Synthesis of sceptrin alkaloids

[reaction: see text] A concise synthetic route to the marine alkaloids (+/-)-sceptrin and (+/-)-dibromosceptrin has been developed.     

Photoluminescence of tetrahedral quantum-dot quantum wells

Taking into account the tetrahedral shape of a quantum-dot quantum well (QDQW) when describing excitonic states, phonon modes, and the exciton-phonon interaction in the structure, we obtain within a nonadiabatic approach a quantitative interpretation of the photoluminescence spectrum of a single CdS/HgS/CdS QDQW. We find that the exciton ground state in a tetrahedral QDQW is bright, in contrast to the dark ground state for a spherical QDQW. The position of the phonon peaks in the photoluminescence spectrum is attributed to interface optical phonons. We also show that the experimental value of the Huang-Rhys parameter can be obtained only within the nonadiabatic theory of phonon-assisted transitions.     

Spreading of block copolymer films and domain alignment at moving terrace steps

We investigate spreading of phase separated copolymer films, where domain walls and thickness steps influence polymer flow. We show that at early stages of spreading its rate is determined by slow activated flow at terrace steps (i.e., thickness steps). At late stages of spreading, on the other hand, the rate is determined by the flow along terraces, with diffusionlike time dependence t(-1/2). This dependence is similar to de Gennes and Cazabat's prediction for generic layered liquids [P. G. de Gennes and A. M. Cazabat, C.R. Acad. Sci. Paris II 310, 1601 (1990)], as opposed to the classical Tanner's law of drop spreading. We also argue that chain hopping at the spreading terrace steps should lead to the formation of aligned, defect-free domain patterns on the growing terraces.     

Rifampicin inhibits alpha-synuclein fibrillation and disaggregates fibrils

The aggregation of alpha-synuclein in dopaminergic neurons of the substantia nigra is a critical step in the pathogenesis of Parkinson's disease. We show that the antibiotic rifampicin inhibited alpha-synuclein fibrillation and disaggregated existing fibrils in a concentration-dependent manner. Size-exclusion chromatography data indicated that rifampicin stabilized alpha-synuclein as both a monomer and soluble oligomers comprised of partially folded alpha-synuclein. Experiments using aged samples of rifampicin indicated that the most active species in inhibiting fibrillation and disaggregating fibrils is an oxidation product of rifampicin, which was confirmed in experiments under anaerobic conditions. These results indicate that rifampicin-mediated inhibition of alpha-synuclein fibrillation and disaggregation of fibrils involves preferential stabilization of monomeric and soluble oligomeric forms, and that rifampicin potentially may have therapeutic application for Parkinson's disease.     

Preparation and characterization of regioisomerically pure 1,7-disubstituted perylene bisimide dyes

A detailed study on bromination and subsequent imidization of perylene bisanhydride with cyclohexylamine is reported. The present results reveal that previously reported 1,7-difunctionalized perylene bisimides are presumably contaminated with the respective 1,6 regioisomers. N,N'-Dicyclohexyl-1,7-dibromoperylene bisimide 1,7-3 is obtained for the first time in isomerically pure form, and its structure is unequivocally confirmed by X-ray analysis. By using regioisomerically pure 1,7-dibromoperylene bisimide 1,7-3, 1,7-dipyrrolidinylperylene bisimides 4a-c and 1,7-dipyrrolidinylperylene bisanhydride 5 as well as the unsymmetrically difunctionalized 1-bromo-7-pyrrolidinyl- and 1-cyano-7-pyrrolidinylperylene bisimides 7 and 8 are synthesized in good yield.     

Highly efficient catalysts for the hydrogenation of nitro-substituted aromatics

Nanoparticles of Co and NiPd, derived from colloidal precursors and supported on commercially available non-ordered mesoporous silica, are highly effective, cheap, recyclable and industrially viable catalysts for the hydrogenation of a range of nitro-substituted aromatics under mild conditions.     

Selective steroid recognition by a partially bridged resorcin[4]arene cavitand

The partially bridged resorcin[4]arene cavitand featuring a cleft-shaped recognition site formed by two anti-quinoxaline bridges and four convergent HO-groups was prepared in three steps and characterised by X-ray crystallography; cavitand was found to be a selective receptor for steroidal substrates in CDCl3, with the best binding observed for steroids with a flat A-ring and two H-bonding sites on rings A and C/D.     

A previously unrecognised hydronium di-cation in the crystal structure of a cucurbituril derivative

Examination of the crystal structure of the adduct of hydronium tetrachloroferrate dichloride with cucurbituril resulted in the discovery that the hydronium cation present therein is not the well known H7O3+ species; rather, it is an unprecedented cyclic species of composition (H14O6)2+, templated by the formation of five hydrogen bonds to cucurbituril.