Free energy calculations of small molecules in dense amorphous polymers. Effect on the initial guess configuration in molecular dynamics studies

The excess free energy of small molecules in the amorphous polymers poly(ethylene) and poly(dimethylsiloxane) was calculated, using the test-particle-insertion method. The method was applied to polymer configurations obtained from molecular dynamics simulations with differently prepared initial guess configurations. It was found that the calculated solubility coefficients strongly depend on the quality of the initial guess configuration. Slow compression of dilute systems, during which process only the repulsive parts of the nonbonded Lennard-Jones potentials are taken into account, yields polymer melts which are better relaxed, and which offer lower solubilities for guest molecules compared with polymer melts generated at the experimental density or prepared by compressing boxes with soft-core nonbonded potentials. For the last two methods initial stresses relax by straining the internal modes (bond angles, torsion angles) of the chain

Characterization of hemodialysis membranes by inverse size exclusion chromatography

Inverse size exclusion chromatography (i-SEC) was used to characterize three different cellulosic hollow fiber hemodialysis membranes, i.e. low-flux cuprophan and hemophan and high-flux RC-HP400A. With the i-SEC technique the pore size distribution and porosity of a membrane can be determined and adsorption phenomena can be studied. The membranes showed clear differences in pore size and porosity, the high-flux RC-HP400A membrane has a larger pore size as well as a higher porosity. For all the membranes it was found that the elution curves were best described by a homoporous pore volume distribution. It appeared that the bound or non-freezing water in the membranes was at least partly accessible to solutes. The test molecules creatinine and vitamin B 12 both adsorbed to the cellulosic membranes. The adsorption behavior of creatinine was strongly dependent on the NaCl concentration present. The observations could be explained by assuming that cuprophan and RC-HP400A are negatively charged whereas hemophan is positively charged due to the modification with N,N-diethylaminoethyl ether. The net charge of the hemophan is smaller

Assymetric bipolar membranes in acid-base electrodialysis

In this experimental study, the influence of asymmetric bipolar membranes on the salt impurities in the acid and base product is investigated. The thickness of one, the other, or both ion-permeable layers of a bipolar membrane is increased. With increased layer thickness, the current-voltage curves of the electrodialysis repeat unit recorded in a pilot-scale module show a reduced limiting current density, and thus they indicate an overall higher selectivity of these arrangements. Furthermore, these curves indicate water transport limitations for some membrane arrangements. Electrodialysis experiments with the same module at a high current density confirm the overall salt ion flux reduction. Moreover, these acid-base electrodialysis experiments directly reveal an increased asymmetry of the salt ion fluxes which can be utilized to design custom-made bipolar membranes with very high purity of either the produced acid or the base while keeping the bipolar membrane functioning without water transport limitations. The presented experiments also show that the bipolar membrane behavior can be characterized in situ, i.e., as a part of a electrodialysis repeat unit mounted in a pilot-scale electrodialysis module