In situ Raman spectroscopic measurements with 785 nm excitation were carried out in aqueous solutions containing bipyridine derivatives. Intense Raman signals were observed when the Ag dimer structure was optimized. The SERS activity was dependent upon on the structure of the Ag dimer with a distinct gap distance, suggesting that the intense SERS originates from the gap part of the dimer. Characteristic time-dependent spectral changes were observed. Not only a spectrum which was the superposition of two bipyridine spectra but also spectra which can be assigned to one of the bipyridine derivatives were frequently observed. Observation using solutions with different concentrations proved that the spectra originated from very small numbers of molecules at the active SERS site of the dimer.
Diffusion of target molecules incorporated in the self-spreading lipid bilayer was controlled by the introduction of periodic array of metallic architecture on solid surface. Retardation of the progress of target molecules became significant when the size of gap between small metal architectures was less than a few hundred nanometers. The self-spreading dynamics of the lipid bilayer depending on the size of the small gap were analyzed semiquantitatively. Estimated change in the driving force of the spreading layer suggests that highly localized compression of the spreading layer causes selective segregation of molecules.
A new methodology for nanoscopic molecular filtering was developed using a substrate with a periodic array of metallic nanogates with various widths between 75 and 500 nm. A self-spreading lipid bilayer was employed as the molecular transport and filtering medium. Dye-labeled molecules doped in the self-spreading lipid bilayer were filtered after the spreading less than a few tens of micrometers on the nanogate array. Quantitative analysis of the spreading dynamics suggests that the filtering effect originates from the formation of the chemical potential barrier at the nanogate region, which is believed to be due to structural change such as compression imposed on the spreading lipid bilayer at the gate. A highly localized chemical potential barrier affects the ability of the doped dye-labeled molecules to penetrate the gate. The use of the self-spreading lipid bilayer allows molecular transportation without the use of any external field such as an electric field as is used in electrophoresis. The present system could be applied micro- and nanoscopic device technologies as it provides a completely nonbiased filtering methodology.
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