The First Water-Soluble Copper(I) Calix[6]arene Complex Presenting a Hydrophobic Ligand Binding Pocket: A Remarkable Model for Active Sites in Metalloenzymes
Yannick Rondelez
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorGildas Bertho
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorOlivia Reinaud
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorYannick Rondelez
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorGildas Bertho
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorOlivia Reinaud
Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques CNRS UMR 8601, Université René Descartes 45 rue des Saints-Pères, 75270 Paris Cedex 06 (France) Fax: (+33) 1-42-86-83-87
Search for more papers by this authorWe would like to thank Dr. Michèle Salmain (ENSCP, Paris) for her help with the IR spectroscopy experiments performed in water, and express our gratitude to Dr. Olivier Laprevotte (ICSN, Gif-sur-Yvette) for electron spray mass spectra.
Graphical Abstract
Deutliche Stabilisierung erfährt ein Kupfer(i)-Zentrum im gezeigten Trisulfonatocalix[6]aren-Komplex, der die Bezeichnung „biomimetisch“ wirklich verdient, da er wasserlöslich ist und eine freie Bindungsstelle für z. B. CO aufweist. Damit imitiert er die erste Koordinationssphäre von Kupferenzymen und die hydrophobe Mikroumgebung des aktiven Zentrums.
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The Δδ shifts for Ha vs Hd and Hb vs He are 1.09 and 1.01, respectively. This is much higher than the shift by ca. 0.5 expected for a simple electronic effect due to the bromo and sulfonato substituents. For para-substituted toluenes the ortho protons (relative to Br or SO
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