There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO2 reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO2 photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH4 comparable to those obtained with a precious metal-based [Ru­(phen)3]­(PF6)2 sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

We report on the formation of bulk gels by mixing oppositely charged supramolecular and covalent polymers. Complexation at the interface of the solutions creates a diffusion barrier that can encapsulate proteins.

The extracellular matrix is a dynamic framework bearing chemical and morphological cues that support many cellular functions, and artificial analogs with well-defined chemistry are of great interest for biomedical applications. Herein, we describe hierarchical, extracellular-matrix-mimetic microgels, termed “superbundles” (SBs) composed of peptide amphiphile (PA) supramolecular nanofiber networks created using flow-focusing microfluidic devices. We explore the effects of altered flow rate ratio and PA concentration on the ability to create SBs and develop design rules for producing SBs with both cationic and anionic PA nanofibers and gelators. We demonstrate the morphological similarities of SBs to decellularized extracellular matrices and showcase their ability to encapsulate and retain proteinaceous cargos with a wide variety of isoelectric points. Finally, we demonstrate that the novel SB morphology does not affect the well-established biocompatibility of PA gels.