ISMSC 2007 - Università degli Studi di Pavia
ISMSC 2007 - Università degli Studi di Pavia
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 />
1 2 3<br />
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NH<br />
N +<br />
HN<br />
R<br />
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R<br />
O<br />
O<br />
N +<br />
O<br />
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O HN<br />
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IL 7<br />
IL 8<br />
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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NH HN<br />
N<br />
H<br />
N<br />
N<br />
isoamethyrin<br />
Ph Ph<br />
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NH HN<br />
N<br />
NH HN<br />
BP-DPM<br />
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R<br />
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cyclo[8]pyrrole<br />
Figure 1: Novel receptors and sensors relevant to this presentation.<br />
N<br />
S S<br />
Me Me<br />
Me<br />
Me<br />
N<br />
S H S S<br />
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S H S S<br />
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Me Me<br />
S S<br />
[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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PrS<br />
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PrS SPr<br />
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PrS<br />
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SPr<br />
TTF calix[4]pyrrole<br />
SPr<br />
SPr