Thermodynamics of complexation of monovalent metal cations by the ionophore monensin free acid in acetonitrile

The standard Gibbs functions, enthalpies, and entropies for the formation of the complexes of monensin acid with monovalent metal cations in acetonitrile were obtained using various methods (conductometry, potentiometry, and calorimetry). Complexation is appreciable (from 2.0 to 4.5 in terms of association constant logarithm) and controlled mainly by the enthalpic effect. Comparison with formation of the corresponding neutral complexes permits a comparison to the process of monensin mediated transport of cation in membranes. A two-step process involving first the formation of the acidic complex is suggested.     

A Bistable Microelectromechanical System Actuated by Spin-Crossover Molecules

We report on a bistable MEMS device actuated by spin-crossover molecules. The device consists of a freestanding silicon microcantilever with an integrated piezoresistive detection system, which was coated with a 140 nm thick film of the [Fe(HB(tz)₃)₂] (tz=1,2,4-triazol-1-yl) molecular spin-crossover complex. Switching from the low-spin to the high-spin state of the ferrous ions at 338 K led to a reversible upward bending of the cantilever in agreement with the change in the lattice parameters of the complex. The strong mechanical coupling was also evidenced by the decrease of approximately 66 Hz in the resonance frequency in the high-spin state as well as by the drop in the quality factor around the spin transition.     

Electrochemistry of 6-methyl-5,6,7,8-tetrahydropterin

The electrochemical oxidation of 6-methyl-5,6,7,8-tetrahydropterin (6-MTHP), the most effective of the synthetic aromatic amino acid hydroxylase pseudo cofactors, has been studied in aqueous solution over a wide pH range at a pyrolytic graphite electrode. The first electrooxidation of 6-WTHP occurs by a quasi-reversible 2e-2H⁺ reaction giving an unstable quinonoid-dihydropterin. The latter undergoes a first order chemical follow-up reaction yielding 6-methyl-7,8-dihydropterin (6-MDHP). At pH values ?5.6 6-MDHP forms an equilibrium mixture of a covalently hydrated species and non-hydrated species. The covalently hydrated form of 6-MDHP is electrooxidized in a 2e-2H⁺ quasi-reversible reaction to another unstable quinonoid that appears to undergo a two-step rearrangement to 6-methylpterin. Non-hydrated 6-MDHP is electrooxidized at the most positive potential in an irreversible 2e-2H⁺ reaction giving 6-methylpterin.     

Phosphine Oxide-Functionalized Terthiophene Redox Systems

Main group systems capable of undergoing controlled redox events at extreme potentials are elusive yet highly desirable for a range of organic electronics applications including use as energy storage media. Herein we describe phosphine oxide-functionalized terthiophenes that exhibit two reversible 1e⁻ reductions at potentials below −2 V vs Fc/Fc⁺ (Fc=ferrocene) while retaining high degrees of stability. A phosphine oxide-functionalized terthiophene radical anion was synthesized in which the redox-responsive nature of the platform was established using combined structural, spectroscopic, and computational characterization. Straightforward structural modification led to the identification of a derivative that exhibits exceptional stability during bulk 2 e⁻ galvanostatic charge–discharge cycling and enabled characterization of a 2 e⁻ redox series. A new multi-electron redox system class is hence disclosed that expands the electrochemical cell potential range achievable with main group electrolytes without compromising stability.     

Solving a robotic assembly line balancing problem using efficient hybrid methods

In this paper we are studying a robotic assembly line balancing problem. The goal is to maximize the efficiency of the line and to balance the different tasks between the robots by defining the suitable tasks and components to assign to each robot. We are interested in a robotic line which consists of seizing the products on a moving conveyor and placing them on different location points. The performances evaluations of the system are done using a discret event simulation model. This latter has been developed with C++ language. As in our industrial application we are bounded by the execution time, we propose some resolution methods which define the suitable component and point positions in order to define the strategy of pick and place for each robot. These methods are based on the ant colony optimization, particle swarm optimization and genetic algorithms. To enhance the quality of the developed algorithms and to avoid local optima, we have coupled these algorithms with guided local search. After that, an exact method based on full enumeration is also developed to assess the quality of the developed methods. Then, we try to select the best algorithm which is able to get the best solutions with a small execution time. This is the main advantage of our methods compared to exact methods. This fact represents a great interest taking in consideration that the selected methods are used to manage the functioning of real industrial robotic assembly lines. Numerical results show that the selected algorithm performs optimally for the tested instances in a reasonable computation time and satisfies the industrial constraint.     

A roe-type Riemann solver for hyperbolic systems with relaxation based on time-dependent wave decomposition

Summary. The paper is devoted to the construction of a higher order Roe-type numerical scheme for the solution of hyperbolic systems with relaxation source terms. It is important for applications that the numerical scheme handles both stiff and non stiff source terms with the same accuracy and computational cost and that the relaxation variables are computed accurately in the stiff case. The method is based on the solution of a Riemann problem for a linear system with constant coefficients: a study of the behavior of the solutions of both the nonlinear and linearized problems as the relaxation time tends to zero enables to choose a convenient linearization such that the numerical scheme is consistent with both the hyperbolic system when the source terms are absent and the correct relaxation system when the relaxation time tends to zero. The method is applied to the study of the propagation of sound waves in a two-phase medium. The comparison between our numerical scheme, usual fractional step methods, and numerical simulation of the relaxation system shows the necessity of using the solutions of a fully coupled hyperbolic system with relaxation terms as the basis of a numerical scheme to obtain accurate solutions regardless of the stiffness. Received October 7, 1994 / Revised version received September 27, 1995     

A spatial scan statistic for case event data based on connected components

We propose a new spatial scan statistic based on graph theory as a method for detecting irregularly-shaped clusters of events over space. A graph-based method is proposed for identifying potential clusters in spatial point processes. It relies on linking the events closest than a given distance and thus defining a graph associated to the point process. The set of possible clusters is then restricted to windows including the connected components of the graph. The concentration in each of these possible clusters is measured through classical concentration indices based on likelihood ratio and also through a new concentration index which does not depend on any alternative hypothesis. These graph-based spatial scan tests seem to be very powerful against any arbitrarily-shaped cluster alternative, whatever the dimension of the data. These results have applications in various fields, such as the epidemiological study of rare diseases or the analysis of astrophysical data.     

Einstein-Weyl structures on lightlike hypersurfaces

We study Weyl structures on lightlike hypersurfaces endowed with a conformal structure of certain type and specific screen distribution: the Weyl screen structures. We investigate various differential geometric properties of Einstein-Weyl screen structures on lightlike hypersurfaces and show that, for ambient Lorentzian space ? ₁ ⁿ⁺² and a totally umbilical screen foliation, there is a strong interplay with the induced (Riemannian) Weyl-structure on the leaves.     

Structured probabilistic inference

Probabilistic inference is among the main topics with reasoning in uncertainty in AI. For this purpose, Bayesian Networks (BNs) is one of the most successful and efficient Probabilistic Graphical Model (PGM) so far. Since the mid-90s, a growing number of BNs extensions have been proposed. Object-oriented, entity-relationship and first-order logic are the main representation paradigms used to extend BNs. While entity-relationship and first-order models have been successfully used for machine learning in defining lifted probabilistic inference, object-oriented models have been mostly underused. Structured inference, which exploits the structural knowledge encoded in an object-oriented PGM, is a surprisingly unstudied technique. In this paper we propose a full object-oriented framework for PRM and propose two extensions of the state-of-the-art structured inference algorithm: SPI which removes the major flaws of existing algorithms and SPISBB which largely enhances SPI by using d-separation.     

Integrability of subdifferentials of directionally Lipschitz functions

Using a quantitative version of the subdifferential characterization of directionally Lipschitz functions, we study the integrability of subdifferentials of such functions over arbitrary Banach space.