Accuracy of free energies of hydration for organic molecules from 6-31g*-derived partial charges

Absolute free energies of hydration have been computed for 13 diverse organic molecules using partial charges derived from ab initio 6-31G* wave functions. Both Mulliken charges and charges fit to the electrostatic potential surface (EPS) were considered in conjunction with OPLS Lennard–Jones parameters for the organic molecules and the TIP4P model of water. Monte Carlo simulations with statistical perturbation theory yielded relative free energies of hydration. These were converted to absolute quantities through perturbations to reference molecules for which absolute free energies of hydration had been obtained previously in TIP4P water. The average errors in the computed absolute free energies of hydration are 1.1 kcal/mol for the 6-31G* EPS charges and 4.0 kcal/mol for the Mulliken charges. For the EPS charges, the largest individual errors are under 2 kcal/mol except for acetamide, in which case the error is 3.7 kcal/mol. The hydrogen bonding between the organic solutes and water has also been characterized. © John Wiley & Sons, Inc.     

A novel method for crack detection in beam-like structures by measurements of natural frequencies

A novel method is proposed for calculating the natural frequencies of a multiple cracked beam and detecting unknown number of multiple cracks from the measured natural frequencies. First, an explicit expression of the natural frequencies through crack parameters is derived as a modification of the Rayleigh quotient for the multiple cracked beams that differ from the earlier ones by including nonlinear terms with respect to crack severity. This expression provides a simple tool for calculating the natural frequencies of the beam with arbitrary number of cracks instead of solving the complicated characteristic equation. The obtained nonlinear expression for natural frequencies in combination with the so-called crack scanning method proposed recently by the authors allowed the development of a novel procedure for consistent identification of unknown amount of cracks in the beam with a limited number of measured natural frequencies. The developed theory has been illustrated and validated by both numerical and experimental results.     

Estimation of radon and thoron caused dose at exraction and processing sites of mineral sand mining area in Vietnam (HA TINH province)

Mineral sands are mined in several countries to supply to the titanium and zircon producing industries. Coastal black mineral sands usually contain, besides ilmenite (FeTiO₃) and rutile (TiO₂), radioactive minerals such as zircon (ZrSiO₄) and monazite (RePO₄). Radon and thoron activity concentration originated from natural radioactive contents of the black mineral sand was monitored at the extraction and processing for black minerals in the coastal areas of Ha Tinh Province, one of the around 40 coastal mineral sand deposits in Vietnam. The survey was carried out with the Raduet chambers made by Radosys Ltd—Hungary. The obtained results for 25 investigated points show that the measured values are not high in the residential houses and in case of the sand extraction site as well. At the titanium processing plant the measured values were higher than outside the facility (Radon: 18–55 Bq/m³ with average of 34 Bq/³ and Thoron 33–118 Bq/m³ with average of 58 Bq/m³) but still comparable to the average concentration of the world published by UNSCEAR. The typical outdoor levels of radon and thoron gas are each of the order of 10 Bq/m³. Although the radon concentrations were low in the zircon and titanium processing plants, the thoron concentrations in the houses for separating rutile and zircon were very high. At zircon processing factory, the thoron concentration could reach 2,931 Bq/m³ and the estimated annual effective dose would be 21.4 mSv/a. Intervention has to be taken in order to reduce the thoron level in this factory since the level of thoron and its progenies corresponding to an annual occupational effective dose is beyond the action level of 6 mSv/a.     

Topography Influence on the Lake Equations in Bounded Domains

We investigate the influence of the topography on the lake equations which describe the two-dimensional horizontal velocity of a three-dimensional incompressible flow. We show that the lake equations are structurally stable under Hausdorff approximations of the fluid domain and L ^p perturbations of the depth. As a byproduct, we obtain the existence of a weak solution to the lake equations in the case of singular domains and rough bottoms. Our result thus extends earlier works by Bresch and Métivier treating the lake equations with a fixed topography and by Gérard-Varet and Lacave treating the Euler equations in singular domains.     

On the No-Gap Second-Order Optimality Conditions for a Discrete Optimal Control Problem with Mixed Constraints

Motivated by our recent works on optimality conditions in discrete optimal control problems under a nonconvex cost function, in this paper, we study second-order necessary and sufficient optimality conditions for a discrete optimal control problem with a nonconvex cost function and state-control constraints. By establishing an abstract result on second-order optimality conditions for a mathematical programming problem, we derive second-order necessary and sufficient optimality conditions for a discrete optimal control problem. Using a common critical cone for both the second-order necessary and sufficient optimality conditions, we obtain “no-gap” between second-order optimality conditions.     

A note on Prandtl boundary layers

This note concerns nonlinear ill‐posedness of the Prandtl equation and an invalidity of asymptotic boundary layer expansions of incompressible fluid flows near a solid boundary. Our analysis is built upon recent remarkable linear illposedness results established by Gérard‐Varet and Dormy and an analysis by Guo and Tice. We show that the asymptotic boundary layer expansion is not valid for nonmonotonic shear layer flows in Sobolev spaces. We also introduce a notion of weak well‐posedness and prove that the nonlinear Prandtl equation is not well‐posed in this sense near nonstationary and nonmonotonic shear flows. On the other hand, we are able to verify that Oleinik's monotonic solutions are well‐posed. © 2011 Wiley Periodicals, Inc.     

Radial distribution of RNA genomes packaged inside spherical viruses

The problem of RNA genomes packaged inside spherical viruses is studied. The RNA-capsid attraction is assumed to be nonspecific and occurs at the inner capsid surface only. For weak attraction, RNA concentration is maximum at the center of the capsid to maximize their configurational entropy. For stronger attraction, RNA concentration peaks near the capsid surface. In the latter case, the competition between the branching of RNA secondary structure and its adsorption to the inner capsid results in the formation of a dense layer of RNA near capsid surface. The layer thickness is a slowly varying (logarithmic) function of the capsid inner radius. Consequently, the amount of RNA packaged is proportional to the capsid area (or the number of proteins) instead of its volume. The numerical profiles describe reasonably well the observed RNA concentration profiles of various viruses.     

Mordukhovich subgradients of the value function to a parametric discrete optimal control problem

This paper is devoted to the study of the first-order behavior of the value function of a parametric discrete optimal control problem with nonconvex cost functions and control constraints. By establishing an abstract result on the Mordukhovich subdifferential of the value function of a parametric mathematical programming problem, we derive a formula for computing the Mordukhovich subdifferential of the value function to a parametric discrete optimal control problem.     

Two new simple iridoids from the ant-plant Myrmecodia tuberosa and their antimicrobial effects

Six iridoid derivatives (1–6), including two new compounds myrmecodoides A and B (1 and 2), were isolated from the ant-plant Myrmecodia tuberosa. Their structures were determined on the basis of spectroscopic data (¹H and ¹³C NMR, HSQC, HMBC, ¹H-¹H COSY, NOESY and HR-ESI-MS) and by comparison with the literature values. Among isolates, 3 and 4 exhibit weak antibacterial effect against Staphylococcus aureus subsp. aureus with MIC value of 100.0 μg/mL.