Smartphone-Based Attomolar Cyanide Ion Sensing Using Au-Graphene Oxide Cryosoret Nanoassembly and Benzoxazolium-Based Fluorophore in a Surface Plasmon-Coupled Enhanced Fluorescence Interface

Abstract

Photoplasmonic platforms are being demonstrated as excellent means for bridging nanochemistry and biosensing approaches at advanced interfaces, thereby augmenting the sensitivity and quantification of the desired analytes. Although resonantly coupled electromagnetic waves at the surface plasmon-coupled emission (SPCE) interface are investigated with myriad nanomaterials in order to boost the detection limits, rhodamine moieties are ubiquitously used as SPCE reporter molecules in spite of their well-known limitations. In order to overcome this constraint, in this work, a benzoxazolium-based fluorescent molecule, (E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide (DSBO), was synthesized to selectively detect the cyanide (CN^-) ions in water samples. To this end, the sensitivity of the fabricated SPCE substrates is tested in spacer, cavity, and extended cavity nanointerfaces to rationalize the configurational robustness. The performance of the sensor is further improved with the careful engineering of gold (Au)-graphene oxide (GO) cryosoret nanoassemblies fabricated via an adiabatic cooling technology. The unique dequenching (turn-on) of the quenched (turn-off) fluorescent signal is demonstrated with the hybridized metal-π plasmon synergistic coupling in the nanovoids and nanocavities assisting delocalized Bragg and localized Mie plasmons. The spectro-plasmonic analysis yielded highly directional, polarized (>95%), and enhanced emission attributes with an attomolar limit of detection of 10 aM of CN^- ions with high linearity (R² = 0.996) and excellent reliability, in addition to an exceptional correlation with the theoretically obtained TFclac simulations. The CN^- ion sensing is experimentally validated with the smartphone-based cost-effective SPCE detection technology to render the device amenable to resource-limited settings. We believe that the unique fluorophore-cryosoret nanoassemblage presented here encourages development of frugal, unconventional, and highly desirable strategies for the selective quantitation of environmentally and physiologically relevant analytes at trace concentrations for use in point-of-care diagnostics.