科研成果

As a representative folding system that features a conjugated backbone, a series of monodispersed (o-phenyleneethynylene)-alt-(p-phenyleneethynylene) (PE) oligomers of varied chain length and different side chains were studied. Molecules with the same backbone but different side-chain structures were shown to exhibit similar helical conformations in respectively suitable solvents. Specifically, oligomers with dodecyloxy side chains folded into the helical structure in apolar aliphatic solvents, whereas an analogous oligomer with tri(ethylene glycol) (Tg) side chains adopted the same conformation in polar solvents. The fact that the oligomers with the same backbone manifested a similar folded conformation independent of side chains and the nature of the solvent confirmed the concept that the driving force for folding was the intramolecular aromatic stacking and solvophobic interactions. Although all were capable of inducing folding, different solvents were shown to bestow slightly varied folding stability. The chain-length dependence study revealed a nonlinear correlation between the folding stability with backbone chain length. A critical size of approximately 10 PE units was identified for the system, beyond which folding occurred. This observation corroborated the helical nature of the folded structure. Remarkably, based on the absorption and emission spectra, the effective conjugation length of the system extended more effectively under the folded state than under random conformations. Moreover, as evidenced by the optical spectra and dynamic light-scattering studies, intermolecular association took place among the helical oligomers with Tg side chains in aqueous solution. The demonstrated ability of such a conjugated foldamer in self-assembling into hierarchical supramolecular structures promises application potential for the system.

Enantiopure trans-3-trifluoromethylsulfonylamino-4-silyloxypyrrolidines efficiently catalyse the asymmetric alpha-aminoxylation of aldehydes. At 1% catalyst loading (solvent-free conditions) or at 2% catalyst loading (acetonitrile solution) aldehydes are completely converted in short reaction times leading to alpha-aminoxylation products with very high (96-99%) enantioselectivity.

Highly efficient plasmonic nanofocusing is proposed and demonstrated in a T-shape micro-slit surrounded by multi-slits. The nanofocusing phenomenon is achieved based on the multimode interference in the micro-slit, the constructive interference in the T-shape slit, and also the multiple-beam interference of the light radiated from the multi-slits and the transmitted light from the T-shape micro-slit. Because of the large illumination areas of the incident light on the wide slit aperture in the proposed structure, a large amount of light can pass through the wide slit. This leads to a highly efficient nanofocusing. Meanwhile, the wide slit means easy fabrication. In the experiment, the focusing phenomenon in the proposed structure was successfully demonstrated with a scanning near-field optical microscopy (SNOM) technology. (C) 2012 Optical Society of America