Ionic gradients shape the spatial organization and dynamics of supramolecular polymers

Abstract

Living supramolecular materials such as microtubules and actin filaments assemble and function in dynamic, heterogeneous environments, subject to chemical concentration gradients. Their rapid and precise response to such gradients---via aggregation, disassembly, or autonomous motion---underlies the fine spatiotemporal control typical of living systems. Reproducing such responsiveness in synthetic materials is a central challenge in materials science and requires a molecular-level understanding of how gradients couple to supramolecular structure and dynamics, which remains difficult to access experimentally. To this end, we combine implicit-solvent coarse-grained molecular dynamics (MD) with the constant chemical potential MD (C$μ$MD) technique to investigate, at molecular resolution, the coupling of two prototypical supramolecular polymer models with externally imposed ionic concentration gradients. Despite their contrasting responses to homogeneous ionic conditions, both systems undergo pronounced spatial reorganization under the gradient, generating regions of locally enhanced supramolecular activity that are inaccessible to homogeneous systems with the same overall content of self-assembling species. Crucially, the local supramolecular dynamics is largely determined by the local concentrations, consistent with the formation of local quasi-equilibria: this direct connection between spatial composition and supramolecular activity emerges as a common governing principle across the two models. These findings shed light on the spatially complex supramolecular response that can be triggered by chemical gradients, and show how a single gradient simulation can encode this response across a continuous range of local chemical environments, thus providing a general strategy to investigate and design materials operating under spatially heterogeneous conditions.