Polystyrenesulfonate (PSS), as one of the most important categories of polyelectrolytes, has received increasing attention due to its great potential in the applications of energy-and biomedical-related fields. However, most of the previous studies only focused on linear PSS and its derivatives, but little attention was paid to nonlinear topological PSSs. So far, the synthesis of nonlinear PSSs with well-defined structures is still a challenging task, and the main obstacle lies in the stability issue of functional chemical linkages during the sulfonation process of polystyrene (PS) precursors, such as the carbon−oxygen-containing linkages. Herein, by rationally designing the chemical structure of the functional linkage, we introduce a versatile and efficient strategy for the preparation of topological PSSs. Specifically, by embedding firm triazole linkages (without carbon−oxygen linkages) into the backbone structure of cyclic and hyperbranched PS precursors, the backbone and functional linkages are found to present excellent chemical stability under certain sulfonation conditions, which eventually lead to the successful preparation of cyclic and hyperbranched PSSs. By using two sets of PSS samples with varied molar masses, the scaling relations between the number of repeating units and the sedimentation coefficient are established for both linear and cyclic PSSs. We believe that our proposed synthetic strategy is universal and could be extended to the synthesis of other types of topological PSSs.

Gold nanorod (AuNRs) modified by reduction-responsive amphiphilic copolymer poly(ε-caprolactone)-b-poly[(oligoethylene glycol)acrylate] (LA–PCL–SS–POEGA) can enhance the cellular uptake of AuNRs, presumably due to the aggregation under reducing environment in the cells.