Solution-Based Thermodynamically Controlled Conversion from Diblock Copolymers to Janus Nanoparticles.

Nanosized polymeric Janus particles (NPJPs) have important applications in a variety of theoretical and practical research fields. However, the methods that are versatile and can prepare NPJPs highly efficiently are very limited. Herein, we reported a two-step thermodynamically controlled preparation of NPJPs with a high yield using a diblock copolymer as the precursor. At the first step, A--B coassembled in the solution with a partner diblock copolymer C--B to form the mixed shell micelles (MSMs) with B core and A/C mixed shell. Then, intramicellarly covalently cross-linking the A block chains resulted in the complete phase separation of A and C chains in the mixed shell, leading to the direct conversion of the MSMs into NPJPs. The first step, diblock copolymer micellization, is known as a thermodynamically controlled process, and we also made the second step, conversion from MSMs to NPJPs, be thermodynamically controlled due to the application of covalent cross-linking. As the result, the conversion efficiency is close to 100%. Besides, it was further confirmed that the method can be applied to different systems and used to tune the Janus balance. Therefore, this conversion should be very significant for the fabrication and application of the NPJPs.