Dual-Excitation Nanocellulose Plasmonic Membranes for Molecular and Cellular SERS Detection

We demonstrate that cellulose nanofiber (CNF) biomaterials with high transparency and mechanical robustness can be combined with gold nanorods to form a multifunctional porous membrane for dual-mode surface enhanced Raman scattering (SERS) detection of both small molecules and cells. The nanoporous nature of the nanofiber membranes allows for effective molecular filtration and preconcentration of the analytes, further boosting the SERS performance. Specifically, because of the low fluorescence and Raman background of the CNF matrix, extremely low loading density of gold nanorods can be used. The nanorod assemblies within the CNF network can be resonantly driven by a 532 nm laser (transverse plasmonic mode) and near resonantly driven at by a 785 nm laser (longitudinal mode), facilitating dual operational modes at two excitation wavelengths. The shorter wavelength excitation mode yields better Raman scattering efficiency and has been demonstrated to be capable of detecting rhodamine 6G (R6G) dyes down to picomolar concentrations. On the other hand, the longer wavelength excitation mode provides autofluorescence suppression for the better detection of microorganisms such as Escherichia coli, shortening the required integration time from hours to minutes. Upon drastically lowering the spectral background noise and utilizing nanofiltration, the plasmonic CNF membranes reported here show significantly improved SERS sensitivity and detection fidelity as compared to traditional metal, metal oxide, synthetic polymer, and paper SERS substrates.