Bis{bis­[5‐tert‐butyl‐2‐oxido‐3‐(1‐pyridinio­methyl)­phenyl]­methane}­dioxouranium bis­(tri­fluoro­methane­sulfonate) pyridine disolvate: a uranyl bis­(diphenoxide) complex resulting from homooxacalixarene cleavage

The title compound, [UO₂(C₃₃H₃₈N₂O₂)₂](CF₃SO₃)₂·2C₅H₅N, has been obtained by reaction of U^IV tri­fluoro­methane­sulfonate with p‐tert‐butyl­tetrahomodioxacalix­[4]­arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square‐planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety.     

Determination of filbertone in spiked olive oil samples using headspace-programmed temperature vaporization-gas chromatography–mass spectrometry

A sensitive method for the fast analysis of filbertone in spiked olive oil samples is presented. The applicability of a headspace (HS) autosampler in combination with a gas chromatograph (GC) equipped with a programmable temperature vaporizer (PTV) and a mass spectrometric (MS) detector is explored. A modular accelerated column heater (MACH^TM) was used to control the temperature of the capillary gas chromatography column. This module can be heated and cooled very rapidly, shortening total analysis cycle times to a considerable extent. The proposed method does not require any previous analyte extraction, filtration and preconcentration step, as in most methods described to date. Sample preparation is reduced to placing the olive oil sample in the vial. This reduces the analysis time and the experimental errors associated with this step of the analytical process. By using headspace generation, the volatiles of the sample are analysed without interference by the non-volatile matrix, and by using injection in solvent-vent mode at the PTV inlet, most of the compounds that are more volatile than filbertone are purged and the matrix effect is minimised. Use of a liner packed with Tenax-TA? allowed the compound of interest to be retained during the venting process. The limits of detection and quantification were as low as 0.27 and 0.83 μg/L, respectively, and precision (measured as the relative standard deviation) was 5.7%. The method was applied to the determination of filbertone in spiked olive oil samples and the results revealed the good accuracy obtained with the method.     

Matching Points with Squares

Given a class of geometric objects and a point set P, a -matching of P is a set of elements of such that each C _i contains exactly two elements of P and each element of P lies in at most one C _i . If all of the elements of P belong to some C _i , M is called a perfect matching. If, in addition, all of the elements of M are pairwise disjoint, we say that this matching M is strong. In this paper we study the existence and characteristics of -matchings for point sets in the plane when is the set of isothetic squares in the plane. A consequence of our results is a proof that the Delaunay triangulations for the L _∞ metric and the L ₁ metric always admit a Hamiltonian path.     

Determination of benzene in gasoline using direct injection-mass spectrometry

A high-speed determination of benzene in gasoline samples using a non-separative method based on direct injection into the mass spectrometer is proposed. The results obtained are very similar to those provided with fast GC-MS.The calibration set was made up of gasoline samples in which the benzene was determined chromatographically and samples of gasoline subjected to a process of evaporation - until the complete disappearance of the original benzene - to which known concentrations of this compound had been added. A PLS1 multivariate calibration model was constructed. Cross-validation was used to select the optimum number of PLS components. The prediction capacity of the model was checked with an additional group of gasoline samples that had not been used either in the construction or in the validation of the model.With the direct injection method proposed here it was possible to analyse 24 samples over a period of 1 h. The direct injection method is rapid, simple and - in view of the results - highly suitable for the determination of benzene in gasoline samples.     

Mass and heat transfer modeling of bio-substrates during packaging

Perishable bio-substrate behavior can be modeled during packaged storage. Local mass and heattransfer have been coupled to respiration rate and microbial growth. Validating measurements have also been performed, and a multi-objective optimization was employed to tune the model. The model is able to simulate gas composition history and local bacteria spoilage in storage modes commonly adopted by the food industry, depending on product features and temperature. Exploitation of this mathematical tool would allow for informed technical and management decisions.     

Programming configurational changes in systems of functionalised polymers using reversible intramolecular linkages

ABSTRACT

We study polymers functionalised by complexes forming intramolecular linkages. Simulations of chains forming reversible linkages are difficult due to entropic barriers that hamper the sampling of different connectivity states specified by the list of pairs of reacted complexes. We address this problem by devising Monte Carlo (MC) moves that change the connectivity state of the system by regrowing parts of the chain while simultaneously reacting bond-forming complexes. Along with moves that link/unlink pairs of complexes, we develop two types of bond-exchange moves. We use these algorithms to study self-assembly of single chain polymeric nanoparticles. When considering monofunctional precursors, we find branched and linear nanoparticle morphologies dominated by long and short intramolecular loops, respectively, along with hierarchical structures in which complexes belonging to different loops are cross-linked. In the strong association limit, equilibrium structures are only reached when using bond-exchange MC moves. We also consider bifunctional precursors in which two different types of complexes decorate the two halves of the chain. We find different types of morphologies featuring different amounts of linkages between complexes of different types. Such findings corroborate our method as a valuable tool to design and predict self-assembly of functional polymers.     

Stabilization by dissipation and stochastic resonant activation in quantum metastable systems

In this tutorial paper we present a comprehensive review of the escape dynamics from quantum metastable states in dissipative systems and related noise-induced effects. We analyze the role of dissipation and driving in the escape process from quantum metastable states with and without an external driving force, starting from a nonequilibrium initial condition. We use the Caldeira–Leggett model and a non-perturbative theoretical technique within the Feynman–Vernon influence functional approach in strong dissipation regime. In the absence of driving, we find that the escape time from the metastable region has a nonmonotonic behavior versus the system-bath coupling and the temperature, producing a stabilizing effect in the quantum metastable system. In the presence of an external driving, the escape time from the metastable region has a nonmonotonic behavior as a function of the frequency of the driving, the thermal-bath coupling and the temperature. The quantum noise enhanced stability phenomenon is observed in both systems investigated. Finally, we analyze the resonantly activated escape from a quantum metastable state in the spin-boson model. We find quantum stochastic resonant activation, that is the presence of a minimum in the escape time as a function of the driving frequency. Background and introductory material has been added in the first three sections of the paper to make this tutorial review reasonably self-contained and readable for graduate students and non-specialists from related areas.     

Preferential sites for InAsP/InP quantum wire nucleation using molecular dynamics

In this paper, stress fields at the surface of the capping layer of self-assembled InAsP quantum wires grown on an InP (001) substrate have been determined from atomistic models using molecular dynamics and Stillinger-Weber potentials. To carry out these calculations, the quantum wire compositional distribution was extracted from previous works, where the As and P distributions were determined by electron energy loss spectroscopy and high-resolution aberration-corrected Z-contrast imaging. Preferential sites for the nucleation of wires on the surface of the capping layer were studied and compared with (i) previous simulations using finite element analysis to solve anisotropic elastic theory equations and (ii) experimentally measured locations of stacked wires. Preferential nucleation sites of stacked wires were determined by the maximum stress location at the MD model surface in good agreement with experimental results and those derived from finite element analysis. This indicates that MD simulations based on empirical potentials provide a suitable and flexible tool to study strain dependent atom processes.     

The Mayer Series of the Lennard–Jones Gas: Improved Bounds for the Convergence Radius

We provide a lower bound for the convergence radius of the Mayer series of the Lennard–Jones gas which strongly improves on the classical bound obtained by Penrose and Ruelle 1963. To obtain this result we use an alternative estimate recently proposed by Morais et al. (J Stat Phys 2014) for a restricted class of stable and tempered pair potentials (namely those which can be written as the sum of a non-negative potential plus an absolutely integrable and stable potential) combined with a method developed by Locatelli and Schoen (J Glob Optim 22, 175–190 2002) for establishing a lower bound for the minimal interatomic distance between particles interacting via a Morse potential in a cluster of minimum-energy configurations.     

On ≤k-Edges, Crossings, and Halving Lines of Geometric Drawings of K n

Let P be a set of points in general position in the plane. Join all pairs of points in P with straight line segments. The number of segment-crossings in such a drawing, denoted by $\operatorname {cr}(P)$ , is the rectilinear crossing number of P. A halving line of P is a line passing through two points of P that divides the rest of the points of P in (almost) half. The number of halving lines of P is denoted by h(P). Similarly, a k-edge, 0??k??n/2?1, is a line passing through two points of P and leaving exactly k points of P on one side. The number of ??k-edges of P is denoted by E _??k (P). Let $\overline {\mathrm {cr}}(n)$ , h(n), and E _??k (n) denote the minimum of $\operatorname {cr}(P)$ , the maximum of h(P), and the minimum of E _??k (P), respectively, over all sets P of n points in general position in the plane. We show that the previously best known lower bound on E _??k (n) is tight for k<?(4n?2)/9? and improve it for all k???(4n?2)/9?. This in turn improves the lower bound on $\overline {\mathrm {cr}}(n)$ from $0.37968\binom{n}{4}+\varTheta (n^{3})$ to $\frac{277}{729}\binom{n}{4}+\varTheta (n^{3})\geq 0.37997\binom{n}{4}+\varTheta (n^{3})$ . We also give the exact values of $\overline {\mathrm {cr}}(n)$ and h(n) for all n??27. Exact values were known only for n??18 and odd n??21 for the crossing number, and for n??14 and odd n??21 for halving lines.