Deciphering the Influence of Zwitterionic Surfactants on Pluronic Co-assemblies: A Synergistic Odyssey through Spectroscopic, Microscopic, and Scattering Techniques

Abstract

Fundamental investigations into the photophysical properties and microenvironmental features of pluronic–zwitterionic surfactant mixed assemblies are essential for advancing our understanding of molecular interactions at the nanoscale, setting the stage for innovative solutions in drug delivery, diagnostics, and other applications of pluronic–zwitterionic surfactant assemblies. This investigation explores the intricate photophysics of pluronic–zwitterionic surfactant mixed assemblies, utilizing the twisted intramolecular charge transfer state forming styryl dye trans-2-[(4-dimethylamino) styryl] benzothiazole as a probe. By comparing the behaviors of two distinct poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) block copolymers with block composition of (PEO)_132-(PPO)₅₀-(PEO)₁₃₂ [F108] and (PEO)₁₀₀-(PPO)₆₅-(PEO)₁₀₀ [F127] at concentrations of 5 and 10 wt %, this study systematically examines the impact of the addition of zwitterionic surfactants. Through a comprehensive set of analytical techniques, including UV–visible absorption, steady-state emission, and time-resolved fluorescence emission studies, significant alterations in the emission spectra and quantum yields were observed upon the addition of zwitterionic surfactants. These modifications suggest a dynamic equilibrium for the transitioning of dye molecules between various microenvironments within the assemblies. Additionally, dynamic light scattering, zeta potential (ζ), nuclear Overhauser effect spectroscopy, small-angle neutron scattering, cryogenic transmission electron microscopy, field emission scanning electron microscopy, and fluorescence lifetime imaging microscopy analyses have shed light on the substantial impact of surfactant incorporation on the structural properties of assemblies.