Effect of salt addition on a triblock copolymer-zwitterionic surfactant assembly: insight from excited-state proton transfer†

Abstract

Copolymer-surfactant assemblies are frequently utilized across various fields, from medicine to nanotechnology. Understanding the organization of the mixed assemblies in a saline environment will further expand their application horizons, especially under physiological conditions. Excited-state proton transfer (ESPT) can provide insight into the hydration nature and organization of the non-toxic assembly of a triblock copolymer F127 (poly-(ethylene oxide)₁₀₁ (PEO₁₀₁)-poly(propylene oxide)₅₆ (PPO₅₆)-PEO₁₀₁)) and a zwitterionic sulfobetaine surfactant N-dodecyl-N,N-dimethyl-3-ammoniopropane sulfonate (SB12). Here, we present a comprehensive investigation of the compactness and hydration nature of the F127-SB12 mixed assemblies at different salt concentrations using the ESPT of 8-hydroxy pyrene-1,3,6-trisulfonate (HPTS). In the absence of salts, gradual SB12 addition to a premicellar (0.4 mM) or a post-micellar (4 mM) F127 solution leads to an anomalous modulation of the protonated and deprotonated emission bands. The emission intensity ratio (protonated/deprotonated) first increases to a maximum at a particular SB12 concentration (6 mM and 35 mM for the premicellar and post-micellar F127 assemblies, respectively), and then the ratio decreases with a further increase in the surfactant concentration. Since the intensity ratio is an indicator of the retardation of the ESPT process, the mixed micellar configuration displaying a maximum intensity ratio represents the most compact and least hydrated state. Salt addition to this configuration lowers the intensity ratio, signifying an enhanced ESPT process. Dynamic light scattering (DLS) results indicate that the size of the mixed assembly remains almost unaltered with the addition of salts. Thus, salinity enhances the ESPT process inside the F127-SB12 mixed assemblies without significantly altering the hydrodynamic radius.