Model-driven engineering of supramolecular buffering by multivalency.

Paffen, Tim F E; Teunissen, Abraham J P; de Greef, Tom F A; Meijer, E W · Proc Natl Acad Sci U S A · 2017

basic_science · Level V

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Abstract

A supramolecular system in which the concentration of a molecule is buffered over several orders of magnitude is presented. Molecular buffering is achieved as a result of competition in a ring-chain equilibrium of multivalent ureidopyrimidinone monomers and a monovalent naphthyridine molecule which acts as an end-capper. While we previously only considered divalent ureidopyrimidinone monomers we now present a model-driven engineering approach to improve molecular buffering using multivalent ring-chain systems. Our theoretical models reveal an odd-even effect where even-valent molecules show superior buffering capabilities. Furthermore, we predict that supramolecular buffering can be significantly improved using a tetravalent instead of a divalent molecule, since the tetravalent molecule can form two intramolecular rings with different "stabilities" due to statistical effects. Our model predictions are validated against experimental <sup>1</sup>H NMR data, demonstrating that model-driven engineering has considerable potential in supramolecular chemistry.