It is desirable to extend the surface-enhanced Raman scattering (SERS) from the conventionally used visible range into the infrared region, because the fluorescence background is lower in the long-wavelength regime. To do this, it is important to have a SERS substrate suitable for infrared operation. In this work, we report the near infrared SERS operation based on the substrates employing star-shaped gold/silver nanoparticles and hyperbolic metamaterial (HMM) structure. We first fabricate the SERS substrate in which nanoparticles are separated from a silver film by a thin dielectric layer. Performance of the SERS substrate is investigated with a 1064-nm excitation source. Compared with similar silver film-based substrates employing respectively gold and silver spherical nanoparticles, it is found that, Raman intensity scattered by the substrate with star-shaped nanoparticles is 7.4 times stronger than that with gold nanoparticles, and 3.4 times stronger than that with silver nanoparticles. Following this, we fabricate the SERS substrate where the star-shaped nanoparticles are deposited over a HMM structure. The HMM structure comprises three pairs of germanium-silver multilayers. Further experimental result shows that, with the star-shaped nanoparticles, the HMM-based substrate yields 30% higher Raman intensity for near infrared SERS operation than the silver film-based substrate does.

In this paper, we describe the use of pulsed laser desorption/ionization mass spectrometry (LDI-MS) for the detection of tumor cells through the analysis of gold cluster ions [Aun](+) from aptamer-modified gold nanofilms (Au NFs). We observed not only the transformation of the Au NFs into gold nanoparticles (Au NPs) but also the formation of gaseous gold cluster ions ([Au(n)](+); n = 1-5) under irradiation with a nanosecond pulsed laser. The size and density of the formed Au NPs and the abundance of [Au(n)](+) ions were both highly dependent on the thickness of the Au NFs (10-100 nm). Thin Au NFs tended to form highly dense Au NPs on the substrate and favored the desorption and ionization of gold cluster ions. The signal intensities of the [Au(n)](+) species, monitoring using mass spectrometry, decreased upon increasing the thickness of the Au NF from 10 to 100 nm and after modification with thiolated DNA. Furthermore, we found that Au NFs modified with mucin1-binding aptamer (AptMUC1-Au NFs) could selectively enrich MCF-7 cells (human breast adenocarcinoma cell line) in blood samples; coupled with LDI-MS analysis of the [Au(n)](+) ions, we could detect MCF-7 cells selectively in blood samples at abundances as low as 10 cells. This approach offers the advantages of high sensitivity, selectivity, and throughput for the detection of circulating tumor cells, and has great potential for use as a powerful analytical platform for clinical diagnoses of tumor metastasis.