Cross-Fiber Networking Between Self-Sorted Pyrene and Ferrocene Functionalized GQuadruplex Nanofibers: Gels with Enhanced Mechanical Strength and Self-Healing

Abstract

Cells, as intricate supramolecular systems, integrate multiple bio-supramolecules to execute complex biological functions that surpass the capabilities of individual molecules. Despite significant advances in understanding the assembly of individual (supra)molecules, the interplay between distinct (supra)molecular systems in mixtures remains poorly understood. This study demonstrates that pyrene (Py) and ferrocene (Fc) conjugated G-quadruplex fibers undergo selfsorting in mixtures, driven by stronger π–π interactions between Py-Py pairs than Fc-Py interactions. Notably, these self-sorted fibers form preferential inter-fiber cross-links through complementary, weak interactions between Py and Fc units,1 as evidenced by fluorescence spectroscopy and transmission electron microscopy. This multipoint cross-fiber networking enhances gelation efficiency and mechanical strength in the mixed gel, outperforming individual GPy and GFc gels. Moreover, the mixed gel exhibits rapid self-recovering properties, reconciling the typically mutually exclusive relationship between hydrogel toughness and rapid selfrecovery.2 These findings highlight the strategic potential of leveraging weak, complementary interactions to improve the structural and functional properties of supramolecular biomaterials, with implications for applications such as controlled drug delivery.