Convergent route to the purpuromycin bisphenolic spiroketal: hydrogen bonding control of spiroketalization stereochemistry

A mild and efficient [3+2] nitrile oxide/olefin cycloaddition provided a rapid and convergent entry into precursors of bisphenolic spiroketals, a structural type unique to the rubromycin family of natural products. In addition, implementation of the premise that a hydrogen bond from the C4-OH controls the stereochemistry of the purpuromycin core resulted in moderate diastereocontrol in the spiroketalization. Spectroscopic and X-ray data of these systems have provided the first assignment of the relative configuration of purpuromycin.     

Angular self-intersections for closed geodesics on surfaces

In this note we consider asymptotic results for self-intersections of closed geodesics on surfaces for which the angle of the intersection occurs in a given arc. We do this by extending Bonahon's definition of intersection forms for surfaces.

     

Dielectric properties of a hydrated sulfonated poly(styrene-ethylene/butylenes-styrene) triblock copolymer

The present study showed that sulfonated poly(styrene-ethylene/butylenes-styrene) (S-SEBS) triblock copolymer ionomers can be made to exhibit dielectric constants on the order of a hundreds thousand. Although they are too lossy at this point to use as dielectric materials in capacitors or as electrostrictive Maxwell effect transducer materials because of their high hydrogen ion conductivity, the results of these initial dielectric studies as a function of ion content were used to try to understand the effects of a polar plasticizer, water, on dielectric properties of the acid form of this ionomer. This was done before moving on to more tightly bound ions (rather than the hydrogen ions of the sulfonic acid groups used here) and to other polar, less mobile plasticizers (which also interact strongly with the ionic dipoles). The discovery of such high dielectric constants suggested the possibility that low dielectric loss versions of this type of polymer, as well as other members of the class known as ionomers, might find future applications as extremely high dielectric constant materials in capacitors or transducers. Experimental results for films with degrees of sulfonation on the order of 10% or more showed dielectric constants on the order of ?′ ∼ 100,000 but dielectric loss tangents near D = tan δ ∼ 0.3, when the materials were exposed to high humidity conditions. Experiments to determine the effects of water content on the material's dielectric response showed that water can easily move into and out of the films studied and that this transport behavior is strongly correlated to the relative humidity of the environment and to the degree of sulfonation. Water content, in this case, was thus the primary consideration when attempting to understand the observed high dielectric constants in films with degree of sulfonation greater than 5.5%. However, vacuum-dried films were, also, examined and observed to exhibit a dielectric constant on the order of 2 until the degree of sulfonation was greater than 11%. Above this value, the dielectric constant increased by approximately 100% to a value on the order of 4.     

A computer-assisted proof of Saari's conjecture for the planar three-body problem

The five relative equilibria of the three-body problem give rise to solutions where the bodies rotate rigidly around their center of mass. For these solutions, the moment of inertia of the bodies with respect to the center of mass is clearly constant. Saari conjectured that these rigid motions are the only solutions with constant moment of inertia. This result will be proved here for the planar problem with three nonzero masses with the help of some computational algebra and geometry.

     

Erwiderung

Ohne Zusammenfassung     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.