Oxidation-Induced Breakage of the Imine Bond and Aggregate Transition in a Se-Containing Dynamic Covalent Surfactant.

Abstract

Controlling the dynamic imine bonds upon a novel trigger except for pH and temperature is still a significant challenge. Here, a Se-containing imine-based dynamic covalent surfactant (HOBAB-BSeEA) was developed for the first time by mixing two precursors in situ: an asymmetric double-chain cationic surfactant bearing a formyl group at the terminal of one hydrophobic tail and a Se-containing amine (2-(benzylselanyl)ethan-1-amine) in order to confirm the effect of redox on the imine bonds. The imine bond in HOBAB-BSeEA can be regulated not only upon changing the pH as well as other common imine-based surfactants but also by oxidation. The conversion efficiency of imine bonds is closely related with the degree of oxidation and pH. Complete oxidation can decrease the conversion efficiency from ∼87 to 48%, which is comparable to the result of changing the pH from 10.0 to 7.0. With the formation and breaking of imine bonds, the surfactant can be reversibly switched between symmetric and asymmetric structures, accompanied by a morphological transition from vesicles to spherical micelles. Although oxidation cannot demolish all imine bonds, it can completely convert vesicles to spherical micelles, which is mainly ascribed to an increase in the polarity of the micellar microenvironment stemming from the oxidation of Se. However, this transition can only be achieved by reducing the pH to 5.0 instead of 7.0. Nile red loaded in HOBAB-BSeEA vesicles can be quickly, controllably, and step-by-step released upon oxidation stimulus but not pH. Understanding the mechanism of oxidation-induced breakage of imine bonds and disruption of vesicles would be useful in designing redox-responsive imine-based carriers that can unload cargoes according to the level of the local reactive oxygen species.