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A disulfide made by oxidation of 8-thioguanosine is a supergelator. The hydrogels are redox-responsive, as they disassemble upon either reduction or oxidation of the S–S bond. We also identified this disulfide, and 2 other compounds, as intermediates in oxidative desulfurization of 8-thioG to guanosine. 

Small molecule guests influence the functional properties of supramolecular hydrogels. Molecular-level understanding of such sol-gel compositions and structures is challenging due to the lack of long-range order and inherently heterogeneous sol-gel interface. In this study, insight into the uptake process of biologically relevant small molecules into guanosine-quartet(G4) borate hydrogels is obtained by gel-state magic-angle spinning (MAS) NMR spectroscopy. G4∙K + borate hydrogel can absorb up to 0.3 equivalent of cationic methylene blue (MB) without a significant disruption of the G4 fibrils that make up the gel, whereas the addition of over 0.3 equivalents of MB to the same gel leads to a gel-to-sol transition. The gel-to-sol transition process is characterized ex situ by analyzing and comparing the 1 H and 11 B MAS NMR spectra acquired before and after the MB uptake. In particular, 11 B isotropic chemical shifts and quadrupole interactions were determined by analyzing the 11 B MAS NMR spectra acquired at different magnetic fields, 11.7 T, 14.1 T and 20 T, which enable the different local bonding environments of borate anions in sol- and gel domains to be distinguished and identified. By comparison, uptake of heterocyclic molecules such as adenine, cytosine and 1-methylthymine into G4∙Na + borate hydrogels lead to stiff and clear gels while increasing the solubility of the nucleobases as compared to the solubility of the same compounds in water. G4∙Na + gel can uptake one equiv. of adenine with minimal disruption to the sol-gel framework, thus enhancing the adenine solubility up to an order of magnitude as compared to water. Combined multinuclear ( 1 H, 11 B and 23 Na) NMR spectroscopy analysis and vial inversion tests revealed that the nucleobases are embedded into pores of the sol phase rather than being closely interacting with the G-4 fibrils that make up the gel phase. These results indicate that G-4 hydrogels have potential applications as carrier systems for small molecules. Gel-state MAS NMR spectroscopy can be used to gain insight into host-guest interactions in complex heterogeneous sol-gel systems, which is often difficult to obtain from the conventional techniques such as X-ray scattering, electron microscopy and optical spectroscopy.