ABSTRACT
The influence of seed topologies on seeded supramolecular polymerization was examined using helicoidal and toroidal supramolecular polymer seeds. The addition of these seeds to a supersaturated solution of monomers led to distinct nucleation-growth kinetics, which were attributed to the significant difference between the elongation from helicoid termini and secondary nucleation catalyzed by the toroid surface.
ABSTRACT
A judicious combination of ring-closing supramolecular polymerization and secondary nucleation can hierarchically organize a diphenylnaphthalene barbiturate monomer bearing a 3,4,5-tri(dodecyloxy)benzyloxy unit into self-assembled nano-polycatenanes composed of nanotoroids. In our previous study, nano-polycatenanes of variable length have been formed uncontrollably from the monomer that provides nanotoroids with sufficiently wide inner void space wherein secondary nucleation is driven by non-specific solvophobic interaction. In this study, we found that the elongation of the alkyl chain length of the barbiturate monomer decreases the inner void space of nanotoroids while increasing the frequency of secondary nucleation. These two effects resulted in an increase in the yield of nano-[2]catenane. This unique property observed in our self-assembled nanocatenanes might be extended to a controlled synthesis of covalent polycatenanes using non-specific interactions.
