Strengthened cooperativity of DNA-based cyclic hydrogen-bonded rosettes by subtle functionalization

Area of Science:

• Supramolecular Chemistry
• Computational Chemistry
• Biomolecular Design

Background:

• Hydrogen-bonded supramolecular systems benefit from cooperative effects for enhanced stability.
• Guanine-cytosine motifs are fundamental building blocks in supramolecular chemistry.
• Understanding and enhancing cooperativity is key to designing advanced functional materials.

Purpose of the Study:

• To design a novel monomer for hydrogen-bonded rosettes that maximizes cooperative effects.
• To investigate the synergistic enhancement of supramolecular systems through tailored molecular design.
• To computationally evaluate the cooperative strength of the designed system.

Main Methods:

• Relativistic dispersion-corrected density functional theory (DFT) computations were employed.
• A Janus-type guanine-cytosine motif was utilized as the basis for rosette design.
• The design focused on a monomer with three aligned hydrogen bonds to strengthen interactions.

Main Results:

• The designed monomer resulted in shorter hydrogen bonds and stronger donor-acceptor interactions.
• Electrostatic interactions were found to be more attractive in the new rosette structure.
• The designed guanine-cytosine rosette demonstrated triple the cooperativity of natural guanine quadruplexes.

Conclusions:

• The novel guanine-cytosine monomer significantly enhances cooperativity in hydrogen-bonded supramolecular systems.
• This design offers a pathway to create highly stabilized supramolecular structures.
• The findings provide a new strategy for designing synergistic supramolecular materials.