Surface Enhanced Raman Spectroscopy of Carbon Nanotubes in Aqueous Solution

Carbon nanotubes (CNTs) exhibit intrinsic spectroscopic properties and are potential Raman and NIR florescence probes for bioimaging. However, the weak Raman intensity greatly obstructs such applications. Surface-enhanced Raman scattering (SERS) has shown to be an effective way to increase the Raman signal. SERS has been widely studied for solid samples. However, solid state is distinctly different from the environment in biosystems. Herein, we studied the SERS of Aunanoparticle-decorated CNTs in aqueous solution, which offers a similar environment to biosystems. We found that the functionalization of CNTs with -SH groups can improve the attachment of Au nanoparticles on tube surfaces thus benefit the SERS effect. The particle size is another important issue for SERS. Particles of 50 nm show much stronger enhancement than those of 12 nm. The Raman intensity of CNTs increases with the increase of the concentration of Au nanoparticles. Hexamethylene diamine molecules can act as the hi-linkers between Au nanoparticles, compressing the interparticle distance. This was proved by the red-shift of the band at ca. 540 nm and the appearance of a broad band around 700 nm in the absorption spectra of Au nanoparticles. Therefore the addition of hexamethylene diamine can further increase the Raman signal of CNTs by the strong coupling of the surface plasma from the Au nanoparticles with very small interparticle distances. Two kinds of commonly used small molecule Raman probes p-aminothiophenol and Rhodamine B both show remarkably enhanced Raman intensity when added to the aqueous dispersion of Au/CNT hybrids. This shows that these Raman probe molecules can absorb onto the Au/CNT hybrids and their Raman spectra are able to be greatly enhanced by Au nanoparticles decorated on CNTs. Because various Raman bands from either CNTs or Raman probe molecules can be used for Raman imaging, this kind of Raman probe molecule/Au/CNT tri-component hybrid systems may be used as a potential nanostructured platform for multiplexed Raman imaging based on SERS effect.