Integrating Plasmonic Supercrystals in Microfluidics for Ultrasensitive, Label-Free, and Selective Surface-Enhanced Raman Spectroscopy Detection

Surface-enhanced Raman spectroscopy (SERS) microfluidic chips for label-free and ultrasensitive detection are fabricated by integrating a plasmonic supercrystal within microfluidic channels. This plasmonic platform allows the uniform infiltration of the analytes within the supercrystal, reaching the so-called hot spots. Moreover, state-of-the-art simulations performed using large-scale supercrystal models demonstrate that the excellent SERS response is due to the hierarchical nanoparticle organization, the interparticle separation (IPS), and the presence of supercrystal defects. Proof-of-concept experiments confirm the outstanding performance of the microfluidic chips for the ultradetection of (bio)molecules with no metal affinity. In fact, a limit of detection (LOD) as low as 10^-19 M was reached for crystal violet. The SERS microfluidic chips show excellent sensitivity in the direct analysis of pyocyanin secreted by <i>Pseudomonas aeruginosa</i> grown in a liquid culture medium. Finally, the further integration of a silica-based column in the plasmonic microchip provides charge-selective SERS capabilities as demonstrated for a mixture of positively and negatively charged molecules.