The nano-assembly of charged polyelectrolytes via layer-by-layer (LbL) technology on porous silicon (PSi) interferometers is here demonstrated as an effective biofunctionalization approach for high-sensitivity/selectivity labelfree optical biosensing, using streptavidin/biotin affinity detection as case study. Nanostructured PSi interferometers are biofunctionalized with a nano-assembly of a positively-charged polyelectrolyte, namely, PAH (poly(allylamine hydrochloride)), and a negatively-charged biotinylated polyelectrolyte, namely, b-PMAA (poly(methacrylic acid)), via LbL technology. The nano-assembly is stable under operating conditions and enables the selective and sensitive detection of streptavidin with a sub-picomolar detection limit (namely, DL=0.6 pM), which is 105-fold lower than that achieved with PSi interferometers biofunctionalized using standard silane chemistry. Remarkably, the analytical performance achieved for LbL-biofunctionalized PSi interferometers is comparable to those of state-of-the-art label-free photonic and plasmonic platforms.
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