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Abstract Naturally occurring polymeric structures often consist of 1D polymer chains intricately folded and entwined through non‐covalent bonds, adopting precise topologies crucial for their functionality. The exploration of crystalline 1D polymers through dynamic covalent chemistry (DCvC) and supramolecular interactions represents a novel approach for developing crystalline polymers. This study shows that sub‐angstrom differences in the counter‐ion size can lead to various helical covalent polymer (HCP) topologies, including a novel metal‐coordination HCP (m‐HCP) motif. Single‐crystal X‐ray diffraction (SCXRD) analysis of HCP−Na revealed that double helical pairs are formed by sodium ions coordinating to spiroborate linkages to form rectangular pores. The double helices are interpenetrated by the unreacted diols coordinating sodium ions. The reticulation of the m‐HCP structure was demonstrated by the successful synthesis of HCP−K. Finally, ion‐exchange studies were conducted to show the interconversion between HCP structures. This research illustrates how seemingly simple modifications, such as changes in counter‐ion size, can significantly influence the polymer topology and determine which supramolecular interactions dominate the crystal lattice.
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Engineering the Nanoscaled Morphologies of Linear DNA Homopolymers
Abstract Supramolecular polymers have unique characteristics such as self‐healing and easy processing. However, the scope of their structures is limited to mostly either flexible, random coils or rigid, straight chains. By broadening this scope, novel properties, functions, and applications can be explored. Here, DNA is used as a model system to engineer innovative, nanoscaled morphologies of supramolecular polymers. Each polymer chain consists of multiple copies of the same short (38–46 nucleotides long) DNA strand. The component DNA strands first dimerize into homo‐dimers, which then further assemble into long polymer chains. By subtly tuning the design, a range of polymer morphologies are obtained; including straight chains, spirals, and closed rings with finite sizes. Such structures are confirmed by AFM imaging and predicted by molecular coarse simulation.
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- PAR ID:
- 10449005
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Rapid Communications
- Volume:
- 42
- Issue:
- 15
- ISSN:
- 1022-1336
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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