Magnetism and plasmonic performance of mesoscopic hollow ceria spheres decorated with silver nanoparticles.

We investigate the role of interfaces and surfaces in the magnetic and surface enhanced Raman spectroscopy (SERS) properties of CeO2 hollow spheres decorated with Ag nanoparticles (H-CeO2@Ag). The composites, H-CeO2@Ag, were synthesized using a newly developed two-step process. The CeO2 hollow sphere diameter ranges from 100 nm to 2 µm and the grafted Ag nanoparticle (NP) size varies from 5 to 50 nm with a controllable coverage ratio. Spectroscopic and microscopic characterization confirms the formation of an interface between the Ag and ceria and shows different charge rearrangements occurring at both the interface and the surface. Room temperature ferro-magnetism was observed in all composites, and is associated mostly with ceria surface defects. A strong SERS effect was reported with a detection limit down to 10-14 M for the rhodamine 6G analyte. Scanning transmission electron microscopy and electron energy loss spectroscopy investigation reveals that hot-spots are associated with the silver NP surfaces and also with the Ag/CeO2 interface. This interfacial hot spot occurs for metallic particles above 30 nm and is strongly red shifted with respect to the Ag surface plasmon. The strong SERS activity is then attributed to the presence of several types of hot-spots and the geometrical features (buoyant hollow sphere and size dispersion) of the composite.

The stereodivergent formation of 2,6-cis and 2,6-trans-tetrahydropyrans: experimental and computational investigation of the mechanism of a thioester oxy-Michael cyclization.

The origins of the stereodivergence in the thioester oxy-Michael cyclization for the formation of 4-hydroxy-2,6-cis- or 2,6-trans-substituted tetrahydropyran rings under different conditions was investigated both computationally and experimentally. Synthetic studies showed that the 4-hydroxyl group was essential for stereodivergence. When the 4-hydroxyl group was present, TBAF-mediated conditions gave the 2,6-trans-tetrahydropyran and trifluoroacetic acid-mediated conditions gave the 2,6-cis-tetrahydropyran. This stereodivergence vanished when the hydroxyl group was removed or protected. Computational studies revealed that: (i) the trifluoroacetic acid catalysed formation of 2,6-cis-tetrahydropyrans was mediated by a trifluoroacetate-hydroxonium bridge and proceeded via a chair-like transition state; (ii) the TBAF-mediated formation of 2,6-trans-tetrahydropyrans proceeded via a boat-like transition state, where the 4-hydroxyl group formed a crucial hydrogen bond to the cyclizing alkoxide; (iii) both reactions are under kinetic control. The utility of this stereodivergent approach for the formation of 4-hydroxy-2,6-substituted tetrahydropyran rings has been demonstrated by the total syntheses of the anti-osteoporotic natural products diospongin A and B.