One-, two-, and three-dimensional hierarchical self-assembly of non-amphiphilic low-entropy chains from nanotubes to nanoribbons and porous net-sheets

The association of some small molecules such as benzene and phthalimide with non-amphiphilic homopolymeric low-entropy chains such as PVAc, PVA, PVP, and PNIPAM has been realized by reversible addition-fragmentation chain transfer reaction (RAFT) method. The as-prepared PT-PVA, PT-PVAc, PT-PVP, and PT-PNIPAM can serve as new building blocks and show the capability in concentration-dependent multidimensional self-assembly from vesicles to nanotubes, nanoribbons, and three-dimensional porous net-sheet structures. The introduction of low-entropy chains enables small molecules to aggregate into the J-type formation, which confers small molecules with the fluorescence-color-tunable ability. Incidentally, due to the essence of loosely stacking of J-type aggregates, reversible disassembly of the systems has also ensued. In particular, biocompatible PT-PVA shows excellent cell-labeling and sustained-drug-release abilities. This system promises potential applications in preparing sophisticated nanostructures and designing new sustained-drug-release systems from simple small molecules.