Visualizing the Heterogeneity in Homogeneous Supramolecular Polymers

The dynamic properties of supramolecular polymers enable new functionality beyond the limitations of conventional polymers. The mechanism of the monomer exchange between different supramolecular polymers is proposed to be closely associated with local disordered domains within the supramolecular polymers. However, a direct detection of such heterogeneity has never been experimentally probed. Here, we present the direct visualization of the local disordered domains in the backbone of supramolecular polymers by a super-resolution microscopy technique: Nile Red-based spectrally resolved point accumulation for imaging in nanoscale topography (NR-sPAINT). We investigate the local disordered domains in trisamide-based supramolecular polymers comprising a (co)assembly of benzene-1,3,5-tricarboxamide (BTA) and a variant with one of the amide bonds inverted (iBTA). The NR-sPAINT allows us to simultaneously map the spatial distribution and polarity of the local disordered domains along the polymers with a spatial precision down to ∼20 nm. Quantitative autocorrelation and cross-correlation analysis show subtle differences in the spatial distribution of the disordered domains between polymers composed of different variants of BTA monomers. Further, statistical analysis unraveled high heterogeneity in monomer packing at both intra- and interpolymer levels. The results reported here demonstrate the necessity of investigating the structures in soft materials at nanoscale to fully understand their intricacy.