1. Cu(I)-Induced G-Quartets: Robust Supramolecular Polymers Exhibiting Heating-Induced Aqueous Phase Transitions Into Gel or Precipitate.
- Author
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Sahu N, Guchhait C, Mohanta I, Suriyaa V, and Adhikari B
- Abstract
Certain proteins and synthetic covalent polymers experience aqueous phase transitions, driving functional self-assembly. Herein, we unveil the ability of supramolecular polymers (SPs) formed by G
4 .Cu+ to undergo heating-induced unexpected aqueous phase transitions. For the first time, guided by Cu+ , guanosine (G) formed a highly stable G-quartet (G4 .Cu+ )/G-quadruplex as a non-canonical DNA secondary structure with temperature tolerance, distinct from the well-known G4 .K+ . The G4 .Cu+ self-assembled in water through π-π stacking, metallophilic and hydrophobic interactions, forming thermally robust SPs. This enhanced stability is attributed to the stronger coordination of Cu+ to four carbonyl oxygens of G-quartet and the presence of Cu+ - - -Cu+ attractive metallophilic interactions in Cu+ -induced G-quadruplex, exhibiting a significantly higher interaction energy than K+ as determined computationally. Remarkably, the aqueous SP solution exhibited heating-induced phase transitions-forming a hydrogel through dehydration-driven crosslinking of SPs below cloud temperature (Tcp ) and a hydrophobic collapse-induced solid precipitate above Tcp , showcasing a lower critical solution temperature (LCST) behavior. Notably, this LCST behavior of G4 .Cu+ SP originates from biomolecular functionality rather than commonly exploited thermo-responsive oligoethylene glycols with supramolecular assemblies. Furthermore, exploiting the redox reversibility of Cu+ /Cu2+ , we demonstrated control over the assembly and disassembly of G-quartets/G-quadruplex and gelation reversibly., (© 2025 Wiley-VCH GmbH.)- Published
- 2025
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