. Le, DMF est alors évaporé sous pression réduite et le résidu lavé par 50 mL d'eau puis extrait par 3 fois 50 mL de dichlorométhane. Les phases organiques rassemblées sont séchées sur MgS0 4 et évaporées à sec sous pression réduite, Le mélange obtenu est purifié sur colonne de gel de silice (CH 2 Cb

. Cale, C% = 49,95 ; H% = 5,62, p.37

. Trouv, C% = 49,03 ; H% = 5,71, p.41

R. 13c, CD 3 SOCD 3 , 25°C; 0 = ppm) : 103 (Cl), C4, vol.84, issue.52 3, pp.73-71

R. Cdch, COCH 3 ), Cl)C4, vol.975221, issue.77C6, pp.171-169

F. Schardinger, ??ber thermophile Bakterien aus verschiedenen Speisen und Milch, Zeitschrift f??r Untersuchung der Nahrungs- und Genu??mittel, vol.6, issue.19, p.865, 1903.
DOI : 10.1007/BF02067497

H. Pringsheim, Chemistry of the Saccharides, p.280, 1932.

H. Pringsheim, R. P. Walton, and . Ed, A Comprehensive SU1ï J ey of Starch Chemistly, p.35, 1928.

P. Karrer and C. Nageli, Polysaccharide II. Zur Konstitution der Diamylose, Helvetica Chimica Acta, vol.45, issue.1, p.169, 1921.
DOI : 10.1002/hlca.19200030159

A. Miekeley and . Ber, Bemerkung zur Existenz der ??-Diamylose, Berichte der deutschen chemischen Gesellschaft (A and B Series), vol.64, issue.1, p.69, 1932.
DOI : 10.1002/cber.19310640841

K. Freudenberg, W. Rapp, and . Ber, Zur Kenntnis der St??rke und der Schardinger-Dextrine, Berichte der deutschen chemischen Gesellschaft (A and B Series), vol.494, issue.9, p.2041, 1936.
DOI : 10.1002/jlac.19324940105

K. Freudenberg, M. Meyes-delius, and . Ber, ??ber die Schardinger - Dextrine aus St??rke, Berichte der deutschen chemischen Gesellschaft (A and B Series), vol.518, issue.8, p.1596, 1938.
DOI : 10.1002/jlac.19355180107

K. Freudenberg, G. Blomquist, L. Ewald, K. Soff, and . Ber, Hydrolyse und Acetolyse der St??rke und der Schardinger-Dextrine, Berichte der deutschen chemischen Gesellschaft (A and B Series), vol.68, issue.6, p.1258, 1936.
DOI : 10.1002/hlca.19320150179

G. Caesar, Starch and Derivatives, p.290, 1986.

F. Y. Lichtentaler and S. Immel, Cyclodextrins, cyclomannins, and cyclogalactins with five and six (1???4)-linked sugar units: A comparative assessment of their conformations and hydrophobicity potential profiles1, Tetrahedron: Asymmetry, vol.5, issue.11, p.2045, 1994.
DOI : 10.1016/S0957-4166(00)86283-7

H. W. Frijlink, Biopharmaceutical aspects of cyclodextrins. Thesis. Groningen : Rijksuniversitet Groningen, 1990.

. Tabushi, Reactions of Inclusion Complexes formed by cyclodextrins and their derivatives Inclusion Compounds

. Szetjli, Industrial Applications ~f Cyclodextrins, Inclusion Compounds, vol.1, issue.3, p.331, 1984.

D. W. Armstrong, Cyclodextrins in Analytical Chemistry
DOI : 10.1007/978-94-009-2637-0_63

E. Smolkova-keulemansova, Cyclodextrins in Chromatography

D. Sybilska and E. Smolkova-keulemansova, Applications of Inclusion Compounds in Chromatography, Inclusion Compounds, vol.3, p.173, 1984.

J. Szejtli, The metabolism, toxicity and biological effects of cyclodextrins Cyclodextrins and their industrial uses, p.173, 1987.

J. Lehn and . La, Chimie Supramoléculaire : Concepts et Perspectives, 1997.

R. Breslow, M. Hammond, and M. Lauer, Selective transamination and optical induction by a .beta.-cyclodextrin-pyridoxamine artificial enzyme, Journal of the American Chemical Society, vol.102, issue.1, p.421, 1980.
DOI : 10.1021/ja00521a093

R. Breslow, A. Graff, and . Am, Geometry of enolization using a bifunctional cyclodextrin-based catalyst, Journal of the American Chemical Society, vol.115, issue.23, p.10988, 1993.
DOI : 10.1021/ja00076a066

R. Breslow, The chelate effect in binding, catalysis, and chemotherapy, Recueil des Travaux Chimiques des Pays-Bas, vol.88, issue.11, p.493, 1994.
DOI : 10.1073/pnas.68.2.378

R. Breslow and N. Nesnas, Burst kinetics and turnover in an esterase mimic, Tetrahedron Letters, vol.40, issue.17, p.3335, 1999.
DOI : 10.1016/S0040-4039(99)00460-8

R. Deschenaux, T. Ruch, P. Deschenaux, A. Juris, and R. Ziessel, Synthesis, Characterization, and Electrochemical and Photophysical Properties of Rhenium(I) and ruthenium(II) complexes of 2,2?-bipyridine ligand functionalized ?-cyclodextrins, Helvetica Chimica Acta, vol.55, issue.3, p.619, 1995.
DOI : 10.1016/S0022-0728(81)80457-3

Z. Pikramenou and D. G. Nocera, Luminescent supramolecular architectures: a cyclodextrin modified with a europium(III) crown swing, Inorganic Chemistry, vol.31, issue.4, p.532, 1992.
DOI : 10.1021/ic00030a002

T. A. Kaden, Advances in Supramolecular Chemistry 3, p.65, 1993.

J. Van-alphen, On aliphatic polyamines IV, Recueil des Travaux Chimiques des Pays-Bas, vol.38, issue.4, p.343, 1937.
DOI : 10.1002/recl.19370560405

B. Bosnich, C. K. Poon, and M. L. Tobe, Complexes of Cobalt(III) with a Cyclic Tetradentate Secondary Amine, Inorganic Chemistry, vol.4, issue.8, p.1102, 1965.
DOI : 10.1021/ic50030a003

M. D. Glick, D. P. Gavel, L. L. Diaddario, and D. B. Rorabacher, Structure of the 14-membered macrocyclic tetrathia ether complex of copper(II). Evidence for undistorted geometries in blue copper protein models, Inorganic Chemistry, vol.15, issue.5, p.1190, 1976.
DOI : 10.1021/ic50159a041

N. Jubran, G. Ginzberg, H. Cohen, and D. Meyerstein, Stabilization of the monovalent nickel complex with 1,4,8,11-tetraazacyclotetradecane in aqueous solutions by N- and C-methylation. An electrochemical and pulse radiolysis study, Inorganic Chemistry, vol.24, issue.3, p.251, 1985.
DOI : 10.1021/ic00197a002

C. M. Che, T. Lai, and K. Wong, Synthesis, reactivities, and structural studies on high-valent ruthenium oxo complexes. Ruthenium(IV), ruthenium(V), and ruthenium(VI) oxo complexes of tertiary amine ligands, Inorganic Chemistry, vol.26, issue.14, p.2289, 1987.
DOI : 10.1021/ic00261a025

C. L. Schmid, M. Neuburger, M. Zehnder, T. Kaden, and . Helv, Metal Complexes with Macrocyclic Ligands. Part XLIII. Tetraazamacrocyclic nickel(II) and copper(II) complexes with aliphatic methylthio- and methoxy-substituted pendant chains, Helvetica Chimica Acta, vol.48, issue.1, p.241, 1997.
DOI : 10.1016/B978-0-444-42815-8.50005-3

M. J. Young, J. Chin, and . Am, Dinuclear copper(II) complex that hydrolyzes RNA, Journal of the American Chemical Society, vol.117, issue.42, p.10577, 1995.
DOI : 10.1021/ja00147a022

D. H. Vance, A. Czarnik, and . Am, Functional group convergency in a binuclear dephosphorylation reagent, Journal of the American Chemical Society, vol.115, issue.25, p.12165, 1993.
DOI : 10.1021/ja00078a065

. Tabushi, Y. Kurodam, and . Am, Bis(histamino)cyclodextrin-zinc-imidazole complex as an artificial carbonic anhydrase, Journal of the American Chemical Society, vol.106, issue.16, p.4580, 1984.
DOI : 10.1021/ja00328a047

R. Breslow and S. Singh, Phosphate ester cleavage catalyzed by bifunctional zinc complexes: Comments on the ???p-nitrophenyl ester syndrome???, Bioorganic Chemistry, vol.16, issue.4, p.408, 1988.
DOI : 10.1016/0045-2068(88)90026-0

R. Breslow, L. E. Oyerman, and . Am, "Artificial enzyme" combining a metal catalytic group and a hydrophobic binding cavity, Journal of the American Chemical Society, vol.92, issue.4, p.1075, 1970.
DOI : 10.1021/ja00707a062

. Tabushi, N. Shimizu, T. Sugimoto, K. Yamamura, and . Am, Cyclodextrin flexibly capped with metal ion, Journal of the American Chemical Society, vol.99, issue.21, p.7100, 1977.
DOI : 10.1021/ja00463a073

E. U. Akkaya and A. Czarnik, Synthesis and transacylating activity of isomeric Co(III)-cyclodextrin artificial metalloenzymes, Journal of Physical Organic Chemistry, vol.95, issue.8, p.540, 1992.
DOI : 10.1002/poc.610050817

S. D. Dong and R. Breslow, Bifunctional cyclodextrin metalloenzyme mimics, Tetrahedron Letters, vol.39, issue.51, p.9343, 1998.
DOI : 10.1016/S0040-4039(98)02160-1

R. Breslow, B. Zhang, and . Am, Cleavage of Phosphate Esters by a Cyclodextrin Dimer Catalyst That Binds the Substrates Together with La3+ and Hydrogen Peroxide, Journal of the American Chemical Society, vol.116, issue.17, p.7893, 1994.
DOI : 10.1021/ja00096a055

F. Sallas, . Marsura, . Petot, J. Pintér, . Koyacs et al., Synthesis and Study of New ??-Cyclodextrin ???Dimers??? Having a Metal Coordination Center and carboxamide or urea linkers, Helvetica Chimica Acta, vol.94, issue.3-4, p.632, 1998.
DOI : 10.1016/S0304-5102(94)87047-0

R. Breslow, X. Zhang, R. Xu, and M. Maletic, Selective Catalytic Oxidation of Substrates That Bind to Metalloporphyrin Enzyme Mimics Carrying Two or Four Cyclodextrin Groups and Related Metallosalens, Journal of the American Chemical Society, vol.118, issue.46, p.11678, 1996.
DOI : 10.1021/ja962295f

L. Jullien, . Canceill, B. Valeur, E. Bardez, -. Lefèvre et al., Multichromophoric Cyclodextrins. 4. Light Conversion by Antenna Effect, Journal of the American Chemical Society, vol.118, issue.23, p.5432, 1996.
DOI : 10.1021/ja954332t

E. D. Gutsche and . Calixarenes, The Royal Society ofChemistry : Cambridge, 1989.

R. Vngaro and . Pochini, A In Calixarenes a versatile Class of macrocylic compounds, 1991.

D. 'alessandro, F. Gulino, F. G. Impellizeri, G. Pappalardo, G. Rizzarelli et al., A new water soluble host compound possessing two different hydrophobic recognition cavities: Calix[4]arene derivative conjugated with monofunctionalized ??-cyclodextrin, Tetrahedron Letters, vol.35, issue.4, p.629, 1994.
DOI : 10.1016/S0040-4039(00)75856-4

R. E. Petter, E. T. Sikorski, and D. Waldeck, Inclusion complexation by bis(cyclodextrins) in the presence of phospholipid vesicles, Journal of the American Chemical Society, vol.113, issue.6, p.2325, 1991.
DOI : 10.1021/ja00006a074

H. Staudinger and . Meyer, ??ber neue organische Phosphorverbindungen III. Phosphinmethylenderivate und Phosphinimine, Helvetica Chimica Acta, vol.2, issue.1, p.635, 1919.
DOI : 10.1002/hlca.19190020164

1. Pintér, J. Kovàcs, and G. Toth, Synthesis of sugar ureas via phosphinimines, Carbohydrate Research, vol.273, issue.1, p.99, 1995.
DOI : 10.1016/0008-6215(95)00029-S

A. Bertho and . Ber, ??ber Azidoderivate der Glucose, Berichte der deutschen chemischen Gesellschaft (A and B Series), vol.1, issue.II, p.836, 1930.
DOI : 10.1002/hlca.19180010109

S. Boudon, Introduction io Molecular Mechanics Calculations and Molecular Dynamics Simulations

R. C. Petter, J. S. Salek, C. T. Silorski, G. Kumaravel, and T. Lin, Cooperative binding by aggregated mono-6-(alkylamino)-.beta.-cyclodextrins, Journal of the American Chemical Society, vol.112, issue.10, p.3860, 1990.
DOI : 10.1021/ja00166a021

L. Jicsinszky, Catalytic transfer hydrogenation of cyclodextrin azides and benzylated glucose derivatives, Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, vol.34, issue.3, p.247, 1994.
DOI : 10.1007/BF00708731

B. Linton, Formation of Artificial Receptors by Metal-Templated Self-Assembly, Chemical Reviews, vol.97, issue.5, p.1669, 1997.
DOI : 10.1021/cr960375w

F. Charbonnier, One-pot synthesis of a thioureido-??-cyclodextrin dimer, Tetrahedron Letters, vol.40, issue.36, p.6581, 1999.
DOI : 10.1016/S0040-4039(99)01313-1

H. Schneider, F. Hacket, and V. Rüdiger, NMR Studies of Cyclodextrins and Cyclodextrin Complexes, Chemical Reviews, vol.98, issue.5, p.1755, 1998.
DOI : 10.1021/cr970019t

F. S. Richardson, Terbium(III) and europium(III) ions as luminescent probes and stains for biomolecular systems, Chemical Reviews, vol.82, issue.5, p.541, 1982.
DOI : 10.1021/cr00051a004

T. Logvren, I. Hemmila, K. Petterson, and O. Halonen, Alternative Immunoassays, p.2, 1985.

J. Lehn, . Ed, and V. Balzani, Supramolecular Chemislly, p.27, 1987.

J. Bünzli, Lanthanides Probes in Life, Medical, and Environmental Sciences, p.7, 1989.

F. Rouessac and A. Rouessac, Analyse Chimique, 1997.

B. Alpha, Thèse de l'Université Louis Pasteur, 1987.

S. I. Weissman, Intramolecular Energy Transfer The Fluorescence of Complexes of Europium, The Journal of Chemical Physics, vol.10, issue.4, p.214, 1942.
DOI : 10.1002/andp.19374210315

G. A. Crosby, R. Whan, and R. M. Alire, Intramolecular Energy Transfer in Rare Earth Chelates. Role of the Triplet State, The Journal of Chemical Physics, vol.1, issue.3, p.743, 1961.
DOI : 10.1063/1.1699044

G. A. Crosby, R. E. Whan, and J. J. Freeman, SPECTROSCOPIC STUDIES OF RARE EARTH CHELATES, The Journal of Physical Chemistry, vol.66, issue.12, p.2493, 1962.
DOI : 10.1021/j100818a041

J. M. Harrowfield, M. !. Odgen, A. H. White, and F. R. Wilner, = p-t-Butyl-Calix[8]arene), Australian Journal of Chemistry, vol.42, issue.6, p.949, 1989.
DOI : 10.1071/CH9890949

G. Templeton, F. F. Pollak, and A. , Spectroscopic characterization of 1,10-phenanthroline-2,9- dicarboxylic acid and its complexes with europium (III): Luminescent europium chelates useful for analytical applications in aqueous solution, Journal of Luminescence, vol.43, issue.4, p.195, 1989.
DOI : 10.1016/0022-2313(89)90002-1

P. Pellet-rostaing, Thèse de l, 1997.

L. Zelikovich, J. Libman, and A. Shanzer, Molecular redox switches based on chemical triggering of iron translocation in triple-stranded helical complexes, Nature, vol.374, issue.6525, p.790, 1995.
DOI : 10.1038/374790a0

T. Nabeshima, T. Inaba, and N. Furukawa, Transition metal induced selective alkaline metal ion transport by asynthethic ionophore with double recognition sites for metals, Tetrahedron Letters, vol.28, issue.49, p.6211, 1987.
DOI : 10.1016/S0040-4039(00)61849-X

K. Rohatgi, Mikherjee "Fundamentals ofPhotochemisf1y, 1978.

J. E. Guillet and . Po, ymer Photophysics and PhotochemiSf1y

R. Breslow and B. Zhang, Cleavage of Phosphate Esters by a Cyclodextrin Dimer Catalyst That Binds the Substrates Together with La3+ and Hydrogen Peroxide, Journal of the American Chemical Society, vol.116, issue.17, pp.7893-7894, 1994.
DOI : 10.1021/ja00096a055

S. Amin, J. R. Morrow, C. Lake, and R. Haner, 0 (Cb6)1 (C a 6); 41.0 (CH2, cyclarn) ESMS : 1227, Cl Angew. Chem.lnt. Ed. Engl, vol.823333, issue.42, pp.7-72, 1994.

L. Jicsinszky, Catalytic transfer hydrogenation of cyclodextrin azides and benzylated glucose derivatives, Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, vol.34, issue.3, pp.247-254, 1994.
DOI : 10.1007/BF00708731

. Abstnu, The present work describes the one-pot symhesis of an heptakis-{bipyridinyl-ureido)-p-cyclodextrin in a high coupling average (82%) by the "phosphinimine" approach. The subsequent complexation of J with EuCI] or TbCl] gives stable complexes 4. Preliminary results on complexation and fluorescence properties are reported, 1999.

W. H. Sasse, D. Fh, . Nmr, and . Bruker, DRX-400 spectrometer, FTIR spectra were recorded on a Perkin-ElmerI600; UY-Vis on a Safas UVmc l . Luminescence experiments were performed on a Spex Fluorolog II photon counting spectrofluorimeter equipped with a 450W xenon continous wave irradiation source Mass spectra were recorded in FAB positive mode on a ZAB-SEQ mass spectrometer. The new compounds gave satisfaclory spectroscopic data Beptakis~5-metbyleDe-ureido-5'-metbyI-2.2'-bipyridiDyl}-<:yclomaltobeptaose. Obtained by condensation of 1 (0.006 mmol, 0.077g,1 equiv95 mmol, 0.20g, 16 equiv.) and triphenyl phosphane (4.10 mmol, 1.075g, 70 equiv.) After evaporation of the DMF, the residue was treated with dielhyl ether, filtered, treated with methylene chloride then filtered once more to give 3, an orange pure powder (0.13g, 82%); UY-Vis (À max nm) : 250 (shoulder), C=O urea), 1557 (C=C aromatics); IH NMR (DJ)MSO, 25°) 0 (ppm) : 8.48 cyclodextrin and CH] bipyridin»CH J , bipyridin». DC NMR (DJ)MSO, 25°) 0 (ppm) : 158.0 (N-CO-NH), pp.1347-1350, 1961.

R. S. Dickins, J. A. Howard, C. Lehman, J. Moloney, D. Parker et al., Structural Rigidity and Luminescence of Chiral Lanthanide Tetraamide Complexes Based on 1,4,7,10-Tetraazacyclododecane, Angewandte Chemie International Edition in English, vol.36, issue.5, pp.521-523, 1997.
DOI : 10.1002/anie.199705211

*. Corresponding, Fax: 33 (03) 83.17.88.63; e-mail: marsura@srsmc.u-nancy.fr t Present address, PO Box, vol.1799, pp.40-4039

L. Jicsinszky, Catalytic transfer hydrogenation of cyclodextrin azides and benzylated glucose derivatives, Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, vol.34, issue.3, pp.247-254, 1994.
DOI : 10.1007/BF00708731

1. Nmr, Cla, C)b), 25°C), pp.172-171

O. Analn-h, Bis- [cyclomaltoheptaosyl-6-thioureido)-1,6-hexamethylenediamine White powder (0.182 g, 93%) TLC (dioxane:NH3 25% 25°C) 8 (ppm): 5.40-5 H h 5», C=S); IH NMR (CDCl)CH2 C),C 4 alkyl); FABMS (thioglycerol): 1379 [M-[NH-CHz-Cd)+2NaTCd-CHz-NH-Cs]+Na+j+, 1176 [Cd-CH 2 -NH-CS]+, pp.1-45