Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

The king's champion: re-enacting Arthurian romance at the English coronation banquet

Recent scholarship has emphasised the extent to which historical events are reflected in medieval romance. This paper seeks to draw attention to an instance where that relationship appears to have been inverted and a romance motif was carefully recreated at a particularly important event in the historical world. From the fourteenth century onwards, a mounted knight ceremonially rode into the English coronation banquet and issued a challenge to all assembled. The visual detail of the ritual strikingly echoes that of the romance motif of the “intruder at the feast”. This motif crops up in numerous romances, and is particularly associated with Arthurian narratives where it usually serves as a catalyst for adventure, providing the court and the king with an opportunity to justify their authority and reputation. This paper analyses the precise nature of the historical ritual and explores how the romance resonances of the ceremony at the coronation feast could be used to underpin political authority and courtly identity. In doing so, it seeks to underscore the centrality of Arthurian romance to English monarchical self-imagining and the symbolic power which could be ascribed to the genre's themes and conventions.