Lanthanide luminescence from supramolecular hydrogels consisting of bio-conjugated picolinic-acid-based guanosine quadruplexes

Kotova, Oxana and O'Reilly, Ciaran and Barwich, Sebastian T. and MacKenzie, Lewis E. and Lynes, Amy D. and Savyasachi, Aramballi J. and Ruether, Manuel and Pal, Robert and Möbius, Matthias E. and Gunnlaugsson, Thorfinnur (2022) Lanthanide luminescence from supramolecular hydrogels consisting of bio-conjugated picolinic-acid-based guanosine quadruplexes. Chem, 8 (5). pp. 1395-1414. ISSN 2451-9294 (https://doi.org/10.1016/j.chempr.2022.01.015)

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Abstract

The formation of bio-inspired healable lanthanide luminescent hydrogels is detailed. These materials are composed of K(I)-stabilized guanosine quadruplexes (G4) that were bio-conjugated to mannose-derived picolinic acid ligand 1 using boric acid chemistry (G4-1). The supramolecular self-assembly between G4-1 and europium (Eu(III)) was confirmed, including the use of time-gated luminescence spectroscopy. The most stable hydrogel was formed when the ratio between 1 and Eu(III) was 1:1, and this gel was found to retain a helical column. The obtained gel samples were further characterized using techniques, such as scanning electron microscopy (SEM), circular dichroism (CD), and luminescence spectroscopy. We demonstrate that a Eu(III)-centered circularly polarized luminescence (CPL) signal from guanosine hydrogels can be observed even via long-range interaction, whereas the rheology of these gels exhibits their healable properties.