Supramolecular Nanotube Reactors for Production of Imine Polymers with Controlled Conformation, Size, and Chirality

A series of supramolecular nanotubes with inner diameters of 1, 4, 9, 12, 16, and 29 nm are prepared from amino acid lipids. The hydrophobic channels of the nanotubes act as reactors for the formation of imine polymers by not only effectively encapsulating the benzaldehyde and diacetyleneamine precursors of the imine monomers but also markedly accelerating imine formation. The nanotube inner diameter determines whether the imine monomers self-assemble into nanoparticles, nanotapes, nanocoils, or twisted nanofibers in the channels. UV-induced polymerization of the diacetylene units in the imine nanostructures followed by decomposition of the nanotubes into molecular dispersions of the constituent amino acid lipids results in expulsion of the polymerized imine nanostructures with retained conformation. The isolated nanocoils and twisted nanofibers retain the helicity and circular dichroism induced by the nanotubes, which exhibits supramolecular chirality, even though the components of the imine monomers are achiral. These supramolecular nanotubes with tunable diameters and functionalizable surfaces can be expected to be useful for the production of polymers with controlled conformation, size, and chirality without the need for rational design or chemical modification of the monomers or optimization of the polymerization conditions.