Regulation of Two-Dimensional Platelet Micelles with Tunable Core Composition Distribution via Coassembly Seeded Growth Approach

Abstract

Seeded growth termed “living” crystallization-driven self-assembly (CDSA) has been identified as a powerful method to create one- or two-dimensional nanoparticles. Epitaxial crystallization is usually regarded as the growth mechanism for the formation of uniform micelles. From this perspective, the unimer depositing rate is largely related to the crystallization temperature, which is a key factor to determine the crystallization rate and regulate the core composition distribution among nanoparticles. In the present work, the coassembly of two distinct crystallizable polymers is explored in detail in a one-pot seeded growth protocol. Results have shown that polylactone containing a larger number of methylene groups (−CH₂−) in their repeating units such as poly(η-octalactone) (POL) has a faster crystallization rate compared to poly(ε-caprolactone) (PCL) with a smaller number of −CH₂– at ambient temperature (25 °C), thus a block or blocky platelet structure with heterogeneous composition distribution is formed. In contrast, when the crystallization temperature decreases to 4 °C, the difference of crystallization rate between both cores become negligible. Consequently, a completely random component distribution within 2D platelets is observed. Moreover, we also reveal that the core component of seed micelles is also paramount for the coassembly seeded growth, and a unique structure of flower-like platelet micelle is created from the coassembly of PCL/POL using POL core-forming seeds. This study on the formation of platelet micelles by one-pot seeded growth using two crystallizable components offers a considerable scope for the design of 2D polymer nanomaterials with a controlled core component distribution.