Abstract
Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function. We herein show an example of such molecular recognition-controlled kinetic assembly/disassembly processes within artificial supramolecular polymer systems using six-membered hydrogen-bonded supramolecular complexes (rosettes). Electron-rich and poor monomers are prepared that kinetically coassemble through a temperature-controlled protocol into amorphous coaggregates comprising a diverse mixture of rosettes. Over days, the electrostatic interaction between two monomers induces an integrative self-sorting of rosettes. While the electron-rich monomer inherently forms toroidal homopolymers, the additional electrostatic interaction that can also guide rosette association allows helicoidal growth of supramolecular copolymers that are comprised of an alternating array of two monomers. Upon heating, the helicoidal copolymers undergo a catastrophic transition into amorphous coaggregates via entropy-driven randomization of the monomers in the rosette.
Highlights
Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function
We envisaged that the incorporation of a molecular recognition process to preorganize polymerizable complexes of an artificial supramolecular polymer[13,14,15] could generate smart macromolecular systems whose assembly and disassembly are controlled by the conformation of the complexes[16,17]
A 1H NMR study of 2 in CDCl3 indicated that its hydrogen-bonding capability was almost identical to 1, atomic force microscopy (AFM) and transmission electron microscopy (TEM) images of self-assembled 2 in methylcyclohexane (MCH) exhibited only indistinct linear fibrils (Fig. 1d and Supplementary Figs. 13–16)
Summary
Molecular recognition to preorganize noncovalently polymerizable supramolecular complexes is a characteristic process of natural supramolecular polymers, and such recognition processes allow for dynamic self-alteration, yielding complex polymer systems with extraordinarily high efficiency in their targeted function. We show an example of such molecular recognition-controlled kinetic assembly/disassembly processes within artificial supramolecular polymer systems using six-membered hydrogen-bonded supramolecular complexes (rosettes). As small conformational changes in the complexes may severely affect the outcome of such hierarchical processes, biological molecular systems behave dynamically: they operate in conditions far from equilibrium and optimize component structures and functions according to environment[2] This is true of the protein ensembles and relatively simple one-dimensional assemblies of proteins, i.e., biological supramolecular polymers[3,4,5,6,7]. Two structurally related polypeptides of α- and β-tubulin monomer subunits complementarily form α–β heterodimer complexes through hydrophobic and electrostatic interactions[8,9,10,11] The resulting thermodynamically stable helicoidal copolymers are thermally stable to a specific temperature, but above this transition catastrophically into a kinetic mixture of the rosette complexes due to the internal disorganization of the integrated rosette complex
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