Sol–gel selection of hybrid G-quadruplex architectures from dynamic supramolecular guanosine libraries

Abstract

We report an original strategy to transcribe and to fix the self-assembly of G-quadruplex architectures in self-organized nanohybrids. In the first resolution step the G-quartet is pre-amplified in solution in the presence of metal cations from a dynamic pool of ribbon-type or cyclic supramolecular architectures. Then in a second selection sol-gel step the G-quadruplex is irreversibly fixed in a siloxane inorganic network. The interface between the guanosine moiety and the heterosiloxane 3 is based on a double reversible covalent iminoboronate connection. This contributes to the high levels of adaptability and correlation in the self-organization of the supramolecular G-quadruplex and the inorganic siloxane systems. Biomimetic-type hybrids can be generated by using this strategy.

Applications of guanine quartets in nanotechnology and chemical biology

“…The strategy of using cryptands to modulate Gribbon/Gquartet interconversion was previously described in organic solution by Spada and colleagues with LipoG (2) 101 and a 5′Ooligothiophene guanine derivative 102 . Higherorder, selforganized, hybrid organic/inorganic materials have also been built on Gquartetbased organogels formulated from a guanine-siloxane derivative (15) in the presence of K + or barium (Ba 2+ ) ions 103 . The polymerization of -SiR 2 -OEt into -SiR 2 -O-SiR 2 -was triggered by water, leading to higherordered hybrid materials with micro metric crystallinerod morphologies (Fig.…”

Self‐Assembled Supramolecular Channels: Toward Biomimetic Materials for Directional Translocation

“…The resolution of such dynamic supramolecular libraries may be achieved by sol‐gel processes, thereby resulting in the amplification of the most‐compact architectures, owing to the combined hydrophobic/H‐bonding affinities in the final constitutional structure of the resultant hybrid materials, compared with the unpolymerized powders . This strategy has also been used to transcribe the supramolecular chirality of the G‐quadruplex ( 20 ) on the nanoscale and microscale to obtain chiral hybrid materials ( 21 ) by using achiral guanosine‐heteropolysiloxane starting components (Figure ) . Stacked G‐quartet superstructures that are stabilized by templating K + cations induce an important increase in the conductivity by a factor of 1000 of G‐quartet membrane films compared to the non‐templated G‐ribbon membrane, which presents very low conductivity .…”

Dynamic Covalent Chemistry of Aldehyde Enamines: BiIII‐ and ScIII‐Catalysis of Amine–Enamine Exchange

“…The emergence of constitutional dynamic chemistry, relying on reversible reactions/interactions to change the constitution of systems, has led to the establishment of a range of applications . For example, the design and discovery of ligands, receptors, reactions, and catalysts have been established, a range of materials have been produced, and a basic understanding of complex networks and systems has been established . To meet with the operational requirements of generating and applying complex systems, new types of exchange reactions that enable novel constitutional diversity are in high demand.…”