Nonequilibrium assembly mechanisms of Janus-polymer-grafted carbon nanotubes during surface-initiated...

Surface-initiated polymerization on anisotropic templates provides a useful framework for exploring polymerization-driven self-assembly under nonequilibrium conditions. Here, we investigate surface-initiated polymerization-coupled assembly on idealized Janus-polymer-grafted carbon nanotube (CNT) templates using dissipative particle dynamics coupled with a stochastic reaction model. The term "polymerization-coupled assembly" is used in a generic mechanistic sense to describe concurrent surface chain growth and assembly, rather than a direct implementation of a specific experimental PISA protocol. The polymerization exhibits effective first-order kinetics, while aggregation of solvophobic grafted chains leads to diffusion-induced retardation at later stages. By systematically varying the packing fraction f_{p}, aspect ratio L/D, and average grafted chain length n, we identify distinct nonequilibrium morphologies ranging from lamellar micelles to multilayer vesicles. Multivariate analysis reveals that packing fraction primarily controls assembly size and complexity, aspect ratio governs curvature and orientational ordering, and chain length modulates interlayer spacing and vesicle stability. We further uncover a characteristic "G"-shaped curling pathway during vesicle formation, highlighting the coupling between polymerization kinetics and anisotropic assembly pathways. The model is intended as a qualitative guide for future experiments on anisotropic polymer/CNT assemblies, not as a direct description of an existing experimental system.