Lithiation and electrophilic substitution of 8-chlorodibenz[b,f][1,4]-oxazepine-10-tert-butylcarbamate: The preparation of novel fused heterocyclic derivatives of 8-chlorodibenzoxazepine

Lithiation of 8-chlorodibenz[b,f][1,4]oxazepine-10-tert-butylcarbamate ( 1 ) is described. Electrophilic substitution of the resulting N-Boc dibenzoxazepine α- lithioamine 2 with ketones, aldehydes, nitriles, iso-cyanates and imines, followed by an in-situ cyclization, gave fused carbamates 5–26 , fused 2H-imidazol-2-ones 27–29 , fused hydantoins 30–32 , and fused ureas 33–35 , respectively, in 11–66% yield.     

Voltammetric sizing of a sphere.

The size of a glass sphere positioned in the center of a microdisk electrode is determined by using a simple electrochemical procedure and is confirmed, additionally, by a microscopical measurement of the sphere at the time of the electrochemical measurement. The cyclic voltammetric response of the naked electrode and of the electrode with the sphere positioned in its center is recorded over a wide range of scan rates (0.002-1.5 V s(-1)). The size of the sphere is then determined by comparison of the experimental voltammogram with simulations for each individual scan rate.     

Molecular approaches to solar energy conversion with coordination compounds anchored to semiconductor surfaces

Strategies toward the realization of molecular control of interfacial charge transfer at nanocrystalline semiconductor interfaces are described. Light excitation of coordination compounds, based on (dpi)6 transition metals, anchored to wide band-gap semiconductors, such as TiO2, can initiate electron-transfer processes that ultimately reduce the semiconductor. Such photoinduced charge-separation processes are a key step for solar energy conversion. The thermodynamics and kinetic rate constants for three different interfacial charge separation mechanisms are discussed. Tuning the energetic position of the semiconductor conduction band relative to the molecular sensitizer has provided new insights into interfacial charge transfer. Supramolecular compounds that efficiently absorb light, promote interfacial electron transfer, and feature additional functions such as intramolecular electron transfer when bound to semiconductor surfaces have also been studied. New approaches for enhancing charge-separation lifetimes for solar energy conversion are presented.     

The application of INAA to the geochemical analysis of single diamonds

Instrumental neutron activation analysis (INAA) has been applied to the analysis of 62 small (0.01–0.5 carat), single, inclusion-bearing and inclusion-free diamonds from South Africa, Brazil and Colorado. Up to 40 elements were detected at the ppb and ppt levels in individual diamonds of the eclogitic (basaltic affinity) and the peridotitic (ultramafic) paragenesis. The data obtained in this study can be used to distinguish between diamonds from the eclogitic and peridotitic parageneses and provides geochemical information on the environment in which diamonds crystallize. Further, the technique may prove to be useful in fingerprinting diamonds of different provenance areas.     

The transparency of polyurethane-poly(methyl methacrylate) interpenetrating and semi-interpenetrating polymer networks

Various combinations of polyurethane (PUR) and poly(methyl methacrylate) (PMMA) were prepared as interpenetrating polymer networks (IPN) or semi-IPNs. In the latter, either the PUR or the PMMA component was crosslinked. The optical transmissions of these materials were measured as a function of the crosslink degrees of both phases. The role of the PUR chain extender, poly(oxypropylene) glycol, is discussed. It is concluded that any means which increases the degree of phase dispersion favours the transparency of PUR/PMMA based IPNs and semi-IPNs.