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J Org Chem. 2014 Sep 5;79(17):8383-96. doi: 10.1021/jo501595k. Epub 2014 Aug 26.

β-sheet-like hydrogen bonds interlock the helical turns of a photoswitchable foldamer to enhance the binding and release of chloride.

Author information

1
Chemistry Department, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.

Abstract

Inspired by halorhodopsin's use of photoisomerization to regulate chloride, aryltriazole-based foldamers have been created to "catch and release" chloride ions upon light irradiation of end-appended azobenzenes. The proposed mode of stabilization exploits a β-sheet-like hydrogen-bonding array to cooperatively interlock the ends of a foldamer together with its helical core. We find that the hydrogen-bonding array has a greater influence on stabilizing the helix than the π-stacked seam under the conditions examined (50:50 MeCN/THF). Thus, we show how it is possible to enhance the difference between Cl(-) binding and release using light-dependent control over the foldamer's degree of helix stabilization. Making and breaking three π-π contacts with light caused an 8-fold change in chloride affinity (40 300 M(-1) ⇄ 5000 M(-1)), five π-π contacts produced a 17-fold change (126 000 M(-1) ⇄ 7400 M(-1)), and strategically located hydrogen-bonding units enabled a greater 84-fold differential (970 000 M(-1) ⇄ 11 600 M(-1)). The improved performances were attributed to stepwise increases in the preorganization of the binding pocket that catches chloride while leaving the cis states with just one π-π contact relatively unchanged.

PMID:
25157797
DOI:
10.1021/jo501595k
[Indexed for MEDLINE]

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