Gelation landscape engineering using a multi-reaction supramolecular hydrogelator system

Foster, Jamie S and Zurek, Justyna M. and Almeida, Nuno M. S. and Hendrikson, Wouter E. and le Sage, Vincent A. A. and Lakshminarayanan, Vasudevan and Thompson, Amber L and Banerjee, Ragul and Eelkema, Rienk and Mulvana, Helen Elizabeth and Paterson, Martin J and van Esch, Jan H and Lloyd, Gareth O. (2015) Gelation landscape engineering using a multi-reaction supramolecular hydrogelator system. Journal of the American Chemical Society, 137 (45). pp. 14236-14239. ISSN 0002-7863 (https://doi.org/10.1021/jacs.5b06988)

[thumbnail of Foster-etal-JACS2015-Gelation-landscape-engineering-using-multi-reaction-supramolecular-hydrogelator-system]
Preview
Text. Filename: Foster_etal_JACS2015_Gelation_landscape_engineering_using_multi_reaction_supramolecular_hydrogelator_system.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo

Download (1MB)| Preview

Abstract

Simultaneous control of the kinetics and thermodynamics of two different types of covalent chemistry allows pathway selectivity in the formation of hydrogelating molecules from a complex reaction network. This can lead to a range of hydrogel materials with vastly different properties, starting from a set of simple starting compounds and reaction conditions. Chemical reaction between a trialdehyde and the tuberculosis drug isoniazid can form one, two, or three hydrazone connectivity products, meaning kinetic gelation pathways can be addressed. Simultaneously, thermodynamics control the formation of either a keto or an enol tautomer of the products, again resulting in vastly different materials. Overall, this shows that careful navigation of a reaction landscape using both kinetic and thermodynamic selectivity can be used to control material selection from a complex reaction network.