A Carbodiimide-Fueled Reaction Cycle That Forms Transient 5(4H)-Oxazolones

Abstract

In life, molecular architectures, like the cytoskeletal proteins or the nucleolus, catalyze the conversion of chemical fuels to perform their functions. For example, tubulin catalyzes the hydrolysis of GTP to form a dynamic cytoskeletal network. In contrast, myosin uses the energy obtained by catalyzing the hydrolysis of ATP to exert forces. Artificial examples of such beautiful architectures are scarce partly because synthetic chemically fueled reaction cycles are relatively rare. Here, we introduce a new chemical reaction cycle driven by the hydration of a carbodiimide. Unlike other carbodiimide-fueled reaction cycles, the proposed cycle forms a transient 5(4H)-oxazolone. The reaction cycle is efficient in forming the transient product and is robust to operate under a wide range of fuel inputs, pH, and temperatures. The versatility of the precursors is vast, and we demonstrate several molecular designs that yield chemically fueled droplets, fibers, and crystals. We anticipate that the reaction cycle can offer a range of other assemblies and, due to its versatility, can also be incorporated into molecular motors and machines.

Bio‐Inspired Far‐From‐Equilibrium Hydrogels: Design Principles and Applications

“…Recently, Boekhoven developed a new system based on EDC. [126] Unlike other carbodiimide-fuelled reaction cycles, the proposed cycle forms a transient 5(4H)oxazolone, which is less prone to undergo side reactions, thus making the system robust under different conditions. Another way is to remove the waste or by-product from the system.…”

“…For example, Boekhoven has developed EDC‐driven chemical reaction cycles, however by‐product (i. e., O ‐acylurea) and its side reaction led to unwanted products and consumed chemical fuels without forming desired anhydride, inhibiting the sustainability of NES. Recently, Boekhoven developed a new system based on EDC [126] . Unlike other carbodiimide‐fuelled reaction cycles, the proposed cycle forms a transient 5( 4H )‐oxazolone, which is less prone to undergo side reactions, thus making the system robust under different conditions.…”

Chemically Fueled Logic AND Gate with Double Encoding in the Time Domain

“…Up to now, however, information processing in supramolecular systems is commonly confined to “static output” documented in truth tables, as seen in supramolecular materials, switchable catalytic machinery, , or bioinformation processing . Recent progress though on out-of-equilibrium materials, dissipative functional chemical systems, and fuel acid-driven catalysis has provided powerful tools for information handling with “dynamic” output in the time domain. ,, Yet, as far as we know, all of these systems operate with a single dynamic output. Thus, enabling information systems with two distinct time domains would lead to an enormous gain in information security.…”

Dynamic supramolecular hydrogels mediated by chemical reactions

“…The group of van Eelkema and van Esch pioneered the development of out-of-equilibrium supramolecular hydrogels using methylation reagents as the fuels. 22,53 After that, various beautiful examples of out-of-equilibrium supramolecular assemblies powered by different chemical fuels, including carbodiimide, 57–62 ATP, 55,63–69 pH regulators, 70–75 enzymatic reactions, 15,66,76–78 carbon dioxide, 79,80 and others, 81–84 have been carefully developed. The resultant supramolecular hydrogels show high dynamics, tunable lifetime and stiffness, and a regenerative capability.…”