LAUSR

Abstract Hierarchical anisotropic superparticles derived from the controlled assembly of individual plasmonic nanoparticles have been recognized as promising building blocks for surface-enhanced Raman spectroscopy (SERS) nanosensors. Thus, the protocols that precisely control the near-field coupling of individual plasmonic nanoparticles and the diffusion of highly diluted analytes to the plasmonic surface are of great interests. Herein, we have synthesized a series of aromatic amphiphilic block copolymers named as polyarylene ether nitrile (amPEN in short), containing a hydrophobic backbone of aromatic moieties with hydrophilic sulfonate/carboxyl and cyano groups in the side chain. Next, the surfactant stabilized water-in-oil (W/O) reverse emulsion is constructed to induce the confined self-assembly of amPEN, leading to the formation of functional micro-reactors for the in-situ synthesis and organization of silver nanoparticles, which finally contribute to the generation of sub-micrometer cube-like plasmonic superparticles (PSPs). Furthermore, the SERS nanosensors are created by drop-casting of synthesized PSPs on silicon substrate followed by depositing an additional thin layer of silver. Finally, the optimized SERS nanosensors with a Raman enhancement factor of 108 are able to detect chlorpyrifos pesticide down to 10-10 M thanks to the presence of abundant Raman hot-spots on the synthesized PSPs and the effective analyte enrichment derived from π-π interaction between pesticide molecules and aromatic backbone of amPEN.