDA are reported. Because the complexes are moderately stable, it was necessary to conduct these titrations using competitive equilibrium methods, competitive cation complexing between PDA and diethylenetriaminepentaacetic acid, and competition between ligand protonation and complex formation. Stability constants and ligand protonation constants were determined at 0.1 mol·L^?1 ionic strength and at 0.5 mol·L^?1 ionic strength nitrate media at 21 ± 1 °C. The stability constants are lower than those predicted from first principles and speciation calculations indicate that Am³⁺ selectivity over Nd³⁺ is less than that exhibited by 1,10-phenanthroline.     

A 57 Fe Mössbauer study on the FeSe and Fe(Se,Te) superconductors: discontinuities in the hyperfine parameters at T c

Polycrystalline samples of FeSe_0.82 and FeSe_0.5Te_0.5 were synthesized using a solid-state reaction route. Bulk superconductivity was confirmed using SQUID magnetometry. The onset of T _c was at 8.0 K for FeSe_0.82 and 12.5 K for FeSe_0.5Te_0.5. Paramagnetic ⁵⁷Fe Mössbauer spectra were recorded at temperatures between 5.4 and 320 K in transmission geometry. All spectra exhibited simple quadrupole splitting. For FeSe_0.5Te_0.5 a small drop in the quadrupole splitting was observed about T _c upon cooling. Additionally, for both samples the isomer shift and the total absorption started to drop around T _c , indicating a softening of the lattice. The drop is estimated to correspond to at least 60 K from the original Debye temperatures.     

A mass spectrometric study on meloxicam metabolism in horses and the fungus Cunninghamella elegans,and the relevance of this microbial system as a model of drug metabolism in the horse

This paper describes a study where the metabolism of the non‐steroidal anti‐inflammatory drug meloxicam was investigated in six horses and in the filamentous fungus Cunninghamella elegans. The metabolites identified were compared between the species, and then the fungus was used to produce larger amounts of the metabolites for future use as reference material. C. elegans proved to be a good model of phase I meloxicam metabolism in horses since all four metabolites found were the same in both species. Apart from the two main metabolites, 5′‐hydroxymethylmeloxicam and 5′‐carboxymeloxicam, a second isomer of hydroxymeloxicam and dihydroxylated meloxicam were detected for the first time in horse urine and the microbial incubations. Phase II metabolites were not discovered in the C. elegans samples but hydroxymeloxicam glucuronide was detected intact in horse urine for the first time in this study. Urine from six horses was further analyzed in a semi‐quantitative sense and 5′‐hydroxymethylmeloxicam gave peaks with much higher intensity compared to the parent drug and the other metabolites, and was detected for at least 14 days after the last given dose in some of the horses. From the results presented in this article, we suggest that analytical methods developed for the detection of meloxicam in horse urine after prohibited use should focus on the 5′‐hydroxymethyl metabolite and that C. elegans can be used to produce large amounts of this metabolite for potential future use as a reference compound. Copyright © 2009 John Wiley & Sons, Ltd.     

Neural Estimator of Information for Time-Series Data with Dependency

Novel approaches to estimate information measures using neural networks are well-celebrated in recent years both in the information theory and machine learning communities. These neural-based estimators are shown to converge to the true values when estimating mutual information and conditional mutual information using independent samples. However, if the samples in the dataset are not independent, the consistency of these estimators requires further investigation. This is of particular interest for a more complex measure such as the directed information, which is pivotal in characterizing causality and is meaningful over time-dependent variables. The extension of the convergence proof for such cases is not trivial and demands further assumptions on the data. In this paper, we show that our neural estimator for conditional mutual information is consistent when the dataset is generated with samples of a stationary and ergodic source. In other words, we show that our information estimator using neural networks converges asymptotically to the true value with probability one. Besides universal functional approximation of neural networks, a core lemma to show the convergence is Birkhoff’s ergodic theorem. Additionally, we use the technique to estimate directed information and demonstrate the effectiveness of our approach in simulations.     

Optimization in forestry

 Optimization models and methods have been used extensively in the forest industry. In this paper we describe the general wood-flow in forestry and a variety of planning problems. These cover planning periods from a fraction of a second to more than one hundred years. The problems are modelled using linear, integer and nonlinear models. Solution methods used depend on the required solution time and include for example dynamic programming, LP methods, branch & bound methods, heuristics and column generation. The importance of modelling and qualitative information is also discussed. Received: January 15, 2003 / Accepted: April 24, 2003 Published online: May 28, 2003 Key words. Forestry – modelling – routing – transportation – production planning Mathematics Subject Classification (2000): 20E28, 20G40, 20C20     

Gleason parts in uniform Fréchet algebras

We prove that Gleason parts in uniform distinguished Fréchet algebras are open and closed in the weak topology.     

Integrated Production and Distribution Planning for Södra Cell AB

In this paper we consider integrated planning of transportation of raw material, production and distribution of products of the supply chain at Södra Cell AB, a major European pulp mill company. The strategic planning period is one year. Decisions included in the planning are transportation of raw materials from harvest areas to pulp mills, production mix and contents at pulp mills, distribution of pulp products from mills to customer via terminals or directly and selection of potential orders and their levels at customers. Distribution is carried out by three different transportation modes; vessels, trains and trucks. We propose a mathematical model for the entire supply chain which includes a large number of continuous variables and a set of binary variables to reflect decisions about product mix and order selection at customers. Five different alternatives regarding production mix in a case study carried out at Södra Cell are analyzed and evaluated. Each alternative describes which products will be produced at which pulp mills.     

Lanthanide-cored fluorinated dendrimer complexes: synthesis and luminescence characterization

Eu³⁺-, Tb³⁺- and Er³⁺-cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer from the peripheral fluorinated phenyl moieties of the dendrons to the lanthanide cation was evidenced spectroscopically for Eu³⁺- and Tb³⁺-cored dendrimer complexes in solution. The excitation of perfluorinated aromatic groups was found to decay with ca. 0.7 ns and a longer decay time 10-13 ns was related to the coordination at the Ln³⁺ focal point. Luminescence from the lanthanide core decays with lifetime in the range 1-1.5 ms over a wide concentration range (μM-mM), similar to the luminescence decay time of the corresponding acetate ion complexes in D₂O. The main quenching mechanism of the lanthanide emission appears to be due to vibrations among surrounding C-H bonds of the intermediate shell of the flexible dendrimer scaffold. Antenna effect and energy harvesting from the surface of the dendrimer and transfer to the core was the main mechanism for luminescecnce in the dendrimer complexes with lanthanide cations.     

Molecular dynamics effects on luminescence properties of oligothiophene derivatives: a molecular mechanics-response theory study based on the CHARMM force field and density functional theory

CHARMM force field parameter values for a class of oligothiophene derivatives have been derived with reference to density functional theory/B3LYP potential energy surfaces. The force field parametrization of these luminescent conjugated polyelectrolytes includes the electronic ground state as well as the strongly light absorbing first excited state. In conjunction with quantum chemical response theory calculations of transition state properties, a molecular dynamical model of the Stokes shift is obtained. The theoretical model is benchmarked against experimental data recorded at room temperature which refer to sodium salts of p-HTAA and p-FTAA with distilled water as a solvent. For p-HTAA the theoretically predicted Stokes shift of 112 nm is in good agreement with the experimental result of 124 nm, given the approximations about exciton localization that were introduced to obtain a force field for the excited state.