Diazapolycyclic compounds. XX. Stereochemistry of some addition reactions to the double bond at the terminal tetrahydropyridazine ring of methyl substituted 4a,12a-diaza-1,4,4a,5,12,12a- and 4a,12a-diaza-3,4,4a,5,12,12a-hexahydronaphthacene-5,12-diones,and the corresponding epoxides

The stereochemistry of N-bromosuccinimide electrophilic additions to the double bond at the terminal tetrahydropyridazine ring moiety of the 4a,12a-diazatetracyclic compounds 1-4 has been studied. These reactions appear as very regio- and stereoselective. Most the of the results obtained support the hypothesis that the N-bromoamide additions to cyclohexenes and heterocyclic analogous do not occur via the usual Ad_E2 mechanism, because the nucleophilic step is the rate-limiting one and the main product-determining factor. On the other hand, epoxidation of the double bond in 1-4 and further opening of the oxirane ring take place in accordance with the normal stereochemical rules.     

The Palais-Smale condition on contact type energy levels for convex Lagrangian systems

We prove that for a uniformly convex Lagrangian system L on a compact manifold M, almost all energy levels contain a periodic orbit. We also prove that below Mañé's critical value of the lift of the Lagrangian to the universal cover, c _u (L), almost all energy levels have conjugate points. We in addition prove that if an energy level is of contact type, projects onto M and $M\ne{\mathbb T}^2We prove that for a uniformly convex Lagrangian system L on a compact manifold M, almost all energy levels contain a periodic orbit. We also prove that below Ma?é's critical value of the lift of the Lagrangian to the universal cover, c _u (L), almost all energy levels have conjugate points.We in addition prove that if an energy level is of contact type, projects onto M and , then the free time action functional of L+k satisfies the Palais-Smale condition.Partially supported by Conacyt, Mexico, grant 36496-E.     

Definition of a nucleophilicity scale

This work deals with exploring some empirical scales of nucleophilicity. We have started evaluating the experimental indices of nucleophilicity proposed by Legon and Millen on the basis of the measure of the force constants derived from vibrational frequencies using a probe dipole H-X (X = F,CN). The correlation among some theoretical parameters with this experimental scale has been evaluated. The theoretical parameters have been chosen as the minimum of the electrostatic potential V(min), the binding energy (BE) between the nucleophile and the H-X dipole, and the electrostatic potential measured at the position of the hydrogen atom V(H) when the complex nucleophile and dipole H-X is in the equilibrium geometry. All of them present good correlations with the experimental nucleophilicity scale. In addition, the BEs of the nucleophiles with two other Lewis acids (one hard, BF(3), and the other soft, BH(3)) have been evaluated. The results suggest that the Legon and Millen nucleophilicity scale and the electrostatic potential derived scales can describe in good approximation the reactivity order of the nucleophiles only when the interactions with a probe electrophile is of the hard-hard type. For a covalent interaction that is orbital controlled, a new nucleophilicity index using information of the frontier orbitals of both, the nucleophile and the electrophile has been proposed.     

The Tree of Hubs Location Problem

This paper presents the Tree of Hubs Location Problem. It is a network hub location problem with single assignment where a fixed number of hubs have to be located, with the particularity that it is required that the hubs are connected by means of a tree. The problem combines several aspects of location, network design and routing problems. Potential applications appear in telecommunications and transportation systems, when set-up costs for links between hubs are so high that full interconnection between hub nodes is prohibitive. We propose an integer programming formulation for the problem. Furthermore, we present some families of valid inequalities that reinforce the formulation and we give an exact separation procedure for them. Finally, we present computational results using the well-known AP and CAB data sets.     

Use of hydrostatic pressure in determining the nature of DX centers in GaAiAs-Si

Abstract

We report on activated capture and emission experiments obtained under hydrostatic pressure. The observed structures in the thermostimulated capture curves are interpreted as a competition between capture and emission from the different configurations of the DX center, which are related to the local environment of the Si atom. The analysis of the capture kinetic experiments supports the hypothesis of the negative charge state of the DX center.     

The temperature dependent amide I band of crystalline acetanilide

The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.     

Molecular dynamics assessment of doxorubicin–carbon nanotubes molecular interactions for the design of drug delivery systems

Carbon nanotubes (CNTs) constitute an interesting material for nanomedicine applications because of their unique properties, especially their ability to penetrate membranes, to transport drugs specifically and to be easily functionalized. In this work, the energies of the intermolecular interactions of single-walled CNTs and the anticancer drug doxorubicin (DOX) were determined using the AMBER 12 molecular dynamics MM/PBSA and MM/GBSA methods with the aim of better understanding how the structural parameters of the nanotube can improve the interactions with the drug and to determine which structural parameters are more important for increasing the stability of the complexes formed between the CNTs and DOX. The armchair, zigzag, and chiral nanotubes were finite hydrogen-terminated open tubes, and the DOX was encapsulated inside the tube or adsorbed on the nanotube surface. Pentagon/heptagon bumpy defects and polyethylene glycol (PEG) nanotube functionalization were also studied. The best interaction occurred when the drug was located inside the cavity of the nanotube. Armchair and zigzag nanotubes doped with nitrogen, favored interaction with the drug, whereas chiral nanotubes exhibited better drug interactions when having bumpy defects. The π-π stacking and N-H…π electrostatic interactions were important components of the attractive drug-nanotube forces, enabling significant flattening of the nanotube to favor a dual strong interaction with the encapsulated drug, with DOX–CNT equilibrium distances of 3.1–3.9 Å. These results can contribute to the modeling of new drug-nanotube delivery systems.

     

On the accuracy of a nonlinear finite volume method for the solution of diffusion problems using different interpolations strategies

In this paper, we consider a nonlinear finite volume method to solve the steady‐state diffusion equation in nonhomogeneous and non‐isotropic media. The method is nonlinear even if the original problem is linear. In its original form, the scheme is monotone, because the coefficient matrix is monotone under certain assumptions and, as a consequence, whenever the analytic operator demands, it preserves the positivity of numerical solutions. On the other hand, the scheme is unable to reproduce piecewise linear solutions exactly. In order to recover this interesting feature, we use two different interpolation strategies. In this case, even though we are unable to prove monotonicity, we show some numerical evidences that the combined method has an improved behavior, producing second order accurate solutions, even for nonhomogeneous and strongly anisotropic media. Copyright © 2013 John Wiley & Sons, Ltd.