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ISMSC 2007 - Università degli Studi di Pavia

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Anion bin<strong>di</strong>ng as a conformational and self-assembly trigger<br />

Jonathan W. Steed<br />

Chemistry Department, Durham University, Durham DH1 3LE, UK. Jon.steed@durham.ac.uk<br />

We have designed a number of anion-bin<strong>di</strong>ng containers exhibiting dynamic conformational<br />

behaviour. These systems range from macrobicyclic cryptands (1) exhibiting conformational<br />

twisting to tripodal (2) and tetrapodal hosts (3) exhibiting significant flexibility of the pendant<br />

arms. The containers’ dynamic properties are modulated by anion bin<strong>di</strong>ng. Anion bin<strong>di</strong>ng may<br />

also be used to modulate self-assembly and hence rheological properties in supramolecular gel<br />

phase systems. This lecture explores the scope and uses of this kind of fundamental process in<br />

preparing new supramolecular sensors and materials.<br />

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Oligopyrrole-based chemosensors for potentially hazardous materials<br />

Jonathan L. Sessler † , Marcin Stpie † , Patricia Melfi † , Kent Nielsen †,‡ , Jan Jeppesen, ‡ Evgeny<br />

Katayev †,§ , Bertrand Donnio , Jackie Veauthier ° , and Andrew M. Shaw <br />

† Department of Chemistry & Biochemistry, The University of Texas at Austin, 1 University<br />

Station A5300, Austin, TX 78712-0165 USA<br />

‡ Dept. of Physics and Chemistry, University of Southern Denmark, Campusvej 55, DK-5230,<br />

Odense M, Denmark<br />

§ Institute for Organoelement Chemistry, Russian Academy of Sciences, Vavilova st. 28,<br />

Moscow, 119991, Russia<br />

Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 (CNRS-Université<br />

Louis Pasteur), 23 rue du Loess BP 43, 67034 Strasbourg Cedex 2, France<br />

° C-IIAC (Inorganic, Isotope, & Actinide Chemistry), Los Alamos National Laboratory, MS J514,<br />

Los Alamos, NM 87545, USA<br />

EvanesCo Ltd, 4 &5 Forde Court, Forde Road, Newton Abbot, TQ12 4AD, United Kingdom<br />

The design and synthesis of novel receptors with the ability to recognize selectively and signal<br />

selected analytes through easy-to-visualize changes in color constitutes a critical goal in<br />

macrocyclic and supramolecular chemistry. We have approached this broad objective via the<br />

construction of both cyclic and acyclic pyrrole-based receptors that are able to interact with<br />

cationic, anionic, and neutral substrates through various combinations of metal coor<strong>di</strong>nation,<br />

hydrogen bon<strong>di</strong>ng, electrostatic, and donor-acceptor interactions. In this presentation the focus<br />

will be on systems, such as those shown in Figure 1, that allow for the specific colorimetric<br />

detection of potentially hazardous analytes, inclu<strong>di</strong>ng such canonical risks as high-valent<br />

ra<strong>di</strong>oactive actinide cations, the pertechnetate anion, and electron deficient nitroarene<br />

explosives. Several lead references are given below.<br />

The work in the presenter’s laboratory was supported by the National Institutes of Health, the<br />

National Science Foundation, and the U.S. Department of Energy.<br />

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Figure 1: Novel receptors and sensors relevant to this presentation.<br />

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[1] Nielsen, K. A.; Cho, W.-S.; Jeppesen, J. O.; Lynch, V. M.; Becher, J.; Sessler, J. L. J. Am.<br />

Chem.Soc. 2004, 126, 16296-16297.<br />

[2] Sessler, J. L.; Katayev, E. A.; Pantos, G. D.; Reshetova, M. D.; Khrustalev, V. N.; Lynch, V.<br />

M.; Ustynyuk, Y. A. Angew. Chem. Int. Ed. 2005, 44, 7386-7390.<br />

[3] Stpie, M.; Donnio, B.; Sessler, J. L. Angew. Chem. Int. Ed. <strong>2007</strong>, 46, 1431–1435.<br />

[4] Sessler, J. L.; Melfi, P. J.; Seidel, D.; Gorden, A. V.; Ford, D. K.; Palmer, P. D.; Tait, C. D.<br />

Tetrahedron, 2004, 60, 11089-11097.<br />

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