Polyelectrolyte chain conformation matters in macroscopic supramolecular self-assembly

We demonstrate molecular-conformation-dependent macroscopic supramolecular self-assembly (MSA) driven by electrostatic interactions. Evidence from single molecular force spectroscopy reveals that polyelectrolytes modified on MSA component surfaces make MSA possible with a loop conformation, while those with a flat conformation lead to no assembly, which is attributed to distinct molecular mobility. We believe that this finding is also applicable in fundamental phenomena such as surface adsorption and adhesion regarding polymers.