Mechanisms and Möbius strips: understanding dynamic processes in annulenes

Exploratory computational studies on annulenes with planar, Möbius, and two‐twist topologies have resulted in new mechanisms to explain facile thermal configuration change (cis‐trans isomerization) for medium‐sized annulenes ([12]‐ to [16]annulene). Möbius π‐bond shifting through both aromatic and antiaromatic transition states, two‐twist π‐bond shifting, and planar nondegenerate π‐bond shifting can all be invoked to explain experimental results. Moreover, a simple bond‐shift rule, which is based on the change in number of trans C?C double bonds (Δtrans), was developed that predicts the topology of the transition state(s) necessary to effect the desired cis‐trans isomerization. The bond‐shift rule was also applied to configuration change in dehydro[12]annulene. Finally, extensive investigation of the [14]annulene hypersurface revealed that numerous Möbius minima exist within 10 kcal/mol of the global minimum. Copyright © 2012 John Wiley & Sons, Ltd.     

Lancaster delftware: a Raman spectroscopy,electron microscopy and Mössbauer spectroscopy compositional study

In 2008, excavations were conducted by the Northern Ceramic Society at the site of the former Lancaster delftware potworks, which operated between 1754 and about 1790. The recovered sherds have been non‐destructively examined by Raman and electron microscopies and the iron phases in the biscuit by Mössbauer spectroscopy. These methods have provided a new understanding of the mineralogy of the delftware produced at Lancaster using clay imported from Carrickfergus in Ireland and blended with the local ferruginous‐aluminous clays. This has implications for the attribution of delftware produced at Liverpool, Bristol, Scotland and Ireland. The Carrickfergus clay has been found to be highly dolomitic resulting in the body of the delftware forming diopside and the magnesian olivine forsterite, when fired. Brookite had not converted to rutile, nor had tridymite, nor cristobalite formed; the K‐feldspars did not undergo further chemical reactions, and the observation of metakaolin would suggest that the biscuit firing temperature was in the order of 800–900 °C. Chalcedony containing moganite was established as the silica source. A cobalt‐containing lead‐tin glaze was applied to the biscuit body and, after decorating, was fired. The mineralogy of the pigments used to decorate the objects indicate the yellow to be the PbSbSn triple oxide, the green to be a copper silicate mixed with lead‐tin yellow, the purple and browns to be manganese silicates and the blue to contain cobalt spinels and cobalt pyroxenes. Diopside crystals together with recrystallised tin agglomerates have been observed floating within the glaze. Copyright © 2015 John Wiley & Sons, Ltd.