Abstract Polystyrol (Ia) kann zu (Ib) bromiert und dann nach Metallierung zu (Ic) mit Disulfiden (II) in die Thioether (III) übergeführt werden.
Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g/L) densities to be achieved by 2015. From our continuous efforts on hydrogen storage, it is believed that metalation of highly porous solids with high-valence metals is promising and provides a rational direction to realize high volumetric hydrogen density near room temperature. This grant was focused on the study of high surface area covalent organic frameworks (COFs) with these specific objectives (1) to introduce potential metal binding sites through the COF synthesis and (2) to implement metalation experiments and evaluate their respective hydrogen adsorption properties. To maximize our efforts, simulation calculations were also performed (prior to experiments) for the prediction of binding enthalpy of hydrogen for molecular building units containing transition metals and promising COF structures to increase volumetric hydrogen uptake at room temperature. In this effort, first molecular building units with optimal binding energy for hydrogen storage (20 kJ/mol) were designed by quantum mechanical (QM) methods. Employing these results, it was revealed that one of metalated COFs takes up 60 g/L (total) of H2 at 100 bar and 298 K. To realize proposed COF structures, chemistry of COF synthesis has been developed; for instance, new air stable COFs were synthesized via hydrazone (COF-41 to 43) and imine condensation (COF-301, 320, 340, and 366) and some of them were tested the effect on metalation. Finally, a new triazine COF with high volumetric hydrogen uptake capacity was presented as a proposed future direction.
Metallic glasses are commonly found to favor denser packing structures and icosahedral order in experiments, simulations, and theoretical models. Here we present a molecular dynamics simulation study of Cu-Zr metallic glasses, prepared through a pressure-mediated pathway. The resulting glasses exhibit anomalous structure-property relationships; these glasses are less energetically stable, concomitant with a denser atomic packing and a significant increase in icosahedral short-range order. The enhanced icosahedral order is shown to be accompanied by a pressure-mediated change in chemical short-range order. The results demonstrate that in amorphous alloys (nonmonatomic), theoretical frameworks of the two-order-parameter model must be generalized to account for chemical degrees of freedom.
The photo-Fries rearrangement which was first reported (1,2) in the early 1960's has some potential in the design of photoresist materials since it involves the transformation of molecules such as phenolic esters into free phenols, thereby providing a route to selective image development by differential dissolution. Initial interest in the photo-Fries rearrangement of aromatic polyesters was mainly due to the fact the reaction is accompanied by the formation of o-hydroxy aromatic compounds which possess great photostability. This interesting property of the rearranged products can be used to design polymers containing photostabilizing ortho-hydroxy aromatic groups (3-6); the photostabilizing action of such compounds has been recently reviewed (7-8). Scheme 1 shows the reaction which occurs when an aromatic polyester such as [I] is subjected to UV irradiation (5). The polymer first undergoes main-chain cleavage with subsequent rearrangement to polymer [II] which is photostable and can be used as a thin coating to