Osmotically induced morphological changes of extruded dioctadecyldimethylammonium chloride (DODAC) dispersions

Extruded vesicles, which are often used as models for living cells, can change their morphology when they are diluted into a hyperosmotic medium. Different morphological changes were observed with extruded dioctadecyldimethylammonium chloride (DODAC) vesicles after dilution with a nonionic (sucrose) and ionic (CaCl2) osmotic agent above and below the gel-to-liquid crystalline transition temperature. By means of turbidimetry, dynamic light scattering, and cryo-transmission electron microscopy, it was seen that the vesicles only deflated when they were in the gel state, whereas in the liquid crystalline state, an ionic osmotic agent could induce twinning of the vesicles, reminiscent to endocytosis. The latter could occur as a result of the combined effects of reduced repulsion, local dehydration, and reduced bending rigidity induced by the ionic agent.     

A liquid chromatography – tandem mass spectrometry method to measure a selected panel of uremic retention solutes derived from endogenous and colonic microbial metabolism

Chronic kidney disease (CKD) is associated with an increased risk of mortality and cardiovascular disease, which is, at least partly, mediated by the accumulation of so-called uremic retention solutes. Although there has been an increasing interest in the behavior of these solutes, derived from both the endogenous and colonic microbial metabolism, methods to simultaneously and accurately measure a broad panel of relevant uremic retention solutes remain scarce.     

Green's-function reaction dynamics: a particle-based approach for simulating biochemical networks in time and space

We have developed a new numerical technique, called Green's-function reaction dynamics (GFRD), that makes it possible to simulate biochemical networks at the particle level and in both time and space. In this scheme, a maximum time step is chosen such that only single particles or pairs of particles have to be considered. For these particles, the Smoluchowski equation can be solved analytically using Green's functions. The main idea of GFRD is to exploit the exact solution of the Smoluchoswki equation to set up an event-driven algorithm, which combines in one step the propagation of the particles in space with the reactions between them. The event-driven nature allows GFRD to make large jumps in time and space when the particles are far apart from each other. Here, we apply the technique to a simple model of gene expression. The simulations reveal that spatial fluctuations can be a major source of noise in biochemical networks. The calculations also show that GFRD is highly efficient. Under biologically relevant conditions, GFRD is up to five orders of magnitude faster than conventional particle-based techniques for simulating biochemical networks in time and space. GFRD is not limited to biochemical networks. It can also be applied to a large number of other reaction-diffusion problems.     

Selective oxidation of methane by the bis(mu-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites

This work reports on the capability of the O2-activated Cu-ZSM-5 and Cu-MOR zeolites to selectively convert methane into methanol at a temperature of 398 K. A strong correlation between (i) the activity and (ii) the intensity of the 22 700 cm-1 UV-vis band, assigned to the bis(mu-oxo)dicopper core, is found (i) as a function of the reaction temperature, (ii) as a function of the Cu loading of the zeolite, and (iii) in comparison to other Cu materials. These three lines of evidence firmly support the key role of the bis(mu-oxo)dicopper core in this selective, low-temperature hydroxylation of methane.     

Computational Fluid Dynamic Design of Jet Stirred Reactors for Measuring Intrinsic Kinetics of Gas‐Phase and Gas‐Solid Reactions

Nonreactive and reactive computational fluid dynamic simulations were applied to optimize the design of a laboratory scale jet stirred reactor for measuring intrinsic kinetics of gas‐phase and gas‐solid reactions, i.e. kinetics determined by chemical steps only and not by heat or mass transfer. In the past these reactors were designed and tested based on empirical design criteria and residence time distribution experiments. This work shows that these do not always capture important local effects that are vital for kinetic studies. First the degree of macro–mixing was evaluated for three different geometries (down case, 45° case and 90° case) by performing in silico residence time distribution experiments at 900 K, showing that with these type of experiments only minor differences are observed. However, the ethane steam cracking simulations revealed major differences, with the 45° case being the most uniform in terms of temperature and the 90° case being by far the worst. The species nonuniformity in all geometries was acceptable and was in some cases even partly masked by important shortcut streams such as those observed in the 90° case. The existing gradients on the substrate surface are sufficiently small to be neglected in modeling efforts. As temperature is the major parameter determining the rate of the surface reactions, the 45° case is suggested as the best geometry for measuring intrinsic kinetics.     

Biosynthesis of PR toxin by Penicillium roqueforti, Part 2 evidence for an hydride shift from 2H N.M.R. spectroscopy

The biosynthesis of the eremophilane sesquiterpenoid PR toxin is shown to involve an 1,2-hydride migration from C(5) to C(4) of the molecule.     

Ultrafiltration of a polymer-electrolyte mixture

We present a mathematical model to describe the ultrafiltration behaviour of polymer-electrolyte mixtures. The model combines the proper thermodynamic forces (pressure, chemical potential and electrical potential differences) with multicomponent diffusion theory. The model is verified with experimental data on the ultrafiltration of aqueous solutions of PEG-4000 and potassium phosphate. The single solute rejection of PEG-4000 goes through a maximum as also found by others. The single solute rejection of potassium phosphate depends on the ionic strength of the solution. At low ionic strength rejections are found of 50%. Solutions containing a high concentration of PEG-4000 and potassium phosphate show a negative rejection for potassium phosphate. This is caused by the strongly non-ideal behaviour of these aqueous solutions. The model predicts the behaviour of single solute experiments quite well, but some deviations are found with the mixed solute experiments. However, negative rejections found in the mixed solute experiments are predicted by the model.     

DFT study on H2O activation by stepped and planar Rh surfaces

In this research the effect of steps (lower coordinated surface atoms) and the presence of pre-adsorbed oxygen on the activation energy of water are studied with DFT. Without oxygen water activation is found to be structure insensitive. When oxygen is adsorbed on the surface and acts as the acceptor for the hydrogen at the step edge, the barrier will decrease significantly.     

Interplay between structure and size in a critical crystal nucleus

We study the kinetics of crystal nucleation of an undercooled Lennard-Jones liquid using various path-sampling methods. We obtain the rate constant and elucidate the pathways for crystal nucleation. Analysis of the path ensemble reveals that crystal nucleation occurs along many different pathways, in which critical solid nuclei can be small, compact, and face centered cubic, but also large, less ordered, and more body centered cubic. The reaction coordinate thus includes, besides the cluster size, also the quality of the crystal structure.