Photocatalytic Aqueous CO2 Reduction to CO and CH4 Sensitized by Ullazine Supramolecular Polymers.

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.

Hybrid gels via bulk interfacial complexation of supramolecular polymers and polyelectrolytes.

Hierarchical self-assembly leading to organized supramolecular structures across multiple length scales has been of great recent interest. Earlier work from our laboratory reported the complexation of peptide amphiphile (PA) supramolecular polymers with oppositely charged polyelectrolytes into a single solid membrane at a macroscopic interface. We report here the formation of bulk gels with many internal interfaces between the covalent and supramolecular polymer components formed by the rapid chaotic mixing of solutions, one containing negatively charged PA nanofibers and the other the positively charged biopolymer chitosan. We found that formation of a contact layer at the interface of the solutions locks the formation of hydrogels with lamellar microstructure. The nanofiber morphology of the supramolecular polymer is essential to this process since gels do not form when solutions of supramolecular assemblies form spherical micelles. We found that rheological properties of the gels can be tuned by changing the relative amounts of each component. Furthermore, both positively and negatively charged proteins are easily encapsulated within the contact layer of the gel, which provides an interesting biomedical function for these systems.

Biomimetic Extracellular Scaffolds by Microfluidic Superstructuring of Nanofibers.

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.