Visualizing nanostructures in supramolecular hydrogels: a correlative study using confocal and cryogenic scanning...

Solvated supramolecular hydrogels present unique challenges in nanoscale morphological characterization because of their fragile fibrous nature and low concentration of the solid component. In this study, imidazolium-based hydrogels containing either diketopyrrolopyrrole (DPP) or zinc(II) phthalocyanine (ZnPc) fluorophores were imaged using confocal laser scanning microscopy (CLSM) of fully solvated gels and cryogenic scanning electron microscopy (cryo-SEM) was used to observe the corresponding xerogels. The DPP@Gel systems exhibit strong fluorescence and are effectively imaged using CLSM, with fibre morphologies that closely correlate with those seen with cryo-SEM. In contrast, the analogous imidazolium gel system containing a sulfonated zinc phthalocyanine (ZnPc@Gel) yields poor CLSM images because of the relatively weak emission and sample disruption during compression, whereas cryo-SEM enables clear visualization of the native fibrous network. These results demonstrate the complementary nature of CLSM and cryo-SEM and highlight the value of cryo-SEM as a very useful tool for imaging soft nanomaterials with low fluorescence or limited optical contrast.