Analytical optimization of nanocomposite surface‐enhanced Raman spectroscopy/scattering detection in microfluidic separation devices

Abstract

Adding vibrational spectroscopies to the arsenal of detection modes for microfluidics (mufluidics) offers benefits afforded by structurally descriptive identification of separated electrophoretic bands. We have previously applied surface-enhanced Raman spectroscopy (SERS) detection with nanocomposite metal-elastomer substrates as a detection mode in mufluidic channels. To create these mufluidic-SERS devices, silver-PDMS substrate regions are integrated into the architecture of a separation chip fabricated from PDMS or glass. Herein, we investigate analytical figures of merit for integrated mufluidic-SERS devices by implementing improvements in fluidic and SERS substrate fabrication as well as data collection strategies. Improvements are achieved by chemical modification of the PDMS channel, increasing effective detection efficiency by minimizing analyte partitioning into nonsensing walls rendering more analyte available to the metallized cover slide of channels and also by uniquely fabricating deep channels that have larger volume to SERS surface area ratios than conventional channels. A method is developed to exploit the inherent concentration profile of analyte material within an electrophoretic band in order to extend the linear dynamic range of detection on the SERS nanostructured surface. This is accomplished by spatially interrogating the Gaussian concentration profile of said bands. The subtleties of this technique give insight into the analytical utility of SERS detection in general. Finally, SERS substrates uniquely created via electron beam lithography with controllable morphologies are integrated into mufluidic-SERS devices to prove feasibility of such a coupling for future work. A separation of endocrine disrupting chemicals in a hybrid SERS nanocomposite-glass device is the capstone of this work.

SERS and Separation Science

“…An integrated separation and SERS detection micro-fluidic device was reported by Connatser et al [31], as shown in Figure 7.7. Designed patterns for substrates were written into an e-beam-sensitive layer using e-beam lithography and then coated with 25 nm of silver or gold via vapour deposition.…”

Progress in Thermal Lens Spectrometry and Its Applications in Microscale Analytical Devices

“…To achieve more detailed and richer information about an analyte (Baker et al, 2009), TLS could also be combined with other detection techniques, such as fluorescence detection, electrochemical analysis, MS, surface-enhanced Raman scattering (qualitatively identifying analytes; Connaster et al, 2008), and surface plasmon resonance (studying binding interactions in biological assays without use of labels; Luo et al, 2008).…”

SERS and Microfluidics

“…Surface-immobilized SERS substrates have been prepared on the elastomer surface [9] by deposition of thin silver films into nanowells for the detection of rhodamine 6G and adenosine. SERS substrates formed by the deposition of silver composites and fabrication of three-dimensional nanostructures by electron beam lithography [10] have been applied for the detection of rhodamine 6G, resorufin, para-aminobenzoic acid, ortho-phenanthroline, 6-amino-2-naphthoic acid and terephthalic acid. Other approaches are the deposition of nanoparticles (see also Chapter 2) or nanostructured noble-metal films.…”