Single-molecule resolution of the conformation of polymers and dendrimers with solid-state nanopores

Polymers and dendrimers are macromolecules, possessing unique and intriguing characteristics, that are widely applied in self-assembled functional materials, green catalysis, drug delivery and sensing devices. Traditional approaches for the structural characterization of polymers and dendrimers involve DLS, GPC, NMR, IR and TG, which provide their physiochemical features and ensemble information, whereas their unimolecular conformation and dispersion also are key features allowing to understand their transporting profile in confined ionic nanochannels. This work demonstrates the nanopore approach for the determination of charged homopolymers, neutral block copolymer and dendrimers under distinct bias potentials and pH conditions. The nanopore translocation properties reveal that the dispersion and transporting of PEI is pH-dependent, and its capture rate is much lower than that of PAA. The neutral block copolymer with longest molecular chain threads through with longest blockage duration, its highest capture rate was achieved in 0.5 M KCl at pH 5 with slow diffusion and high temporal resolution. The two generations of neutral dendrimers could also translocate under bias potentials, probably due to the ions adsorption on the dendrimers and driven by Brownian force. The TEG-81 with larger molecular size translocates with longer residence time and higher blockage ratio, as expected. Both of the dendrimers exhibit a higher blockage ratio at pH 7.4 than either acidic or alkalic condition, indicating a larger stretched conformation adopted under neutral condition. This work presents the analysis of unimolecular charged and neutral polymers and dendrimers, which will be insightful in understanding the self-assembly motion and transfer of synthetic macromolecules in confined space. It also provides a good indication for deciphering the macromolecule-nanopore interplay under electrophoretic condition.