Controlling the orientation of probe molecules on surface-enhanced Raman scattering substrates: A novel strategy to improve sensitivity.

Typically, the surface-enhanced Raman scattering (SERS) technique is employed in precious metallic substrates with spontaneously adsorbed probing molecules to acquire signals. Preferred chemical conditions including aggregate status, hydrophilic/hydrophobic surroundings, and smart linkers were created to enable the detection of targets in very low concentrations (lower than 1.0 × 10-7  M). Although the sensitivity of SERS is applicable to certain areas, it is not satisfied in several cases that require obtaining good resolved signals involving extremely few surface molecules. Thus, further improvements in the sensitivity based on existing SERS techniques pose a challenge and is desirable for all aspects of analytical chemistry. In this study, a novel strategy was employed by constructing a molecular template (MT) on the SERS substrates with spontaneously adsorbed probe molecules to improve the detection sensitivity of probe molecules. The proposed MT-assisted SERS technique differed from previous methods as it provides a completely new method for improving the limit of detection (LOD) of SERS by controlling molecular orientations. The surface selection rules of SERS spectra were first introduced as an effective strategy to improve the detection sensitivity, and this was extremely beneficial with respect to analytical applications. The use of the MT-assisted SERS technique indicated that the LOD of probe molecules of p-aminobenzenethiol (8.0 × 10-9  M) and 4-mercaptobenzoic (1.0 × 10-7  M) acids on noble metallic substrates exhibited nearly one order of magnitudes. Hence, the proposed method paves a way to detect the molecules under improved sensitivity at extreme low concentrations. The study corresponded to a proof-of-concept study of MT-assisted SERS for SERS-based applications in ultra-sensitive analysis.