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Experimental evidence for the functional relevance of anion-pi interactions

Dawson, Ryan E. and Hennig, Andreas and Weimann, Dominik P. and Emery, Daniel and Ravikumar, Velayutham and Montenegro, Javier and Takeuchi, Toshihide and Gabutti, Sandro and Mayor, Marcel and Mareda, Jiri and Schalley, Christoph A. and Matile, Stefan . (2010) Experimental evidence for the functional relevance of anion-pi interactions. Nature Chemistry, 2 (7). pp. 533-538.

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Official URL: http://edoc.unibas.ch/dok/A5839688

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Abstract

Attractive in theory and confirmed to exist, anion–π interactions have never really been seen at work. To catch them in action, we prepared a collection of monomeric, cyclic and rod-shaped naphthalenediimide transporters. Their ability to exert anion–π interactions was demonstrated by electrospray tandem mass spectrometry in combination with theoretical calculations. To relate this structural evidence to transport activity in bilayer membranes, affinity and selectivity sequences were recorded. π-acidification and active-site decrowding increased binding, transport and chloride > bromide > iodide selectivity, and supramolecular organization inverted acetate > nitrate to nitrate > acetate selectivity. We conclude that anion–π interactions on monomeric surfaces are ideal for chloride recognition, whereas their supramolecular enhancement by π,π-interactions appears perfect to target nitrate. Chloride transporters are relevant to treat channelopathies, and nitrate sensors to monitor cellular signaling and cardiovascular diseases. A big impact on organocatalysis can be expected from the stabilization of anionic transition states on chiral π-acidic surfaces.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Molecular Devices and Materials (Mayor)
UniBasel Contributors:Mayor, Marcel and Gabutti, Sandro
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Nature
ISSN:1755-4330
e-ISSN:1755-4349
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:05 Apr 2017 13:50
Deposited On:14 Sep 2012 06:58

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