Dissipative supramolecular systems driven by chemical fuels
Abstract
Bottom-up approaches to spontaneously self-assemble molecules have resulted in well-ordered and sophisticated architectures, many of which are able to exert specific functions.1 Whereas traditionally the equilibrium properties of the assemblies were studied, in more recent years the focus has shifted to kinetical studies of the assembly process. The latter studies have provided new mechanistic insights (e.g., nucleation effects and multiple couple equilibria), and have shown that the sequence and rate of experimental procedures (e.g., dilution, heating/cooling, stirring/shaking) determines the “pathway selection” of the assembly process.2–4 Recently, we have demonstrated an approach where redox reactions are used to achieve pathway selection, which will be one of the topics of my presentation.5In addition, we demonstrate that chemical fuels can be used to obtain so-called dissipative self-assembly. Specifically, we use a self-assembling system that is controlled by phosphorylation and dephosphorylation cycles powered by adenosine-5’-triphosphate (ATP) as a chemical fuel. Using dissipative self-assembly approaches we hope to go beyond the current switchable (and stimuli-responsive) supramolecular systems, and make structures that resemble natural microtubules both in structure as well as in function.As a small bonus, I will show our work on chiral separation of enantiomers using strong shear flows.6 We start from cm-sized model systems and describe the scaling down to the single molecule level. Our hope is to achieve chiral separation without the need of a stationary chiral phase, as is common in high pressure liquid chromatography.
REFERENCES
1. Lehn, J.-M. Supramolecular Chemistry: Concepts and Perspectives. (Wiley, 1995)
2. Korevaar, P. A. et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012)
3. Tantakitti, F. et al. Energy landscapes and functions of supramolecular systems. Nat. Mater. advance online publication, (2016)
4. Tidhar, Y., Weissman, H., Wolf, S. G., Gulino, A. & Rybtchinski, B. Pathway-Dependent Self-Assembly of Perylene Diimide/Peptide Conjugates in Aqueous Medium. Chem. – Eur. J. 17, 6068–6075 (2011)
5. Leira-Iglesias, J., Sorrenti, A., Sato, A., Dunne, P. A. & Hermans, T. M. Supramolecular pathway selection of perylenediimides mediated by chemical fuels. Chem. Commun. 52, 9009–9012 (2016)
6. Hermans, T. M., Sato, A., Marichez, V. Method for chiral resolution and device therefor WO2016020532 (2016)
Host: Wim Noorduin
