Abstract

Highly ordered microporous films of silver-containing regular arrays of spherical pores of differing diameters were prepared by electrochemical deposition into the interstitial spaces of a template formed by nanosphere lithography. These nanostructured electrodes in conjunction with a Raman microprobe spectrometer were used to obtain surface-enhanced Raman spectra (SERS) of beta-thioglucose (beta-TG) under potential control. The SERS results were compared with SERS of beta-TG on an electrochemically roughened silver electrode surface. The bands in the experimental spectra were assigned to particular vibrations with the help of ab initio predictions of the spectra. The results of this study show that beta-TG self-assembled at a silver electrode forms a hydrophilic film that may be used in biomimetic research to enhance interactions between the electrode and the hydrophilic portion of a model membrane, and to prevent interactions of proteins inserted into this membrane with the metal surface. However, in contact with the aqueous electrolyte an anomerization reaction takes place and the beta-TG film is a mixture of the alpha- and beta-anomers of thioglucose. A partial oxidation of the self-assembled molecules was also observed. In addition, the orientation of the adsorbed molecules changes as a function of the applied potential.

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