The ammonia dimer equilibrium dissociation energy: convergence to the basis set limit at the correlated level

The low-energy region of the intermolecular potential energy hypersurface (PES) of the ammonia dimer was studied at the level of second-order Moller-Plesset perturbation theory (MP2) using a very large basis set. Individual minima were located on the PES employing the counterpoise (CP) correction to account for the basis set superposition error (BSSE). Apart from these canonical MP2 calculations local MP2 (LMP2) calculations were performed. For the latter the BSSE at the correlated level is inherently absent by virtue of the local truncation of the virtual space. Results from canonical and local MP2 calculations are compared and the reliability of the LMP2 method for intermolecular complexes and clusters is discussed. The canonical MP2 calculations predicted five minimum structures, the four most stable ones lying energetically very close. For these four structures single point MP2 energy calculations with a further extended basis set (1024 functions for the ammonia dimer) were performed. The equilibrium dissociation energies so obtained are close to the one-particle basis set limit, as illustrated by a remaining BSSE of less than 0.2 kJ mol^?1. The geometry optimizations at the LMP2 level, using the three most stable canonical MP2 structures as initial geometries, all collapsed to a single minimum corresponding to an asymmetric structural arrangement. A canonical MP2 single point calculation, at that geometry, revealed that the LMP2 minimum structure is virtually as stable as the lowest minima on the canonical MP2 PES. Based on these calculations the global minimum of the ammonia dimer was assigned to a part of the PES represented by an asymmetric structure with an equilibrium dissociation energy of 13.5±0.3 kJ mol^?1     

Superhydrophobic materials for tunable drug release: using displacement of air to control delivery rates

We have prepared 3D superhydrophobic materials from biocompatible building blocks, where air acts as a barrier component in a porous electrospun mesh to control the rate at which drug is released. Specifically, we fabricated poly(ε-caprolactone) electrospun meshes containing poly(glycerol monostearate-co-ε-caprolactone) as a hydrophobic polymer dopant, which results in meshes with a high apparent contact angle. We demonstrate that the apparent contact angle of these meshes dictates the rate at which water penetrates into the porous network and displaces entrapped air. The addition of a model bioactive agent (SN-38) showed a release rate with a striking dependence on the apparent contact angle that can be explained by this displacement of air within the electrospun meshes. We further show that porous electrospun meshes with higher surface area can be prepared that release more slowly than control nonporous constructs. Finally, the entrapped air layer within superhydrophobic meshes is shown to be robust in the presence of serum, as drug-loaded meshes were efficacious against cancer cells in vitro for >60 days, thus demonstrating their applicability for long-term drug delivery.     

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The morphology of fibrillar polyethylene crystals

A comparison has been made of the morphology of fibrillar polyethylene crystals prepared by shear-induced crystallization and heterogeneous Ziegler-Natta catalysis under similar solvent and temperature conditions. Both specimens had a shish-kebab superstructure consisting of lamellar overgrowths on a filamentary backbone. For polyethylenes stirrer-crystallized at small supercoolings, the overgrown lamallae were removed by nitric acid oxidation followed by selective dissolution, leaving naked filamentary ribbons. Thermal analysis of these specimens suggested a dual molecular conformation of both folded and extended chains. The fact that these fibrils did not deform easily under uniaxial stress conforms with a core of extended chains. Thermal and oxidative behavior of polyethylenes prepared at lower crystallization temperatures suggested a greater content of chain folds in the central thread as the degree of supercooling increased. The Ziegler-Natta fibrils were degraded into lamellar fragments on oxidation and their thermal behavior suggested a predominantly folded-chain conformation. Uniaxial deformation occurred on stretching the Ziegler-Natta specimens in harmony with a core of folded chains. Molecular models have been proposed to account for the observed phenomena.     

REBUILDING THE EASTERN BALTIC COD STOCK UNDER ENVIRONMENTAL CHANGE (PART II): TAKING INTO ACCOUNT THE COSTS OF A MARINE PROTECTED AREA

Abstract This study adds a cost analysis of the Eastern Baltic cod fishery to the existing model presented in Röckmann et al. [2007a] . As cost data on this international fishery do not exist, data from Denmark are extrapolated to the whole international fishery. Additionally, unit and total variable costs are simulated, and the sensitivity to a set of different cost–stock and cost–output elasticities is tested. The study supports preliminary conclusions that a temporary marine reserve policy, which focuses on protecting the Eastern Baltic cod spawning stock in the International Council for the Exploration of the Sea (ICES) subdivision 25, is a valuable fisheries management tool to (i) rebuild the overexploited Eastern Baltic cod stock and (ii) increase operating profits. The negative effects of climate change can be postponed for at least 20 years—depending on the assumed rate of future climate change. Including costs in the economic analysis does not change the ranking of management policies as proposed in the previous study where costs were neglected.     

REBUILDING THE EASTERN BALTIC COD STOCK UNDER ENVIRONMENTAL CHANGE–A PRELIMINARY APPROACH USING STOCK,ENVIRONMENTAL, AND MANAGEMENT CONSTRAINTS

ABSTRACT. . The population dynamics of the Eastern Baltic cod (Gadus morhua callarias L.), unlike many other stocks, shows a strong dependency on environmental conditions. To test the implications of different management policies on the stock and the fishery in a system of global environmental change, we apply a spatially disaggregated, discrete time, age‐structured model of the Eastern Baltic cod stock in 50 year simulation analyses. The simulation provides an analysis of stock, yield, and revenue development under various management policies and environmental scenarios. The policy analysis, focusing on different regulations of fishing mortality, is embedded into three environmental scenarios, assuming low, medium, or high climate and environmental change. The environmental assumptions are based on simulation results from a coupled atmosphere‐ocean regional climate model, which project salinity in the Baltic Sea to decrease by 7–47% in the period 2071–2100 relative to the reference period 1961 1990. Our simulation results show that a significant reduction in fishing mortality is necessary for achieving high long‐term economic yields. Moreover, under the environmental scenarios presented, a stock collapse cannot be prevented. It can, however, be postponed by the establishment of a marine reserve in ICES subdivision 25.     

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Analytical and Bioanalytical Chemistry -     

Some topological dynamics properties of discrete-time control systems

This paper is concerned with the study of certain stabilityproperties of discrete-time systems by means of topologicalmethods. It turns out that suitably defined sets guarantee thestability of the reachable sets in the vicinity of compact sets.Furthermore, special properties about affine control systemsare given.