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While Raman spectroscopy is a useful method for analyzing many organic compounds, it is limited by relatively low sensitivity. Therefore, Surface Enhanced Raman Spectroscopy (SERS) based on the adsorption of organic analytes onto gold or silver nanostructures has been used to enhance the signal of chemicals presented at very low concentrations. Although the plasmonic effect of SERS has been shown to play a large role in signal enhancement, the significance of the chemical effect due to the analyte chemisorption on the gold or silver surface is less well understood. In this study, the role of aniline substituents is examined by probing the SERS intensities of various anilines in silver and gold colloids using a Raman spectrometer with an excitation wavelength of 785 nm. The SERS enhancement factors and detection limits for aniline and its mono- and di-substituted ortho derivatives are determined and compared. Both the steric requirements of chemisorption and the inductive effects of electron-withdrawal due to the substituents affect the signal intensities of various vibrational modes of the amino group and the aromatic ring. The degree of enhancement is also related to the methods for preparing the silver and gold colloids, which are characterized by probing the nanoparticle morphology and its degree of aggregation using transmission electron microscopy (TEM).

Chemical Enhancement of the Surface Enhanced Raman Scattering Signals of Anilines via Their &lt;i&gt;Ortho&lt;/i&gt;-Substituents

Chemical Enhancement of the Surface Enhanced Raman Scattering Signals of Anilines via Their <i>Ortho</i>-Substituents