Molecular fiber sensors based on surface enhanced Raman scattering (SERS).

Molecular sensors based on surface enhanced Raman scattering (SERS) and optical fibers have been widely used in biological, environmental and chemical detection procedures due to their unique advantages, such as molecular specificity, high sensitivity and flexibility. In this paper, we review the development and highlight some of the important milestones of SERS fiber sensor development with emphasis on recent work to improve the sensitivity of the fiber sensors. In particular in the area to increase the sensitivity, we've reviewed various methods of sample preparation as well as different fiber SERS sensors. One way is to strengthen the field enhancement around the surface of the probe tip and the other is to increase the number of the interacting particles during the SERS process. These techniques are known as the double substrate "sandwich" structure (DSSS) and the liquid core photonic crystal fiber (LCPCF), and in both cases the sensitivities are significantly improved. These fiber sensors were tested with Rhodamine 6G, human insulin and tryptophan and showed excellent performance.

Competitive binding effects on surface-enhanced Raman scattering of peptide molecules.

Surface enhanced Raman scattering (SERS) has been conducted on tryptophan (W), proline (P) and tyrosine (Y) containing peptides that include W-P-Y, Y-P-W, W-P-P-P-Y, Y-P-P-P-W, W-P-P-P-P-P-Y, and Y-P-P-P-P-P-W to gain insight into molecular binding behavior on a metal substrate to eventually apply in protein SERS detection. The peptides are shown to bind through the molecule's carboxylic end, but the strong affinity of the tryptophan residue to the substrate surface, in conjunction with its large polarizability, dominates each molecule's SERS signal with the strong presence of its ring modes in all samples. These results are important for understanding SERS of protein molecules.

Manipulation and light-induced agglomeration of carbon nanotubes through optical trapping of attached silver nanoparticles.

A simple experimental method has been demonstrated for manipulating multi-walled carbon nanotube (MWCNT) bundles through the optical trapping of attached silver nanoparticles (SNPs). In our experiments, without the SNPs, the MWCNTs cannot be trapped due to their irregular shapes and large aspect ratio. However, when mixed with SNPs, the MWCNTs can be successfully trapped along with the SNPs using a TEM(00) mode laser at 532 nm. This is attributed to the optical trapping of the SNPs and attractive interaction or binding between the SNPs and MWCNTs due to electrostatic and van der Waals forces. Therefore, optical manipulation of MWCNT bundles is achieved through the manipulation of the attached silver nanoparticles/aggregates. In addition, we have observed the phenomenon of light-induced further agglomeration of SNPs/MWCNTs which could potentially be exploited for fabricating patterned MWCNT films for future nanoscale devices and other applications.

Effects of chromophore orientation and molecule conformation on surface-enhanced Raman scattering studied with alkanoic acids and colloidal silver nanoparticles.

Experimental studies have been carried out to gain a better understanding of the effects of chromophore orientation and molecular conformation on surface-enhanced Raman scattering (SERS) based on metal nanostructures. A series of alkanoic acids that contain a phenyl ring separated by methylene groups from the carboxylic acid, including phenylacetic acid, 3-phenylpropionic acid, 4-phenylbutyric acid, 5-phenylvaleric acid, and 6-phenylhexanoic acid, was investigated as model molecules with colloidal silver nanoparticles as SERS substrates. As the number of methylene groups increases, the molecules display an interesting zigzag intensity pattern of the phenyl ring bending mode around 1000 cm(-1) as well as a trend of appearance and disappearance of either the degenerate ring breathing mode or C[Double Bond]O vibrational mode near 1585 and 1630 cm(-1), respectively. Molecules containing an odd number of methylene units display a higher ring bending intensity and degenerate ring breathing mode and are suggested to have a trans conformation on the particle surface. Molecules with an even number of methylene units show a C[Double Bond]O vibrational mode and weaker ring bending in their SERS spectra and are suggested to have a gauche conformation on the silver nanoparticle surface. The different conformation is attributed to the varying interactions of the carboxylic group or the phenyl ring pi electrons with the silver surface. The SERS intensity was found to change little as the length between the phenyl ring and the carboxylic group was increased by adding CH(2) spacers. This is possibly because the effective distance between the phenyl ring and the silver surface does not change much with increasing number of CH(2) spacers as a result of changes in molecular conformation and variations in the phenyl ring orientation with CH(2) addition. The insight gained from this study is important for understanding SERS of complex molecules for which chromophore orientation and molecular conformation must be taken into careful consideration.

Surface-enhanced Raman scattering detection of lysophosphatidic acid.

Surface-enhanced Raman scattering using silver nanoparticles was applied to detect various forms of lysophosphatidic acid (LPA) to examine its potential application as an alternative to current detection methods of LPA as biomarkers of ovarian cancer. Enhancement of the Raman modes of the molecule, especially those related to the acyl chain within the 800-1300 cm(-1) region, was observed. In particular, the C-C vibration mode of the gauche-bonded chain around 1100 cm(-1) was enhanced to allow the discrimination of two similar LPA molecules. Given the molecular selectivity of this technique, the detection of LPA using SERS may eliminate the need for partial purification of samples prior to analysis in cancer screening.