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Stimuli-Responsive Polymer Coatings for the Rapid and Tunable Contact Transfer of Plasmid DNA to Soft SurfacesFree, publicly-accessible full text available October 10, 2023
Influence of Side Chain Hydrolysis on the Evolution of Nanoscale Roughness and Porosity in Amine-Reactive Polymer MultilayersWe report the influence of side chain hydrolysis on the evolution of nanoscale structure in thin films fabricated by the reactive layer-by-layer (LbL) assembly of branched poly(ethylenimine) (PEI) and poly(2-vinyl-4,4-dimethylazlactone) (PVDMA). LbL assembly of PEI and PVDMA generally leads to the linear growth of thin, smooth films. However, assembly using PVDMA containing controlled degrees of side chain hydrolysis leads to the growth of thicker films that exhibit substantial nanoscale roughness, porosity, and have resulting physicochemical behaviors (e.g., superhydrophobicity) that are similar to those of some thicker PEI/PVDMA coatings reported in past studies. Our results reveal that the degree of PVDMA partial hydrolysis (or carboxylic acid group content) influences the extent to which complex film features develop, suggesting that ion-pairing interactions between hydrolyzed side chains and amines in PEI promote the evolution of bulk and surface morphology. Additional experiments demonstrate that these features likely arise from polymer/polymer interactions at the surfaces of the films during assembly, and not from the formation and deposition of solution-phase polymer aggregates. When combined, our results suggest that nanoporous structures and rough features observed in past studies likely arise, at least in part, from some degree of adventitious side chain hydrolysis in the PVDMA used formore »