A Kirkwood-Buff Derived Force Field for Aqueous Alkali Halides

A classical nonpolarizable force field is presented for the simulation of aqueous alkali halide solutions (MX), where M = Li(+), Na(+), K(+), Rb(+), Cs(+) and X = F(-), Cl(-), Br(-), I(-), and their interactions with biomolecules. The models are specifically designed to reproduce the experimental Kirkwood-Buff integrals, and thereby the solution salt activities, as a function of salt concentration. Additionally, we demonstrate that these models reasonably reproduce other experimental properties including ion diffusion constants, dielectric decrements, and the excess heats of mixing. The parameters are developed by considering the properties of aqueous NaX and MCl solutions using a previously established model for NaCl. Transferability of the parameters to other salts is then established by the successful simulation of additional aqueous salt solutions, KI and CsBr, not originally included in the parameterization procedure.     

Semidefinite relaxations for quadratically constrained quadratic programming: A review and comparisons

At the intersection of nonlinear and combinatorial optimization, quadratic programming has attracted significant interest over the past several decades. A variety of relaxations for quadratically constrained quadratic programming (QCQP) can be formulated as semidefinite programs (SDPs). The primary purpose of this paper is to present a systematic comparison of SDP relaxations for QCQP. Using theoretical analysis, it is shown that the recently developed doubly nonnegative relaxation is equivalent to the Shor relaxation, when the latter is enhanced with a partial first-order relaxation-linearization technique. These two relaxations are shown to theoretically dominate six other SDP relaxations. A computational comparison reveals that the two dominant relaxations require three orders of magnitude more computational time than the weaker relaxations, while providing relaxation gaps averaging 3% as opposed to gaps of up to 19% for weaker relaxations, on 700 randomly generated problems with up to 60 variables. An SDP relaxation derived from Lagrangian relaxation, after the addition of redundant nonlinear constraints to the primal, achieves gaps averaging 13% in a few CPU seconds.     

Identifying preferred solutions to Multi-Objective Binary Optimisation problems,with an application to the Multi-Objective Knapsack Problem

In this paper we present a new framework for identifying preferred solutions to multi-objective binary optimisation problems. We develop the necessary theory which leads to new formulations that integrate the decision space with the space of criterion weights. The advantage of this is that it allows for incorporating preferences directly within a unique binary optimisation problem which identifies efficient solutions and associated weights simultaneously. We discuss how preferences can be incorporated within the formulations and also describe how to accommodate the selection of weights when the identification of a unique solution is required. Our results can be used for designing interactive procedures for the solution of multi-objective binary optimisation problems. We describe one such procedure for the multi-objective multi-dimensional binary knapsack formulation of the portfolio selection problem.     

Improper hydrogen bonded cyclohexane C-Hax···Yax contacts: theoretical predictions and experimental evidence from 1H NMR spectroscopy of suitable axial cyclohexane models

C-H(ax)···Y(ax) contacts are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts is investigated in this work. MP2/6-31+G(d,p) calculations predicted the presence of improper hydrogen bonded C-H(ax)···Y(ax) contacts of different strength in substituted cyclohexane rings. To support the theoretical predictions with experimental evidence, several synthetic 2-substituted adamantane analogues (1-24) with suitable improper H-bonded C-H(ax)···Y(ax) contacts of different strength were used as models of a substituted cyclohexane ring. The (1)H NMR signal separation, Δδ(γ-CH(2)), within the cyclohexane ring γ-CH(2)s is raised when the MP2/6-31+G(d,p) calculated parameters, reflecting the strength of the H-bonded C-H(ax)···Y(ax) contact, are increased. In molecules with enhanced improper H-bonded contacts C-H(ax)···Y(ax), like those having sterically crowded contacts (Y(ax) = t-Bu) or contacts including considerable electrostatic attractions (Y(ax) = O-C or O═C) the calculated DFT steric energies of the γ-axial hydrogens are considerably reduced reflecting their electron cloud compression. The results suggest that the proton H(ax) electron cloud compression, caused by the C-H(ax)···Y(ax) contacts, and the resulting increase in Δδ(γ-CH(2)) value can be effected not just from van der Waals spheres compression, but more generally from electrostatic attraction forces and van der Waals repulsion, both of which are improper H-bonding components.     

Double addition of H2 to transition metal-borane complexes: a 'hydride shuttle' process between boron and transition metal centres

The addition of H(2) across a transition metal-borane bond is reported for the first time providing a mechanism for recharging borane functional groups to borohydride.     

Nonvanishing at spatial extremity solutions of the defocusing nonlinear Schrödinger equation

We show local existence of certain type of solutions for the Cauchy problem of the defocusing nonlinear Schrödinger equation with pure power nonlinearity, in various cases of open sets, unbounded or bounded. These solutions do not vanish at the boundary or at infinity. We also show, in certain cases, that these solutions are unique and global.     

On the formation of gap solitons in nonlinear electromagnetic metamaterials

A nonlinear (Kerr‐type) electromagnetic metamaterial, characterized by a double‐Lorentz model of its frequency‐dependent linear effective dielectric permittivity and magnetic permeability, is considered. The formation of gap solitons in the low‐ and high‐frequency band gaps of this metamaterial is investigated analytically. Evolution equations governing the gap solitons, of the form of a nonlinear Klein‐Gordon and a nonlinear Schrödinger equation, are obtained, and the structure of their solutions is discussed.     

Cytoprotective Mechanisms of DJ-1: Implications in Cardiac Pathophysiology

DJ-1 was originally identified as an oncogene product while mutations of the gene encoding DJ-1/PARK7 were later associated with a recessive form of Parkinson’s disease. Its ubiquitous expression and diversity of function suggest that DJ-1 is also involved in mechanisms outside the central nervous system. In the last decade, the contribution of DJ-1 to the protection from ischemia-reperfusion injury has been recognized and its involvement in the pathophysiology of cardiovascular disease is attracting increasing attention. This review describes the current and gaps in our knowledge of DJ-1, focusing on its role in regulating cardiovascular function. In parallel, we present original data showing an association between increased DJ-1 expression and antiapoptotic and anti-inflammatory markers following cardiac and vascular surgical procedures. Future studies should address DJ-1’s role as a plausible novel therapeutic target for cardiovascular disease.