Preparation and characterization of a europium(II) bromide-chloride phase EuBr1.5Cl0.5

A divalent europium chloride-bromide phase, EuBr_1.56(7)Cl_0.46(2) has been prepared and identified on the basis of analytical, X-ray powder diffraction and single-crystal data. Although the phase is considered isostructural with EuCl₂ (PbCl₂ structure type, a = 0.9230 (5), b = 0.7890 (4), c = 0.4613 (3) nm, space group Pbnm), the single-crystal data indicate long-range order in the form of a superstructure which doubles the b parameter. In the pseudocell the square pyramidal anion sites are occupied principally by bromide ions, the tetrahedral sites almost equally by bromide and chlorine ions. Structural details and the long-range order are discussed. Evidence is presented for the existence of another europium(II) mixed halide phase, EuBr_1.8(2)Cl_0.16(2).     

Short and diverse route toward complex natural product-like macrocycles

[reaction: see text] A general strategy toward macrocyclic compounds using multicomponent reaction (MCR) chemistry, e.g., Passerini and Ugi variants, and ring-closing metathesis (RCM) is introduced. The corresponding bifunctional isocyanides carboxylic acids bearing a terminal olefin are easy to prepare from the corresponding commercially available starting materials. Advantageously, this strategy allows fast access to a diverse conformational space of natural product-like macrocycles and could thus be of interest in the discovery of novel bioactive agents.     

Ordered binary crystals via cocrystallisation of quasiracemic Pd(II) complexes in a borderline regime between inertness and lability

Square planar complexes of the type [2-(1-aminoethyl)phenyl-kappa(2)C(1),N]chloro(py-kappaN)palladium(II)(py = pyridine derivative) have been prepared by cyclopalladation of 1-phenylethylamine. When opposite enantiomers of the chiral amine and different pyridine ligands were coordinated to the metal, quasiracemic complexes were obtained. The racemisation speed of solutions containing equimolar amounts of such quasiracemic complexes was used to test the compounds for inertness: slow ligand exchange was found for methylated pyridines. Enantiomerically pure complexes of opposite chirality with the electron rich ligands 2,6-collidine and 2,4,6-lutidine were successfully cocrystallised: they form a well-ordered binary solid in which four independent molecules, two of each constituent, are related by pseudo symmetry operations. This quasiracemate as well as its components and the true racemates of the latter were characterised by single crystal X-ray diffraction. The heterochiral crystals, both the cocrystal as well as the racemates, show better space filling than the homochiral solids.     

Comparison of inductively coupled plasma mass spectrometry techniques in the determination of platinum in urine: quadrupole vs. sector field

In recent years the increasing use of platinum (Pt) both in medical and in industrial applications has caused its growing anthropogenic emission and spread in the environment. Pt is released into the atmosphere by exhaust catalytic converters, and Pt compounds are often used in antitumour therapies. As a consequence, significant amounts of Pt can be detected in hospital wastewaters. This can lead to an increase in the exposure levels to Pt, especially in urban areas. It is therefore necessary to determine Pt reference values in the general population, by using suitable procedures able to achieve adequate analytical performances. Several measurements of Pt in biological fluids have been reported, but the analytical methods used for the determination of Pt often lack information about the uncertainty of the results, especially for low concentrations of urinary Pt in non-occupationally exposed subjects. The present paper considers the measurement of urinary Pt levels in a general population group from central Italy, by both quadrupole (Q) and sector field (SF) inductively coupled plasma mass spectrometry (ICP-MS). The two procedures were validated and their expanded uncertainties were evaluated. The limits of detection (LODs), calculated taking into account dilution factors, were 0.18 and 0.05 ng L(-1) of Pt for the Q and SF procedures, respectively. The median value observed was 4.13 ng L(-1) of Pt in urine, while the relative combined uncertainty at 5 ng L(-1) was below 20% with both ICP-MS techniques. These data are in good agreement with those reported in the literature for similar studies.     

Convergence analysis of a coupled method for time‐dependent convection‐diffusion equations

The coupling of two locally mass conservative methods is formulated and analyzed for the time‐dependent convection‐diffusion problem. Finite volume method is used in some subdomains and interior penalty discontinuous Galerkin method is used in other subdomains. Numerical examples show the advantages of the proposed hybrid method, namely an accurate approximation obtained at a reduced computational cost. © 2013 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 30: 133–157, 2014     

Polymorph formation from solvate desolvation

Spironolactone (C₂₄H₃₂O₄S) usually crystallizes into an orthorhombic phase, named Form II. Another orthorhombic phase, named Form I, is also known but seems difficult to obtain. Studies of the kinetics of desolvation of the ethanol solvate at room temperature showed that these two forms can be obtained through different mechanisms of desolvation.     

α-Well-posedness for Nash Equilibria and For Optimization Problems with Nash Equilibrium Constraints

We present the concepts of α-well-posedness for parametric noncooperative games and for optimization problems with constraints defined by parametric Nash equilibria. We investigate some classes of functions that ensure these types of well-posedness and the connections with α-well-posedness for variational inequalities and optimization problems with variational inequality constraints.