ABSTRACT
Strongly confined electric fields resulting from nanogaps within nanoparticle aggregates give rise to significant enhancement of surface-enhanced Raman scattering (SERS). Nanometer differences in gap sizes lead to drastically different confined field strengths; so much attention has been focused on the development and understanding of nanostructures with controlled gap sizes. In this work, we report a novel petal gap-enhanced Raman tag (GERT) consisting of a bipyramid core and a nitrothiophenol (NTP) spacer to support the growth of hundreds of small petals and compare its SERS emission and localization to a traditional bipyramid aggregate. To do this, we use super resolution spectral SERS imaging that simultaneously captures the SERS images and spectra while varying the incident laser polarization. Intensity fluctuations inherent of SERS enabled super resolution algorithms to be applied, which revealed subdiffraction limited differences in the localization with respect to polarization direction for both particles. Interestingly, however, only the traditional bipyramid aggregates experienced a strong polarization dependence in their SERS intensity and in the plasmon-induced conversion of NTP to dimercaptoazobenzene (DMAB), which was localized with nanometer precision to regions of intense electromagnetic fields. The lack of polarization dependence (validated through electromagnetic simulations) and surface reactions from the bipyramid-GERTs suggests that the emissions arising from the bipyramid-GERTs are less influenced by confined fields.
ABSTRACT
Surface enhanced Raman scattering (SERS) provides a label free method of analyzing molecules from diverse and complex signals, potentially with single molecule sensitivity. The chemical specificity inherent in the SERS spectrum can identify molecules; however signal variability arising from the diversity of plasmonic environments can limit quantification, particularly at low concentrations. Here we show that digitizing, or counting SERS events, can decrease the limit of detection in flowing solutions enabling quantification of single molecules. By using multivariate curve resolution and establishing a score threshold, each individual spectrum can be classified as containing an event or not. This binary "yes/no" can then be quantified, and a linear region can be established. This method was shown to lower the limit of detection to the lowest physical limit, and lowered the limit of detection by an order of magnitude from the traditional, intensity based LOD calculations.
ABSTRACT
Raman scattering provides a chemical-specific and label-free method for identifying and quantifying molecules in flowing solutions. This review provides a comprehensive examination of the application of Raman spectroscopy and surface-enhanced Raman scattering (SERS) to flowing liquid samples. We summarize developments in online and at-line detection using Raman and SERS analysis, including the design of microfluidic devices, the development of unique SERS substrates, novel sampling interfaces, and coupling these approaches to fluid-based chemical separations (e.g., chromatography and electrophoresis). The article highlights the challenges and limitations associated with these techniques and provides examples of their applications in a variety of fields, including chemistry, biology, and environmental science. Overall, this review demonstrates the utility of Raman and SERS for analysis of complex mixtures and highlights the potential for further development and optimization of these techniques.
ABSTRACT
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive technique that can assist in trace analysis for biomedical, diagnostic, and environmental applications. However, a major limitation of SERS is surface contamination of the substrates used, which can complicate the spectral reproducibility, limits of detection, and detection of unknown analytes. This is especially prevalent with commercially available substrates as shipping under a controlled and clean environment is difficult. Here we report a method using dilute bleach solutions to remove surface contamination from commercially available substrates consisting of gold-coated nanopillar arrays that maintains functionality. The results show that this method can be used to remove background signals associated with typical surface contamination in commercially available substrates as well as remove thiolated self-assembled monolayers (SAMs). Results indicate the bleach oxidizes the surface contaminants, which can then be easily washed away. Although the metallic surface also becomes oxidized in this process, the surface can be reduced without loss of SERS activity. The SERS intensity of SAMs improved following bleach treatment across all concentrations studied.
ABSTRACT
Sugars play important roles in numerous biological processes, from providing energy to modifying proteins to alter their function. Glycosylation, the attachment of a sugar residue to a protein, is the most common post translational modification. Identifying the glycans on a protein is a useful tool both for pharmaceutical development as well as probing the proteome and glycome further. Sugars, however, are difficult analytes to probe due to their isomeric nature. In this work, Raman spectroscopy and surface enhanced Raman spectroscopy (SERS) are used to identify different monosaccharide species based on the vibrational modes of these isomeric analytes. The weak scattering of the sugars was overcome through conjugation with phenylboronic acid to provide a larger Raman scattering cross section and induce slight changes in the observed spectra associated with the structure of the monosaccharides. Spontaneous Raman, SERS in flow, and static SERS detection were performed in order to discriminate between arabinose, fructose, galactose, glucose, mannose, and ribose, as well as provide a method for identification and quantification for these sugar conjugates.