ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
2 files

Organocatalytic Control over a Fuel-Driven Transient Esterification Network

preprint
submitted on 06.03.2020 and posted on 09.03.2020 by Michelle van der Helm, Chang-Lin Wang, Mariano Macchione, Eduardo Mendes, Rienk Eelkema

Signal transduction in living systems is the conversion of information into a chemical change and the principal process by which cells communicate. This process enables phenomena such as time-keeping and signal amplification. In nature, these functions are encoded in non-equilibrium (bio)chemical reaction networks (CRNs) controlled by enzymes. While these catalytically controlled processes are an integral part of biocatalytic pathways, man-made analogs are rare. Here, we incorporate catalysis in an artificial fuel driven out-of-equilibrium CRN. The study entails the design of an organocatalytically controlled fuel driven esterification CRN, where the forward (ester formation) and backward reaction (ester hydrolysis) are controlled by varying the ratio of two different organocatalysts: pyridine and imidazole. This catalytic regulation enables full control over ester yield and lifetime. The fuel-driven strategy is subsequently used in the design of a responsive polymer system, where transient polymer conformation and aggregation can be controlled through variation of fuel and catalysts levels. Altogether, we show how organocatalysis is an important tool to exert control over a man-made fuel driven system and induce a change in a macromolecular superstructure, as ubiquitously found in natural non-equilibrium systems.

Funding

European Research Council Consolidation Grant 726381

History

Email Address of Submitting Author

r.eelkema@tudelft.nl

Institution

Delft University of Technology

Country

Netherlands

ORCID For Submitting Author

0000-0002-2626-6371

Declaration of Conflict of Interest

none

Version Notes

pre-submission version

Exports