A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

David T J Morris; Steven M Wales; David P Tilly; Elliot H E Farrar; Matthew N Grayson; John W Ward; Jonathan Clayden

doi:10.1016/j.chempr.2021.06.022

A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

Chem. 2021 Sep 9;7(9):2460-2472. doi: 10.1016/j.chempr.2021.06.022.

Authors

David T J Morris¹, Steven M Wales¹, David P Tilly¹, Elliot H E Farrar², Matthew N Grayson², John W Ward¹, Jonathan Clayden¹

Affiliations

¹ School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
² Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.

Abstract

Communication of information through the global switching of conformation in synthetic molecules has hitherto entailed the inversion of chirality. Here, we report a class of oligomer through which information may be communicated through a global reversal of polarity. Ethylene-bridged oligoureas are constitutionally symmetrical, conformationally flexible molecules organized by a single chain of hydrogen bonds running the full length of the oligomer. NMR reveals that this hydrogen-bonded chain may undergo a coherent reversal of directionality. The directional uniformity of the hydrogen-bond chain allows it to act as a channel for the spatial communication of information on a molecular scale. A binding site at the terminus of an oligomer detects local information about changes in pH or anion concentration and transmits that information-in the form of a directionality switch in the hydrogen-bond chain-to a remote polarity-sensitive fluorophore. This propagation of polarity-encoded information provides a new mechanism for molecular communication.

Keywords: NMR; binding; communication; conformation; dynamic foldamer; hydrogen bonding; information theory; oligomer; stimulus responsive; urea.