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Mimicking Biological Cation‐Transport Based on Sphere‐Surface Supramolecular Chemistry: Simultaneous Interaction of Porous Capsules with Molecular Plugs and Passing Cations
Author(s) -
Merca Alice,
Haupt Erhard T. K.,
Mitra Tamoghna,
Bögge Hartmut,
Rehder Dieter,
Müller Achim
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700294
Subject(s) - chemistry , formamidinium , tetramethylammonium , supramolecular chemistry , ligand (biochemistry) , ion exchange , nuclear magnetic resonance spectroscopy , crystallography , chemical engineering , ion , inorganic chemistry , stereochemistry , molecule , organic chemistry , iodide , biochemistry , receptor , engineering
Spherical capsules of the type [{(Mo)Mo 5 } 12 {Mo 2 (ligand)} 30 ] n − exhibiting 20 {Mo 9 O 9 } pores with crown ether functions allowed us to perform a sophisticated study of the title phenomenon based on synthetic work as well as NMR spectroscopy. The pores of the host system interact in solution specifically with guests that can be noncovalently bonded, such as formamidinium and acetamidinium cations, while having different affinities to the pores. The exchange between the guest species present in solution and in the pores was investigated, including, besides the extreme scenarios of complete pore closing and complete opening, that of stepwise pore plugging. Because of this option it was possible to model for the first time passive transmembrane cation transport based on gated pores/channels. These have the appropriate dimensions and can even adopt different structure flexibilities in response to different cations. The present investigation is based on related syntheses as well as on numerous detailed 7 Li NMR studies of Li + transport/exchange equilibria in dependence of the pore environment/guest situations. One compound containing capsules with sulfate ligands ( 2 ) could be obtained in which all the pores are plugged with formamidinium cations and another corresponding one was obtained with additionally encapsulated Ca 2+ ions ( 3 ); these were taken up after temporary release of some of the formamidinium plugs/guests upon short heating of the related solution.