Abstract
Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.
Highlights
Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures
Crystalline frameworks and nanoscale hydrogels of spherical, vesicular, and cylindrical morphology are controllably assembled from solely a poly(propylene sulfone) (PPSU) homopolymer when transitioning from dimethylsulfoxide (DMSO) solution to the aqueous system
PPSU can be synthesized from the complete oxidation of poly(propylene sulfide) (PPS)[14,15], which is known for its hydrophobic–hydrophilic transition upon oxidation[16,17,18]
Summary
Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. Semi-flexible PPSU chains form electrostatically bound networks that reorganize dynamically as interactions among sulfone repeat units increase This system mimics the dynamic self-assembly of proteins[12] and DNA13, allowing the design and fabrication of diverse superstructures capable of highly efficient molecular encapsulation
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