Single and double pH-driven Cu2+ translocation with molecular rearrangement in alkyne-functionalized polyamino polyamido ligands

A new series of ligands, containing one (L1H(2)-L4H(2)) or two (L5H(4)-L6H(4)) 1,4,8,11-tetraaza-5,7-dione units and functionalized with a propargyl group on the C atom between the C=O moieties, has been synthesized. Protonation constants for the ligands and formation constants of their Cu(2+) complexes have been determined in water, and the coordination geometry of the complexes existing at various pH values has been investigated by coupled pH-metric and spectrophotometric titrations. Ligands capable of simple uptake of Cu(2+) with the formation of neutral, square-planar complexes containing the -2-charged diamino-diimido donor sets and ligands containing further coordinating groups (quinoline or pyridine) capable of single and double cation translocation have been investigated. The role of the substituents on the amino groups and the structural role played by the propargyl group have been examined as regards Cu(2+) complexation and translocation. In the double-translocating ligand L6H(4), when the two Cu(2+) ions move inside the diamino-diamido donor set, the slim propargyl group allows an unprecedented folding of the whole ligand with apical coordination of one pyridine to form a five-coordinate, square-pyramidal Cu(2+) ion. The crystal and molecular structures of this unusual [L6Cu(2)] complex have been determined by X-ray diffraction. Finally, oxidation of Cu(2+) to Cu(3+) has been studied by cyclic voltammetry in water, which revealed that the redox reaction occurs only when the copper cation is within the diamino-diimido compartment. Moreover, both functionalization of the primary amines with bulky substituents and apical coordination of Cu(2+) make access to the 3+ oxidation state more difficult and disrupt the reversibility of the electrochemical process.     

Preparation and structure of novel hexaazaisowurtzitane cages

Hexaazaisowurtzitane or cage molecules have attracted attention concerning their synthesis because hexanitrohexaazaisowurtzitane (HNIW or CL20) is presently the most powerful energetic compound. The synthesis of hexaazaisowurtzitanes was considered to be limited solely to the condensation of certain benzylamines with glyoxal. Here, we present the synthesis and characterization of seven novel non-benzylic hexaazaisowurtzitanes, such as hexapropargylhexaazaisowurtzitane. The substituents on the six nitrogen atoms are different to those of the benzyl or substituted benzyl groups to which previous syntheses were limited. X-ray structures are given for the hexapropargyl and hexa-2-thienylmethylene derivatives. Steric strains limit the synthesis with alpha-substituted benzyl and allyl derivatives. The reaction mechanism and the role of the intermediate diimines are discussed. Some of the novel hexaazaisowurtzitanes are potential precursors of hexanitrohexaazaisowurtzitane.     

X-ray diffraction and theoretical studies for the quantitative assessment of intermolecular arene-perfluoroarene stacking interactions

The arene-perfluoroarene stacking interaction was studied by experimental and theoretical methods. A series of compounds with different possibilities for formation of this recognition motif in the solid state were synthesized, and their crystal structures determined by single-crystal X-ray diffraction. The crystal packing of these compounds, as well as the packing of related compounds retrieved from crystallographic databases, were analyzed with quantitative crystal potentials: total lattice energies and the cohesive energies of closest molecular pairs in the crystals were calculated. The arene-perfluoroarene recognition motif emerges as a dominant interaction in the non-hydrogen-bonding compounds studied here, to the point that asymmetric dimers formed over the stacking motif carry over to asymmetric units made of two molecules in the crystal both for pure compounds and for molecular complexes; however, inter-ring distances and angles range from 3.70 to 4.85 A and from 5 to 21 degrees , respectively. Pixel energy partitioning reveals that whenever aromatic rings stack, the largest cohesive energy contribution comes from dispersion, which roughly amounts to 20 kJ mol(-1) per phenyl ring, while the coulombic term is minor but significant enough to make a difference between the arene-arene or perfluoroarene-perfluoroarene interactions on the one hand, and arene-perfluoroarene interactions on the other, whereby the latter are favored by about 10 kJ mol(-1) per phenyl ring. No evidence of special interaction which can be attributed to HF confrontation was recognizable.     

Maximal time regularity for degenerate evolution integro-differential equations

We provide maximal time regularity properties for the solutions to a class of degenerate first-order integro-differential Cauchy problems in a Banach space X. In particular, we show that an additional condition of space regularity on the data it suffices for restoring the loss of time regularity which arises naturally when dealing with the degenerate case.     

A meta-heuristic approach for solving the Urban Network Design Problem

This paper proposes an optimisation model and a meta-heuristic algorithm for solving the urban network design problem. The problem consists in optimising the layout of an urban road network by designing directions of existing roads and signal settings at intersections. A non-linear constrained optimisation model for solving this problem is formulated, adopting a bi-level approach in order to reduce the complexity of solution methods and the computation times. A Scatter Search algorithm based on a random descent method is proposed and tested on a real dimension network. Initial results show that the proposed approach allows local optimal solutions to be obtained in reasonable computation times.     

Finite Anticlastic Bending of Hyperelastic Solids and Beams

This paper deals with the equilibrium problem in nonlinear elasticity of hyperelastic solids under anticlastic bending. A three-dimensional kinematic model, where the longitudinal bending is accompanied by the transversal deformation of cross sections, is formulated. Following a semi-inverse approach, the displacement field prescribed by the above kinematic model contains three unknown parameters. A Lagrangian analysis is performed and the compressible Mooney-Rivlin law is assumed for the stored energy function. Once evaluated the Piola-Kirchhoff stresses, the free parameters of the kinematic model are determined by using the equilibrium equations and the boundary conditions. An Eulerian analysis is then accomplished to evaluating stretches and stresses in the deformed configuration. Cauchy stress distributions are investigated and it is shown how, for wide ranges of constitutive parameters, the obtained solution is quite accurate. The whole formulation proposed for the finite anticlastic bending of hyperelastic solids is linearized by introducing the hypothesis of smallness of the displacement and strain fields. With this linearization procedure, the classical solution for the infinitesimal bending of beams is fully recovered.     

Characterization and Thermal Behavior of the Iron Dietary Supplement Ferrous Glycine Sulfate Pentahydrate

Ferrous glycine sulfate pentahydrate [Fe(glycine)(SO₄)·5H₂O with glycine = C₂H₅NO₂], contained in the supplement for treating iron deficiency anaemia, commercially known as ferro sanol duodenal^®, was characterized by laboratory X‐ray powder diffraction (XRPD), scanning electron microscope (SEM), and infrared spectroscopy (IR). The thermal behavior was investigated by thermal analysis (TGA and DTA) and temperature‐dependent in situ XRPD measurements. Furthermore, the phase transitions to a less hydrated form [Fe(glycine)(SO₄)·3H₂O] and successively to the anhydrous form were demonstrated to occur in the crystalline solid state. Compared to the crystal structure of the pentahydrate, the trihydrate exhibits a different coordination environment of the iron sites where glycine ligands bridge iron forming a 1D polymeric chain structure. From detailed structural comparison, the mechanism of the phase transitions can be concluded.     

Analytic Hessian derivation for the quasi-one-dimensional Euler equations

The Hessian for the quasi-one-dimensional Euler equations is derived. A pressure minimization problem and a pressure matching inverse problem are considered. The flow sensitivity, adjoint sensitivity, gradient and Hessian are calculated analytically using a direct approach that is specific to the model problems. For the pressure minimization problem we find that the Hessian exists and it contains elements with significantly larger values around the shock location. For the pressure matching inverse problem we find at least one case for which the gradient as well as the Hessian do not exist. In addition, two formulations for calculating the Hessian are proposed and implemented for the given problems. Both methods can be implemented in industrial applications such as large scale aerodynamic optimization.     

Generalized recurrence plots for the analysis of images from spatially distributed systems

We propose a new method for the analysis of images showing patterns emerging from the evolution of spatially distributed systems. The generalized recurrence plot (GRP) and the generalized recurrence quantification analysis (GRQA) are exploited for the investigation of such patterns.We focus on snapshots of spatio-temporal processes such as the formation of Turing structures and traveling waves in the Belousov-Zhabotinsky reaction, satellite images of spatial chlorophyll distribution in seas and oceans (similar to turbulent flows), colonies of Dyctiostelium discoideum, fractals, and noise.The method is based on the GRP and GRQA and particularly on the measures determinism (DET) and entropy (ENT), providing a new criterion for the assessment and classification of images based on the simultaneous evaluation of their global and local structure.The DET-ENT diagram is introduced and compared with the classical image analysis entropy defined on the pixels’ values. The method proposed provides appealing performances in the case of images showing complex spatial patterns.