Molecular Recognition-Driven Supramolecular Topological Reconfiguration

Molecular recognition-driven supramolecular assembly establishes a robust platform for topological morphological regulation and chiral signal transmission. Herein, we employ sugammadex (Sug) as a macrocyclic host that recognizes tetraphenylethylene pyridinium salt (TPE-Py) through synergistic hydrophobic and electrostatic interactions, forming a 2:1 TPE-Py⊂Sug complex exhibiting ratiometric fluorescence (emission redshift: from 555 to 600 nm). Crucially, competitive molecular recognition of neuromuscular blocking agents (NMBAs; e.g., rocuronium [Roc], vecuronium [Vec], pancuronium [Pan]) drives TPE-Py displacement due to Sug’s superior binding affinity for NMBAs, restoring TPE-Py’s intrinsic fluorescence (detection limits: 164.4 nM for Roc, 170.8 nM for Vec, 2187.7 nM for Pan). This recognition event orchestrates supramolecular topological reconfiguration: Electrostatically driven coassembly of displaced TPE-Py with NMBA⊂Sug yields a ternary NMBA⊂Sug@TPE-Py complex, inducing a morphological transition from nanoparticles to nanosheets─a signature of topological reconstruction. Chiral centers in NMBAs further modulate circular dichroism and chiroptical responses; notably for Vec, circularly polarized luminescence inverts from negative to positive (glum value changing from −2.4 × 10–4 to 2.7 × 10–4). Leveraging the fluorescence-concentration linearity with smartphone-based RGB analysis enables portable semiquantitative detection for NMBAs. This work establishes molecular recognition-driven topological reconfiguration as a paradigm for multichannel sensing and chiral regulation.