Chemically Fueled Supramolecular Materials.

In biology, the function of many molecules is regulated through nonequilibrium chemical reaction cycles. The prototypical example is the phosphorylation of an amino acid in an enzyme which induces a functional change, e.g., it folds or unfolds, assembles or disassembles, or binds a substrate. Such phosphorylation does not occur spontaneously but requires a phosphorylating agent with high chemical potential (for example, adenosine triphosphate (ATP)) to be converted into a molecule with lower chemical potential (adenosine diphosphate (ADP)). When this energy is used to regulate an assembly, we speak of chemically fueled assemblies; i.e., the molecule with high potential, the fuel, is used to regulate a self-assembly process. For example, the binding of guanosine triphosphate (GTP) to tubulin induces self-assembly. The bound GTP is hydrolyzed to guanosine diphosphate (GDP) upon assembly, which induces tubulin disassembly. The result is a dynamic assembly endowed with unique characteristics, such as time-dependent behavior and the ability to self-heal. These intriguing, unique properties have inspired supramolecular chemists to create similar chemically fueled molecular assemblies from the bottom up. While examples have been designed, they remain scarce partly because chemically fueled reaction cycles are rare and often complex. Thus, we recently developed a carbodiimide-driven reaction cycle that is versatile and easy to use, quantitatively understood, and does not suffer from side reactions. In the reaction cycle, a carboxylate precursor reacts with a carbodiimide to form an activated species like an anhydride or ester. The activated state reacts with water and thereby reverts to its precursor state; i.e., the activated state is deactivated. Effectively, the precursor catalyzes carbodiimides' conversion into waste and forms a transient activated state. We designed building blocks to regulate a range of assemblies and supramolecular materials at the expense of carbodiimide fuel. The simplicity and versatility of the reaction cycles have democratized and popularized the field of chemically fueled assemblies. In this Account, we describe what we have "learned" on our way. We introduce the field exemplified by biological nonequilibrium self-assembly. We describe the design of the carbodiimide-driven reaction cycle. Using examples from our group and others, we offer design rules for the building block's structure and strategies to create the desired morphology or supramolecular materials. The discussed morphologies include fibers, colloids, crystals, and oil- and coacervate-based droplets. We then demonstrate how these assemblies form supramolecular materials with unique material properties like the ability to self-heal. Besides, we discuss the concept of reciprocal coupling in which the assembly exerts feedback on its reaction cycle and we also offer examples of such feedback mechanisms. Finally, we close the Account with a discussion and an outlook on this field. This Account aims to provide our fundamental understanding and facilitate further progress toward conceptually new supramolecular materials.

A chemically fueled supramolecular glue for self-healing gels.

Chemically fueled supramolecular materials offer unique properties that include spatial and temporal control and even the ability to self-heal. Indeed, a few studies have demonstrated the ability to self-heal, however, the underlying mechanisms remain unclear. Here, we designed a peptide that forms a fibrillar network upon chemical fueling. We were surprised that the hydrogel could self-heal despite the lack of dynamics in the fiber assembly and disassembly. We explain this behavior by a mechanism that involves the chemically fueled peptide molecules that cannot self-assemble due to the lack of nucleation sites. When the fibers are perturbed, new nucleation sites form that help the assembly resulting in the healing of the damaged network. Furthermore, we generalized the behavior for other peptides. We refer to this non-assembling, chemically-fueled peptide as a molecular glue. In future work, we aim to explore whether this self-healing mechanism applies to more complex structures, narrowing the gap between biological and synthetic self-assemblies.

A rotating bioreactor for the production of biofilms at the solid-air interface.

Conventional bioreactors are typically developed for the production of planktonic bacteria or submerged biofilms. In contrast, reactors for the continuous production of biofilms at the solid-air interface are scarce, and they require specific conditions since the bacteria need to attach firmly to the surface and require a permanent supply of moisture and nutrients from below. Recently, research from the field of civil engineering has pinpointed an increased need for the production of terrestrial biofilms: several variants of Bacillus subtilis biofilms have been shown to be useful additives to mortar that increase the water repellency, and, thus, the lifetime of the cementitious material. The bioreactor introduced here allows for the continuous production of such bacterial biofilms at the solid-air interface, and they have virtually identical properties as biofilms cultivated via classical microbiological techniques. This is made possible by equipping a rotating cylinder with a porous membrane that acts as a solid growth substrate the bacterial biomass can form on. In this configuration, nutrient supply is enabled via diffusive transport of a suitable growth medium from the core volume of the cylindrical reactor to the membrane surface. In addition to cultivating bacterial biofilms, the versatile and adaptable set up introduced here also enables the growth of other microbial organisms including the yeast Saccharomyces cerevisiae and the fungus Penicillium chrysogenum.