Supramolecularly Assembled Ratiometric Fluorescent Sensory Nanosystem for "Traffic Light"-Type Lead Ion or pH Sensing

The combination of functional nucleic acids and nanomaterials enables the continuous development of hybrid nanosystems that have found wide applications including chemo/biosensing. Herein, we report the supramolecular assembly of a "sesame biscuit"-like superstructural nanosystem based on aptamer, quantum dot (QD), and graphene oxide (GO), and its diverse applications in Pb²⁺ and pH sensing. The nanosystem was assembled via adsorbing silica-encapsulated green-emitting QD onto the edge of GO by ionic interaction, followed by absorbing aptamer-modified red-emitting QD onto the GO surface via the π-stacking interaction. The nanosystem showed the characteristic of the nonquenched green fluorescence due to silica encapsulation and quenched red fluorescence owing to nanomaterial surface energy transfer. The nanosystem responded to Pb²⁺/pH in ratiometric fluorescence: the red fluorescence varied upon analyte-driven conformational changes of the aptamer, whereas the green one remained constant. Under optimized conditions, the nanosystem was demonstrated to be capable of quantifying Pb²⁺ with a detection limit of 11.7 pM, as well as pH with a sensing resolution of 0.1 pH unit. More importantly, the ratiometric nanosystem facilitated visualization of analytes in a distinct "traffic light" manner, which was exemplified by semiquantification of exogenous Pb²⁺ in living cells. To demonstrate practicality, fluorescent test strips were fabricated by immobilizing the nanosystem on paper. The fluorescent test strips displayed traffic light-type fluorescence color changes, with the capacity for on-site, naked-eye detection of Pb²⁺ in real samples, as well as point-of-care pH testing in routine urinalysis.