Chemical degradation as an enabling pathway to polymersome functionalization†

Readiness and the ability to functionalize are the fundamental features of natural living systems. Understanding the chemical roots of functionalization is a basic quest for the generation of new materials in the laboratory and chemistry-based natural-life-mimicking artificial or synthetic living systems. Using polymerization-induced self-assembly (PISA) and starting from a homogeneous aqueous blend of a few strictly non-biochemical compounds, it is possible to create amphiphiles that can self-boot into submicron supramolecular objects (micelles). These micelles under the control of chemistry can undergo (1) morphological evolution into giant polymersomes and (2) exhibit growth-implosion cycles accompanied by (3) vesicle self-reproduction and population growth. We call the physico-chemical processes underlying these life-like systems “Phoenix dynamics”. Herein, we studied how the emergence of such functions in these systems can occur owing to the combination of the chemical degradation of the macro chain transfer agents involved in the PISA process due to the presence of oxygen and its impact on the physico-chemical evolution of these objects. Results indicated implications for the controllable degradation-triggered functionalization of self-booted synthetic supramolecular self-assembling systems and provided a physicochemical pathway to implement novel functionalities in supramolecular systems. Functionalization of polymersomes is of interest in many areas of science and technology, including biomedical and environmental applications and origins of life studies.