Self-Oscillating Vesicles: Spontaneous Cyclic Structural Changes of Synthetic Diblock Copolymers

A large variety of synthetic vesicles has been created for potential engineering applications and as model systems which mimic living organisms. In most cases, the structure is designed to be thermodynamically stable. However, mimicking dynamic behaviors of living vesicles still remains undeveloped. Herein, we present a synthetic vesicle which shows autonomous disintegration–reconstruction cycles without any external stimuli and which is similar to those in living organisms, such as in the nuclear envelope and synaptic vesicles. The vesicle is composed of a diblock copolymer which has a hydrophilic and a thermosensitive segment. The thermosensitive segment includes a redox moiety that acts as a catalyst for an oscillatory chemical reaction and also controls the aggregation temperature of vesicles. Furthermore, autonomous fusion of vesicles is also observed during the cycles. Making and breaking: Biomimetic self‐oscillating vesicles that undergo autonomous and cyclic structural changes between vesicles and unimers without any external stimuli were developed by using synthetic polymers.