A Diels-Alder route to angularly functionalized bicyclic structures

A Diels-Alder-based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step.     

An efficient large-scale synthesis of gemcitabine employing a crystalline 2,2-difluoro-α-ribofuranosyl bromide

An efficient large-scale synthesis of gemcitabine was achieved without chromatography or fractional crystallization. The key steps include stereospecific conversion of a novel β-ribofuranosyl phosphate into a highly crystalline α-ribofuranosyl bromide and coupling of the α-ribofuranosyl bromide and trimethylsilyl cytosine to produce a β-nucleoside. p-Phenylbenzoyl group was introduced for the protection of one of hydroxy groups in order to enhance the crystallinity of intermediates. Continuous removal of trimethylsilyl bromide, generated during the coupling reaction, by distillation from the reaction medium substantially enhanced the β-selectivity of the crucial coupling reaction.     

Atomic layer deposition of TiO2 nanotubes and its improved electrostatic capacitance

Titanium dioxide (TiO₂) nanotubes are fabricated into anodic aluminum oxide (AAO) membrane via atomic layer deposition (ALD). For the ALD of TiO₂, gaseous precursors, titanium (IV) isopropoxide and water are sequentially applied and chemically reacted with each other. A thickness of nanotubes is precisely controlled by the applied cycle numbers of ALD and the morphology of nanostructures is investigated by SEM and TEM. The amorphous property of TiO₂ nanostructures is revealed by XRD and the composition of nanotubes is measured by TEM–EDX. The impurity contents and binding structure of the nanostructures are analyzed by XPS. The electrostatic capacitance of TiO₂ nanotubes into AAO is 480 μF/cm² and it is about 3 times higher compared with AAO membrane (172 μF/cm²).     

CO preoxidation on Ru-modified Pt(111)

Electrochemical scanning tunneling microscopy was used to study the structural evolution of adsorbed CO during preoxidation on Pt(111) modified with spontaneously deposited Ru. During the preoxidation process, a phase transition was observed from (2 × 2)-3CO-α to (√19 × √19)R23.4°-13CO via the transient structures (2 × 2)-3CO-β and (1 × 1)-CO. A comparison of these structural changes with those that occur on unmodified Pt(111) revealed that the presence of Ru resulted in higher populations of transient structures at lower potentials and a cathodic shift in the potential at which preoxidation is complete. These observations are discussed in terms of increased mobility of adsorbed CO in the presence of Ru.