A density functional theory study of uranium(VI) nitrate monoamide complexes

Density functional theory calculations were performed on uranyl complexed with nitrate and monoamide ligands (L) [UO(2)(NO(3))(2)·2L]. The obtained results show that the complex stability is mainly governed by two factors: (i) the maximization of the polarizability of the coordinating ligand and (ii) the minimization of the steric hindrance effects. Furthermore, the electrostatic interaction between ligands and uranium(vi) was found to be a crucial parameter for the complex stability. These results pave the way to the definition of (quantitative) property/structure relationships for the in silico screening of monoamide ligands with improved extraction efficiency of uranium(vi) in nitrate acidic solution.     

Structural features and protonation site of epibatidine in the gas phase: an investigation through infrared multiphoton dissociation spectroscopy and computational chemistry

The gas phase structures of epibatidine, one of the most potent agonists of nicotinic acetylcholine receptors (nAChRs), are determined by means of infrared multiphoton dissociation (IRMPD) spectroscopy and quantum chemistry calculations. Comparison of the experimental and theoretical spectra provides evidence that about 15% of epibatidine is protonated on the Nsp(2) nitrogen in the gas phase. In contrast, the computational study of deschloroepibatidine shows that in the gas phase, the molecule is present only protonated on the Nsp(2) nitrogen. The main minima of the Nsp(2) protonated forms of the two molecules are strongly stabilized by intramolecular CH···Nsp(3) hydrogen bonds. The fundamental insights obtained in the present study on these two important nAChRs agonists show how subtle chemical modifications can have a deep impact on important physicochemical properties.     

Rotational quenching of monodeuterated water by hydrogen molecules

Cross sections and rate coefficients for low lying rotational transitions in HDO induced by para and ortho-H(2) collisions are presented for the first time. Calculations have been performed at the close-coupling and coupled-states levels with the deuterated variant of the H(2)O-H(2) interaction potential of Valiron et al. [J. Chem. Phys., 2008, 129, 134306]. Rate coefficients are presented for temperatures between 5 and 100 K and are compared to the corresponding rates for H(2)O and D(2)O. Significant differences caused by the isotopic substitution, in particular the C(2v) symmetry breaking, are observed. Finally, our rates are found to be significantly larger (by up to three orders of magnitude at 50 K) than the corresponding HDO-He rates and should lead to a thorough re-estimation of the abundance of interstellar HDO.     

The Existence Problem for Steiner Networks in Strictly Convex Domains

We consider the existence problem for ‘Steiner networks’ (trivalent graphs with 2π/3 angles at each junction) in strictly convex domains, with ‘Neumann’ boundary conditions. For each of the three possible combinatorial possibilities, sufficient conditions on the domain are derived for existence. In addition, in each case explicit examples of nonexistence are given.     

Prediction of tractive response for flexible wheels with application to planetary rovers

Planetary rovers are typically developed for high-risk missions. Locomotion requires traction to provide forward thrust on the ground. In soft soils, traction is limited by the mechanical properties of the soil, therefore lack of traction and wheel slippage cause difficulties during the operation of the rover. A possible solution to increase the traction force is to increase the size of the wheel-ground contact area. Flexible wheels provide this due to the deformation of the loaded wheel and hence this decreases the ground pressure on the soil surface. This study focuses on development of an analytical model which is an extension to the Bekker theory to predict the tractive performance for a metal flexible wheel by using the geometric model of the wheel in deformation. We demonstrate that the new analytical model closely matches experimental results. Hence this model can be used in the design of robust and optimal traction control algorithms for planetary rovers and for the design and the optimisation of flexible wheels.     

Almost continuous orbit equivalence for non-singular homeomorphisms

Let X and Y be Polish spaces with non-atomic Borel measures μ and ν of full support. Suppose that T and S are ergodic non-singular homeomorphisms of (X, μ) and (Y, ν) with continuous Radon-Nikodym derivatives. Suppose that either they are both of type III ₁ or that they are both of type III _λ, 0 < λ < 1 and, in the III _λ case, suppose in addition that both ‘topological asymptotic ranges’ (defined in the article) are log λ · ℤ. Then there exist invariant dense G _δ-subsets X′ ⊂ X and Y′ ⊂ Y of full measure and a non-singular homeomorphism ϕ: X′ → Y′ which is an orbit equivalence between T| _X′ and S| _Y′, that is ϕ{T ⁱ x} = {S ⁱ ϕx} for all x ∈ X′. Moreover, the Radon-Nikodym derivative dν ∘ ϕ/dμ is continuous on X′ and, letting S′ = ϕ ⁻¹ Sϕ, we have T _x = S′ ^n(x) x and S′x = T ^m(x) x where n and m are continuous on X′.     

Microextraction of Reseda luteola-Dyed Wool and Qualitative Analysis of Its Flavones by UHPLC-UV,NMR and MS

Detailed knowledge on natural dyes is important for agronomy and quality control as well as the fastness, stability, and analysis of dyed textiles. Weld (Reseda luteola L.), which is a source of flavone-based yellow dye, is the focus of this study. One aim was to reduce the required amount of dyed textile to ≤50 μg for a successful chromatographic analysis. The second aim was to unambiguously confirm the identity of all weld flavones. By carrying out the extraction of 50 μg dyed wool with 25 μL of solvent and analysis by reversed-phase UHPLC at 345 nm, reproducible chromatographic fingerprints could be obtained with good signal to noise ratios. Ten baseline separated peaks with relative areas ≥1% were separated in 6 min. Through repeated polyamide column chromatography and prepHPLC, the compounds corresponding with the fingerprint peaks were purified from dried weld. Each was unequivocally identified, including the position and configuration of attached sugars, by means of 1D and 2D NMR and high-resolution MS. Apigenin-4′-O-glucoside and luteolin-4′-O-glucoside were additionally identified as two trace flavones co-eluting with other flavone glucosides, the former for the first time in weld. The microextraction might be extended to other used dye plants, thus reducing the required amount of precious historical textiles.     

Polarisabilités optiques moléculaires de dérivés benzèniques en solution déterminées par des mesures d'effet Kerr statique

Une expression théorique simplifiée de la constante de Kerr permet une comparaison cohérente des mesures d'effet Kerr statique et de diffusion Rayleigh dépolarisée. Cette comparaison ainsi que des mesures de moments dipolaires sont effectuées sur une série de composés benzèniques en solution diluée dans le tétrachlorure de carbone. La méthode d'exploitation des résultats expérimentaux conduit à la détermination du tenseur des polarisabilités optiques moléculaires α de ces composés. Un accord satisfaisant est obtenu en comparant la constante spécifique de Kerr S _k et l'anisotropie optique moléculaire γ², calculées à partir de ces polarisabilités, à leurs valeurs expérimentales.     

Boundaries of Coxeter Matroids

The purpose of this paper is to introduce, for a finite Coxeter groupW, the mod 2 boundary operator on the space of all Coxeter matroids (also known asWP-matroids) forWandP, wherePvaries through all the proper standard parabolic subgroups ofW(Theorem 3 of the paper). A remarkably simple interpretation of Coxeter matroids as certain sets of faces of the generalized permutahedron associated with the Coxeter groupW(Theorem 1) yields a natural definition of the boundary of a Coxeter matroid. The latter happens to be a union of Coxeter matroids for maximal standard parabolic subgroupsQ_iofP(Theorem 2). These results have very natural interpretations in the case of ordinary matroids and flag-matroids (Section 3).