Formation of homochiral helical nanostructures in diblock copolymers under the confinement of nanopores

Abstract

The control of the homochirality of helical structures formed in achiral systems is of great interest as it is helpful for understanding the origin of homochirality in life. In this work, we introduce a spiral arrangement of patches into the inner surface of a nanopore to guide the self-assembly of a cylinder-forming AB diblock copolymer melt into a homochiral single helix. We calculate the free energy of the single-helical structures with different handedness using self-consistent field theory (SCFT). Moreover, we simulate the self-assembly process using an iterative process of SCFT solution starting from a disordered state, and count the formation probability of different helical structures. We find that the formation probability of the homochiral helix with favorable free energy increases rapidly, leading to the conclusion that a minuscule difference of 0.5–1.0 × 10⁻⁴k_BT per chain is enough to obtain the homochiral helix by suppressing its counterpart of a higher free energy. However, for a stronger chiral guiding field, other homochiral helical structures with unfavorable handedness and thus increasingly higher free energy become more likely to be formed. Morphological snapshots during the self-assembly process reveal that the formation of these metastable helical structures is induced by their kinetic pathways, which are altered to be favorable by the strong chiral field of the patch pattern. Therefore, our work suggests that both thermodynamics and kinetics are important for controlling the chirality of helical structures.