Donor–Acceptor-Type Supramolecular Polymers Derived from Robust yet Responsive Heterodimeric Tweezers

Abstract

Molecular tweezer/guest recognition has emerged as a novel motif for the construction of supramolecular polymers. However, the overwhelming majority of ADA- or DAD-type (D = donor, A = acceptor) molecular tweezer/guest recognition systems suffer from relatively low binding affinities and inconspicuous variations toward external stimuli. To address this issue, herein a novel heterodimeric DADA-type complex has been designed and constructed. By engineering of donor–acceptor and hydrogen-bonding interactions, it demonstrates 1000 times enhancement for the complexation strength (K a = 2.23 × 106 M–1) than the ADA-type counterpart. Moreover, by modulating the intermolecular hydrogen bonds involved in the system, its binding affinity exhibits significantly large variations toward external stimuli (∼102–103-fold change for K a). The robust yet adaptive heterodimeric complex is employed as a tecton for the fabrication of high-molecular-weight donor–acceptor-type supramolecular polymers, demonstrating the efficiency and versatility to develop self-assembled materials via rational engineering of fundamental noncovalent recognition motifs.

Photoluminescent and Chromic Nanomaterials for Anticounterfeiting Technologies: Recent Advances and Future Challenges

“…Supramolecular chemistry is based on reversible and weak physical interactions between small or large molecules. The physical interactions in supramolecules are hydrogen bonding, hydrophobic forces, van der Waals forces, π–π stacking, and metal–ligand coordination, which are significantly influenced by the chemical structure of the molecules and polarity of the surrounding media. − A wide range of supramolecular materials from different small molecules to large molecules are present, which have various characteristics and applications in biology, bioimaging, drug delivery, gene delivery, chemosensors or biosensors, inkjet printing inks, and, most importantly, anticounterfeiting materials. − The high molecular weight polymer inks with high viscosity could result in blocking of the nozzle and consequently decreasing operational efficiency of the printers. Therefore, the supramolecular inks have been considered in inkjet printing to induce self-assembly of the low molecular weight molecules on a paper surface, where the high molecular weight supramolecular inks display physical and chemical properties similar to polymeric inks without any nozzle blocking problems.…”

In-Depth Analysis of Supramolecular Interfacial Polymerization via a Computer Simulation Strategy

“…A supramolecular polymer is a polymeric array whose monomers are connected via a noncovalent bond, while its behavior is similar to a conventional polymer in solution or in bulk. − The driving force of supramolecular polymerization basically involves noncovalent interactions with high direction or intensity, such as multiple hydrogen bonds, − host–guest interaction, − π–π interactions, − metal coordination − and the cooperation of multiple interactions. − Because of the dynamic and reversible nature of the noncovalent interaction, supramolecular polymers possess special characteristics compared to classical polymers, e.g., reversibility, self-healing, degradability, and stimuli-responsiveness. − ,− Therefore, they are already widely applied in heterogeneous catalysis, polymer gels, and biological imaging/sensing, and they are used as drug carriers in addition to other applications. − Supramolecular polymers are also acknowledged to be potentially utilized for the preparation of intelligent functional materials, environment-friendly materials, photoelectric materials, biomedical materials, and so on. ,, …”

Supramolecular switching of the self-assembly of cyclic peptide–polymer conjugates via host–guest chemistry

“…Supramolecular polymers are defined as polymeric arrays of monomeric units which are held together by highly directional and reversible non-covalent interactions, [1][2][3][4][5][6][7][8][9] such as multiple hydrogen bonding, [10][11][12][13] host−guest interactions, [14][15][16][17][18] metalcoordination interactions, [19,20] donor−acceptor interactions. [21,22] Among these, tubular supramolecular polymers assembled by cyclic peptide-polymer conjugates belong to a relatively new class of self-assembled supramolecular polymers. [23][24][25][26][27][28][29][30] The alternating D-and L-amino acid configuration of the cyclic peptide leads to the formation of a flat ring-like structure.…”