Thermosetting supramolecular polymerization of compartmentalized DNA fibers with stereo sequence and length control

•Supramolecular polymers with blocks of different DNA sequences along their lengths•Unique thermosetting mechanism in which small pieces are fused end-to-end at 90°C•Fiber-fiber interactions controlled by the stereochemical sequence polymer•Protein-like folding DNA-polymer building critical to fiber morphology Supramolecular perform a range important functions nature—from cellular movement muscle contraction—enabled complex nanoscale structure. Realizing this complexity synthetic systems requires hierarchical self-assembly pathway. Branched assemble into supramolecular fibers unique, heat-driven, multistep process. By controlling process, smaller fragments can be “thermoset” together piece-by-piece fashion make segmented that display discrete lengths. Further control is afforded varying stereosequences polymers, resulting fiber-fiber interactions. Due water-based chemistry and biocompatibility, these may used softer, greener technologies require spatial organization components, such as biomaterials or energy-harvesting structures. nanostructures highly addressable compatible biological but often hundreds unique strands for assembly. On other hand, nature structures from identical compartmentalizing process: assembling molecules sub-components bringing across multiple length scales. Inspired we report conjugates through heat-driven form displaying axis polymerization. These one-dimensional retain compartmentalization programmed pre-assembled segments. Length over segments also achieved gel purification cylindrical micelles. Importantly, show hydrophobic core amplified distinctive morphological traits fibers. Molecular dynamics simulations model structure elucidate how manifests itself exciting examples nanomaterials built repetitive molecular units.1De Greef T.F. Smulders M.M. Wolffs M. Schenning A.P. Sijbesma R.P. 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Mg2+—a long observed—we sharp peak q values indicating ordering crystallinity distance 3.27 nm 1E). could correspond spacing phosphodiester backbones ordered crystalline core.39Golder SAXS performed no peaks S15 S16). suggests transformation disordered globular sphere cylinder occurs increased facilitated part We 2A S17). slowly heated sequentially holding 10 min each 30°C, 50°C, 70°C, 90°C. Not up including 90°C, 90°C room temperature, elongated preserved S18). lower temperatures, mixtures intermediate present, converted longer polymers. dependence allowed possibility deliberately manipulating parameters. initial test subsequently increasing heating S19). Without heating, resultant much S20). Based observations, propose possible elongation First, gives preferred due inter-oligomer repulsion. 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Some DNAb suggesting some exchange; however, non-specific labeling controls S30 S31). method “tagging” aids visibility demonstrates organization. sizes changing pre-assemble 3C S32–S34). (?) analysis before after S35 S36). (LN) 23.3 (? 1.00) 41.9 1.34) after. supports statistical mode join stochastically. increases 6.25 3C). Despite dispersity, significance distribution still LN following 204 1.69) 382 1.82), respectively, (p < 0.001). Highly required manner. corona segmentation facilitate super-structured bundles, junctions, networks DNA-DNA truly assemblies, required. In systems, micelles, facilitating structures.23Gilroy Gäd