Osmium(VI) complexes as a new class of potential anti-cancer agents

A nitridoosmium(VI) complex [Os(VI)(N)(sap)(OH(2))Cl] (H(2)sap = N-salicylidene-2-aminophenol) displays prominent in vitro and in vivo anti-cancer properties, induces S- and G2/M-phase arrest and forms a stable adduct with dianionic 5'-guanosine monophosphate.     

Simulating radiative shocks with the CRASH laser package

We present the latest improvements in the Center for Radiative Shock Hydrodynamics (CRASH) code, a parallel block-adaptive-mesh Eulerian code for simulating high-energy-density plasmas. The implementation can solve for radiation models with either a gray or a multigroup method in the flux-limited-diffusion approximation. The electrons and ions are allowed to be out of temperature equilibrium and flux-limited electron thermal heat conduction is included. We have recently implemented a CRASH laser package with 3-D ray tracing, resulting in improved energy deposition evaluation. New, more accurate opacity models are available which significantly improve radiation transport in materials like xenon. In addition, the HYPRE preconditioner has been added to improve the radiation implicit solver. With this updated version of the CRASH code we study radiative shock tube problems. In our set-up, a 1 ns, 3.8 kJ laser pulse irradiates a 20 micron beryllium disk, driving a shock into a xenon-filled plastic tube. The electrons emit radiation in the shocked xenon. This radiation preheats the unshocked xenon. Photons traveling ahead of the shock will also interact with the plastic tube, heat it, and in turn this can drive another shock off the wall into the xenon.     

A comparison study of discrete-ordinates and flux-limited diffusion methods for modeling radiation transport

The Center for Radiative Shock Hydrodynamics (CRASH) is investigating methods of improving the predictive capability of numerical simulations for radiative shock waves that are produced in Omega laser experiments. The laser is used to shock, ionize, and accelerate a beryllium foil into a xenon-filled shock tube. These shock waves, when driven above a threshold velocity of about 60 km/s, become strongly radiative and convert much of the incident energy flux into radiation.Radiative shocks have properties that are significantly different from purely hydrodynamic shocks and, in modeling this phenomenon numerically, it is important to compute radiative effects accurately. In this article, we examine approaches to modeling radiation transport by comparing two methods: (i) a computationally efficient, multigroup, flux-limited-diffusion approximation, currently in use in the CRASH radiation-hydrodynamics code, with (ii) a more accurate discrete-ordinates treatment that is offered by the radiation-transport code PDT. We present a selection of results from a growing suite of code-to-code comparison tests, showing both results for idealized problems and for those that are representative of conditions found in the CRASH experiment.     

Sheared poloidal flow driven by mode conversion in tokamak plasmas

A two-dimensional integral full-wave model is used to calculate poloidal forces driven by mode conversion in tokamak plasmas. In the presence of a poloidal magnetic field, mode conversion near the ion-ion hybrid resonance is dominated by a transition from the fast magnetosonic wave to the slow ion cyclotron wave. The poloidal field generates strong variations in the parallel wave spectrum that cause wave damping in a narrow layer near the mode conversion surface. The resulting poloidal forces in this layer drive sheared poloidal flows comparable to those in direct launch ion Bernstein wave experiments.     

Tris interference in IEF and 2-DE

When dried IPGs are hydrated with protein solutions, the concentration of protein and other ionic constituents is constant throughout the strip. Tris, initially present at a very low concentration, focuses during IEF and accumulates in the gradient at a pH corresponding to its pK(a) at the operative temperature of electrophoresis. Tris focuses more rapidly than many basic proteins, and concentrates into a localized zone of increased conductivity which coincides with a precipitous voltage drop in that vicinity. Basic proteins, already near their pI, are frequently observed to align at the periphery of this zone. Acidic proteins imbibed at the basic end of the gradient must traverse this region before this ionic boundary is formed, or otherwise may fail to migrate to their proper positions in the pH gradient.     

Collaborative comparison of simulation codes for high-energy-density physics applications

Advances in plasma physics, powerful lasers, and pulsed-power machines have made possible experiments allowing detailed exploration and discoveries about states of matter at high energy densities. Since these experiments are expensive to perform and difficult to diagnose, numerical simulations have played an important part in designing and understanding them. A number of sophisticated radiation-hydrodynamic codes have been developed to perform this task. We will describe a new collaboration to compare three of these codes for a variety of test problems. Current members of this collaboration are the Center for Radiative Shock Hydrodynamics (CRASH) at the University of Michigan, the FLASH Center at the University of Chicago, and Los Alamos National Laboratory (LANL). These code comparisons have enabled us to understand differences in numerical methods, physical approximations, microphysical parameters, etc. The net result has been an improvement in the codes and higher confidence in the simulation results. This paper presents the results of a subset of these comparison tests.     

A concise stereoselective synthesis of Preussin, 3-epi-Preussin, and analogues

[reaction: see text] A new stereoselective synthesis of the antifungal and antitumor agents Preussin and 3-epi-Preussin via a Pd-catalyzed carboamination of a protected amino alcohol is described. The key transformation leads to simultaneous formation of the N-C2 bond and the C1'-aryl bond, and allows installation of the aryl group one step from the end of the sequence. This strategy permits the facile construction of a variety of preussin analogues bearing different aromatic groups.     

Migration study of zinc dibutyldithiocarbamate in eye drops solutions

The potential deleterious effects of extractables/leachables in pharmaceutical products and the need to preserve product safety throughout its shelf life have led the three major pharmacopoeias (USP, EP, JP) to require extractable and toxicity testing of container/closure systems. To that, a HPLC/UV method was developed and validated for the detection of zinc dibutyl dithiocarbamate (ZDBC) as potential extractable from pharmaceutical container closure system of eye drops solutions. The method consists of direct extraction of the analyte with chloroform; the lower layer was evaporated to dryness and further reconstituted with acetonitrile. The chromatographic separation was performed on a Nova-Pak C18 column using as mobile phase a mixture of acetonitrile:water. Calibration curves were linear and relative standard deviation was sufficient. Detection limit of ZDBC was found to be 0.015 μg/mL. The HPLC method was further applied in seven currently marketed eye drops solutions, confirming its applicability for monitoring dithiocarbamates migration from container closure systems into the eye drops solutions.     

Proline dipeptides containing fluorine moieties as oganocatalysts for the asymmetric aldol reaction

A series of dipeptide analogues consisting of proline, phenylalanine and aniline- or phenol-fluorine derivatives were synthesized. Their catalytic ability was evaluated in the intermolecular asymmetric aldol reaction, both in organic and aqueous media. Aniline-fluorine derivatives proved to be superior and the best results were obtained, when 2-CF₃ aniline was employed. A diverse substrate scope consisting of both aromatic and aliphatic aldehydes, as well as different ketones was demonstrated, where aromatic aldehydes afforded products in high yields (up to 100%) with excellent diastereo- (up to 95:5) and enantioselectivities (up to 97%), whereas the aliphatic aldehydes afforded also excellent selectivities, but relatively low yield. A simple addition of fluorine to a dipeptide analogue affords organocatalysts with new interesting properties that can catalyze the aldol reaction more efficiently.