In contrast to more polar media, G-quadruplex assembly reveals remarkably high thermodynamic and kinetic stability in toluene solutions. Depending on the substituents installed at the lipophilic guanosine, either a dodecamer or an octamer complex is formed in the presence of K or Na salts that resist conditions of high dilution and elevated temperatures without exhibiting significant dissociation. Moreover, kinetic exchange between complexed and uncomplexed G is slow enough in NMR to monitor G-quadruplex formation along a day time scale.
An imine-based covalent organic framework (COF) decorated in its cavities with uracil groups has shown selective recognition towards adenine in water. These results show how the confinement of the base-pair inside the COF's pores allows a remarkable selective recognition in aqueous media.
In analogy to covalent reactions,t he understanding of noncovalent association pathwaysi sf undamental to influence and control any supramolecular process.F ollowing an approach that is reminiscent of covalent methodologies,w e study here,f or the first time,t he mechanism of G-quadruplex formation in organic solvents.O ur results support ar eaction pathway in whichthe cation shifts the equilibrium towards aGquartet transient intermediate,which then acts as atemplate in the formation of the G-quadruplex product.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
Herein, we show that twisted molecular nanoribbons with as many as 322 atoms in the aromatic core are efficient gelators capable of self-assemblying into ordered π-gels with morphologies that vary...
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