AVS 62nd International Symposium & Exhibition
    Surface Science Tuesday Sessions
       Session SS+AS+EN+NS-TuM

Paper SS+AS+EN+NS-TuM5
Structured Noble Metal Nanosurfaces for Biosensing and Bioanalysis (4): TLC-SERS and In Situ Monitoring of Surface-Adsorbed Target Molecules

Tuesday, October 20, 2015, 9:20 am, Room 112

Session: Nanostructures, Nanoplasmonics and Surface Reactions
Presenter: Hiroyuki Takei, Toyo University, Japan
Authors: H. Takei, Toyo University, Japan
J. Saito, Toyo University, Japan
K. Watanabe, Toyo University, Japan
T. Okamoto, Riken, Japan
H. Vieker, Bielefeld University, Germany
A. Beyer, Bielefeld University, Germany
A. Gölzhäuser, Bielefeld University, Germany
Correspondent: Click to Email

Surface-enhanced Raman spectroscopy, SERS, is a powerful technique for in-situ characterization of chemical species. Requisite noble metal nanosurfaces can be prepared with a variety of techniques, ranging from simple vacuum deposition of a metal followed by annealing to intricate processing by electron beam lithography. Some commercial SERS plates are now available, and it is sometimes possible to detect signals from even single molecules if pure. However, in real-world applications, target molecules are often found in mixtures, either containing other Raman-active chemical species or a background material that can overwhelm the target molecule. It can also happen that one might be interested in directly obtaining SERS spectra of chemical species adsorbed on a solid surface.

When faced with a mixture sample, we can carry out separation before SERS measurement. To do so, we incorporated a SERS layer into a thin layer chromatographic plate. While a number of workers have reported applying noble metal nanoparticles after separation with a conventional TLC plate, we feel that such an additional step is cumbersome and does not guarantee uniformity in SERS signals. Our TLC-SERS is prepared with the following procedure; (1) adsorption of 100 nm diameter SiO2 nanospheres as a dense monolayer on a glass slide, (2) evaporation of gold or silver with thicknesses up to 100 nm, and (3) spreading of chromatography silica gels. Steps (1) and (2) give rise to surface-adsorbed cap-shaped noble metal nanoparticles. We demonstrate that the TLC-SERS can actually separate mixture samples and provide in-situ SERS spectra. Two examples will be used to demonstrate the utility of our TLC-SERS plates. One deals with a mixture of roughly equal portions of Raman-active chemical species, rhodamine 6 G, crystal violet and BPE. The other is skim milk to which a trace amount of melamine has been added. We show that the three-component mixture could be separated and SERS spectra of all three components could be obtained separately and that melamine added to skim milk could be detected after separation but not before.

For detection of surface-adsorbed chemical species, we prepared silver nanoparticles on a PDMS sheet, using the same protocol as above. The PDMS sheet can be made less than 1 mm thick so that with an appropriate pressurization system, pressure can be applied to the PDMS sheet in order to press the silver nanoparticles against a near-by solid surface to which target molecules are adsorbed. Such a system can be utilized to detect, for example, residual pesticides on agricultural produces. We will demonstrate direct detection of ferbam on a grapefruit.