Regulating the self-assembly of rigid sphere-rod amphiphiles via. the side-chain length: coarse-grained molecular dynamics informed by all-atom data

Amphiphilic molecules comprising rigid hydrophilic and hydrophobic blocks can form various self-assembled structures, and their local packing is strongly influenced by the length of the side chains. We investigate how side-chain length modulates molecular packing and mesoscale order, using a transferable coarse-grained (CG) molecular dynamics model parameterized from all-atom simulations via structure and force matching. The CG description enables simulations that are an order of magnitude larger and longer than atomistic trajectories, permitting quantitative assessment of pathway kinetics and steady-state organization.  By systematically comparing amphiphiles with different side-chain lengths, we identify how variations in chain length influence molecular packing, aggregation patterns, and overall structural organization. The CG simulation results show good agreement with both all-atom studies and experimental observations, confirming that the developed CG model reliably captures the key factors governing self-assembly behavior in these systems.