Species differences in the metabolism of arsenic compounds

Humans are exposed via air, water and food to a number of different arsenic compounds, the physical, chemical, and toxicological properties of which may vary considerably. In people eating much fish and shellfish the intake of organic arsenic compounds, mainly arsenobetaine, may exceed 1000 μg As per day, while the average daily intake of inorganic arsenic is in the order of 10–20 μg in most countries. Arsenobetaine, and most other arsenic compounds in food of marine origin, e.g. arsenocholine, trimethylarsine oxide and methylarsenic acids, are rapidly excreted in the urine and there seem to be only minor differences in metabolism between animal species. Trivalent inorganic arsenic (AsIII) is the main form of arsenic interacting with tissue constituents, due to its strong affinity for sulfhydryl groups. However, a substantial part of the absorbed AsIII is methylated in the body to less reactive metabolities, methylarsonic acid (MMA) and dimethylarsinic acid (DMA), which are rapidly excreted in the urine. All the different steps in the arsenic biotransformation in mammals have not yet been elucidated, but it seems likely that the methylation takes place mainly in the liver by transfer of methyl groups from S-adenosylmethionine to arsenic in its trivalent oxidation state. A substantial part of absorbed arsenate (AsV) is reduced to AsIII before being methylated in the liver. There are marked species differences in the methylation of inorganic arsenic. In most animal species DMA is the main metabolite. Compared with human subjects, very little MMA is produced. The marmoset monkey is the only species which has been shown unable to methylate inorganic arsenic. In contrast to other species, the rat shows a marked binding of DMA to the hemoglobin, which results in a low rate of urinary excretion of arsenic.     

Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Sur les valeurs propres d'un oscillateur harmonique perturbé

Sans résumé Dedicated to Professor Shmuel Agmon     

Fully adaptive multiresolution finite volume schemes for conservation laws

The use of multiresolution decompositions in the context of finite volume schemes for conservation laws was first proposed by A. Harten for the purpose of accelerating the evaluation of numerical fluxes through an adaptive computation. In this approach the solution is still represented at each time step on the finest grid, resulting in an inherent limitation of the potential gain in memory space and computational time. The present paper is concerned with the development and the numerical analysis of fully adaptive multiresolution schemes, in which the solution is represented and computed in a dynamically evolved adaptive grid. A crucial problem is then the accurate computation of the flux without the full knowledge of fine grid cell averages. Several solutions to this problem are proposed, analyzed, and compared in terms of accuracy and complexity.

     

Finding nonnormal bent functions

The question if there exist nonnormal bent functions was an open question for several years. A Boolean function in n variables is called normal if there exists an affine subspace of dimension n/2 on which the function is constant. In this paper we give the first nonnormal bent function and even an example for a nonweakly normal bent function. These examples belong to a class of bent functions found in [J.F. Dillon, H. Dobbertin, New cyclic difference sets with Singer parameters, in: Finite Fields and Applications, to appear], namely the Kasami functions. We furthermore give a construction which extends these examples to higher dimensions. Additionally, we present a very efficient algorithm that was used to verify the nonnormality of these functions.     

Disorder arising from the location of enantiomers in a twist-boat structure: 2,6-trans-2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian

Crystals of the title compound are orthorhombic, Pca2₁;a=27.586(4),b=10.509(3),c=11.080(2) Å,V=3212(1) ų,Z=8. The structure was solved by direct methods, from data collected at room temperature on an Enraf-Nonius CAD4 diffractometer, and refined by full-matrix least squares to a finalR value of 0.055 using 2043 reflections. One of the two independent molecules in the asymmetric unit is disordered. The disorder is manifested mainly between the oxygen atom and one sulfur atom and is caused by opposite enantiomers occupying corresponding positions in different unit cells. The endocyclic torsion angles in both independent molecules are very similar but the disposition of the heteroatoms on the twist-boat framework is different in the two molecules. Site occupancy of the two models on this framework in the disordered molecule is in the ratio 2179 with the smaller proportion being very similar to the ordered molecule and the remainder similar to that found in the normal molecule oftrans-4-chloro-2,4,6-tris(trichloromethyl)-1-oxa-3,5-dithian (Irving and Irving, 1988).