- Hemicryptophane-assisted electron transfer: A structural and electronic study
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Three copper(ii)@hemicryptophane complexes with various cavity sizes and shapes, Cu(ii)@1, Cu(ii)@2 and Cu(ii)@3, were synthesized and characterized by near-IR/vis and EPR spectroscopies. The spectroscopic data are consistent with the presence of a trigonal-bipyramidal geometry of the N4Cu· H2O core, in accord with the energy-minimized structures obtained from DFT calculations. Cyclic voltammetry studies in CH2Cl 2 showed irreversible redox processes, whereas electrolysis coulometry indicated that Cu(ii)/Cu(i) complexes could be interconverted. Electrochemistry data of the complexes stress the crucial role of the cage structure of the hemicryptophane in the thermodynamics of the electron transfer. The Royal Society of Chemistry 2013.
- Perraud, Olivier,Tommasino, Jean-Bernard,Robert, Vincent,Albela, Belén,Khrouz, Lhoussain,Bonneviot, Laurent,Dutasta, Jean-Pierre,Martinez, Alexandre
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Read Online
- Azaphosphatrane organocatalysts in confined space: Cage effect in CO 2 conversion
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The endohedral functionalization of a molecular cage by an azaphosphatrane unit has allowed for the creation of highly engineered catalytic cavities for efficient conversion of CO2 into cyclic carbonates. Strong structure/activity/stability correlations have been demonstrated by careful adjustment of the size, shape, and electronic properties of the hemicryptophane host.
- Chatelet, Bastien,Joucla, Lionel,Dutasta, Jean-Pierre,Martinez, Alexandre,Dufaud, Veronique
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Read Online
- Cyclotriveratrylene-BINOL-Based Host Compounds: Synthesis, Absolute Configuration Assignment, and Recognition Properties
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New host compounds combining a cyclotriveratrylene (CTV) unit and three binaphthol moieties have been synthesized enantiomerically and diastereomerically pure. The use of a chemical correlation allows for the assignment of their absolute configuration. The energy barrier of epimerization was measured, suggesting that no intramolecular hydrogen bonding occurs between the hydroxyl groups of the binaphthols. These open-shell host compounds were then tested in the recognition of carbohydrates; a preferential binding of mannose toward glucose was observed, and good diastereoselectivities were reached (up to 1:10). This recognition of sugar derivatives by open-shell CTV-based host compounds is unprecedented and opens up the way for a wider use of this easily accessible class of molecules as chiral sensors.
- Lefevre, Sara,Héloin, Alexandre,Pitrat, Delphine,Mulatier, Jean-Christophe,Vanthuyne, Nicolas,Jean, Marion,Dutasta, Jean-Pierre,Guy, Laure,Martinez, Alexandre
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Read Online
- Design, synthesis, in silico and in vitro studies for new nitric oxide‐releasing indomethacin derivatives with 1,3,4‐oxadiazole‐2‐thiol scaffold
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Starting from indomethacin (IND), one of the most prescribed non‐steroidal anti‐inflammatory drugs (NSAIDs), new nitric oxide‐releasing indomethacin derivatives with 1,3,4‐oxadiazole‐ 2‐thiol scaffold (NO‐IND‐OXDs, 8a‐p) have been developed as a safer and
- Sava, Alexandru,Buron, Frederic,Routier, Sylvain,Panainte, Alina,Bibire, Nela,Constantin, Sandra M?d?lina,Lupa?cu, Florentina Geanina,Foc?a, Alin Viorel,Profire, Lenu?a
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- Enantio- A nd Substrate-Selective Recognition of Chiral Neurotransmitters with C3-Symmetric Switchable Receptors
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We report on the synthesis of C3-symmetric enantiopure cage molecules 1, which exhibit remarkable to exclusive enantioselective recognition properties toward chiral ammonium neurotransmitters. Strong changes in the substrate selectivity are als
- Chatelet, Bastien,Dufaud, Véronique,Dutasta, Jean-Pierre,Guy, Laure,Hérault, Damien,Jean, Marion,Martinez, Alexandre,Mulatier, Jean-Christophe,Pitrat, Delphine,Vanthuyne, Nicolas,Yang, Jian
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supporting information
(2020/02/15)
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- Enantiopure encaged Verkade's superbases: Synthesis, chiroptical properties, and use as chiral derivatizing agent
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Verkade's superbases, entrapped in the cavity of enantiopure hemicryptophane cages, have been synthesized with enantiomeric excess (ee) superior to 98%. Their absolute configuration has been determined by using electronic circular dichroism (ECD) spectros
- Yang, Jian,Chatelet, Bastien,Hérault, Damien,Dufaud, Véronique,Robert, Vincent,Grass, Stéphane,Lacour, Jér?me,Vanthuyne, Nicolas,Jean, Marion,Albalat, Muriel,Dutasta, Jean-Pierre,Martinez, Alexandre
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supporting information
p. 139 - 146
(2019/12/27)
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- High-relaxivity Gd(III)-hemicryptophane complex
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The polytopic hemicryptophane cage HC1 combining a cyclotriveratrylene (CTV) unit and a tris(2-aminoethyl)amine (tren) moiety connected by three 2-hydroxyisophthalamide linkers was synthesized in 12 steps. The resulting highly functionalized covalent host
- Godart, Estelle,Long, Augustin,Rosas, Roselyne,Lemercier, Gilles,Jean, Marion,Leclerc, Sébastien,Bouguet-Bonnet, Sabine,Godfrin, Célia,Chapellet, Laure-Lise,Dutasta, Jean-Pierre,Martinez, Alexandre
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p. 1999 - 2003
(2019/04/11)
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- Large-Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties
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A convenient and efficient gram-scale synthesis for enantiopure hemicryptophane-tren (tren=tris(2-aminoethyl)amine) derivatives has been developed. The four-step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for
- Lefevre, Sara,Zhang, Dawei,Godart, Estelle,Jean, Marion,Vanthuyne, Nicolas,Mulatier, Jean-Christophe,Dutasta, Jean-Pierre,Guy, Laure,Martinez, Alexandre
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p. 2068 - 2074
(2016/02/19)
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- A "Smart" 129Xe NMR biosensor for pH-dependent cell labeling
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Here we present a "smart" xenon-129 NMR biosensor that undergoes a peptide conformational change and labels cells in acidic environments. To a cryptophane host molecule with high Xe affinity, we conjugated a 30mer EALA-repeat peptide that is α-helical at pH 5.5 and disordered at pH 7.5. The 129Xe NMR chemical shift at room temperature was strongly pH-dependent (Δδ = 3.4 ppm): δ = 64.2 ppm at pH 7.5 vs δ = 67.6 ppm at pH 5.5, where Trp(peptide)-cryptophane interactions were evidenced by Trp fluorescence quenching. Using hyper-CEST NMR, we probed peptidocryptophane detection limits at low-picomolar (10-11 M) concentration, which compares favorably to other NMR pH reporters at 10-2-10-3 M. Finally, in biosensor-HeLa cell solutions, peptide-cell membrane insertion at pH 5.5 generated a 13.4 ppm downfield cryptophane-129Xe NMR chemical shift relative to pH 7.5 studies. This highlights new uses for 129Xe as an ultrasensitive probe of peptide structure and function, along with potential applications for pH-dependent cell labeling in cancer diagnosis and treatment.
- Riggle, Brittany A.,Wang, Yanfei,Dmochowski, Ivan J.
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supporting information
p. 5542 - 5548
(2015/05/13)
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- Synthesis and physico-chemical properties of the first water soluble Cu(ii)@hemicryptophane complex
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A hemicryptophane ligand soluble in water at neutral pH was obtained thanks to the derivatization of the cyclotribenzylene unit with three carboxylate groups. The corresponding Cu(ii) complex was then synthesized and its spectroscopic and electrochemical
- Schmitt, Aline,Collin, Solne,Bucher, Christophe,Maurel, Vincent,Dutasta, Jean-Pierre,Martinez, Alexandre
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supporting information
p. 2157 - 2161
(2015/03/05)
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- Remote control of helical chirality: Thermodynamic resolution of a racemic mixture of CTV units by remote stereogenic centers
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Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host-guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote st
- Chatelet, Bastien,Joucla, Lionel,Padula, Daniele,Bari, Lorenzo Di,Pilet, Guillaume,Robert, Vincent,Dufaud, V??ronique,Dutasta, Jean-Pierre,Martinez, Alexandre
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supporting information
p. 500 - 503
(2015/03/05)
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- Synthesis of the first water-soluble hemicryptophane host: Selective recognition of choline in aqueous medium
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The first water-soluble hemicryptophane cage compound, 4, was synthesized in seven steps from commercially available products, and its complexation properties were studied. NMR and ITC experiments indicate that 4 is an efficient receptor for choline in wa
- Schmitt, Aline,Robert, Vincent,Dutasta, Jean-Pierre,Martinez, Alexandre
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supporting information
p. 2374 - 2377
(2014/05/20)
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- Improved hemicryptophane hosts for the stereoselective recognition of glucopyranosides
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Four new enantiomerically and diastereomerically pure hemicryptophane hosts (M-SSS-2/P-SSS-2 and M-RRR-2/P-RRR-2 pairs) were designed for the recognition of sugar derivatives. Their absolute configuration was determined from the circular dichroism spectra
- Schmitt, Aline,Perraud, Olivier,Payet, Elina,Chatelet, Bastien,Bousquet, Benjamin,Valls, Marion,Padula, Daniele,Di Bari, Lorenzo,Dutasta, Jean-Pierre,Martinez, Alexandre
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p. 4211 - 4217
(2014/06/10)
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- Shorter synthesis of trifunctionalized cryptophane - A derivatives
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Efficient syntheses of trisubstituted cryptophane-A derivatives that are versatile host molecules for many applications are reported. Trihydroxy cryptophane was synthesized in six or seven steps with yields as high as 9.5%. By a different route, trihydrox
- Taratula, Olena,Hill, P. Aru,Bai, Yubin,Khan, Najat S.,Dmochowski, Ivan J.
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scheme or table
p. 1414 - 1417
(2011/05/13)
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- Shorter and modular synthesis of hemicryptophane-tren derivatives
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Hemicryptophanes are host molecules with many applications as supramolecular catalysts or in ion selective recognition. A very convenient and efficient modular approach for the synthesis of hemicryptophane-tren (tren, tris(2-aminoethyl)-amine) derivatives
- Chatelet, Bastien,Payet, Elina,Perraud, Olivier,Dimitrov-Raytchev, Pascal,Chapellet, Laure-Lise,Dufaud, Veronique,Martinez, Alexandre,Dutasta, Jean-Pierre
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scheme or table
p. 3706 - 3709
(2011/09/15)
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- A new class of C3-symmetrical hemicryptophane hosts: Triamide- and tren-hemicryptophanes
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Chemical Equation Presented The first hemicryptophanes derived from tris(N-alkylcarbamoylmethyl)amine and tris(2-aminoethyl)amine (tren) have been synthesized following a single synthetic pathway that allows the subsequent formation of the two heteroditopic hosts 3 and 4. X-ray crystal structures show a well-defined cavity encapsulating a solvent guest for both compounds emphasizing their complexation properties.
- Raytchev, Pascal Dimitrov,Perraud, Olivier,Aronica, Christophe,Martinez, Alexandre,Dutasta, Jean-Pierre
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scheme or table
p. 2099 - 2102
(2010/06/12)
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- Control of conformational flexibility in calix[6]arenes: Synthesis and characterisation of triply bridged calix[6]arene - 10, 15-dihydro-5H-tribenzo [a,d,g]cyclononene conjugates
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A series of triply bridged symmetrical terf-butylcalix[6]arene-10,15- dihydro-5H-tribenzo[a,d,g]cyclononene conjugates have been synthesised in excellent yields. It has been observed that the synthesised multi-cavity molecular receptors retain the calix[6
- Chawla, H. Mohindra,Shrivastava, Rahul
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experimental part
p. 347 - 353
(2009/06/18)
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- 129XE BIOSENSORS AND THEIR USE
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This invention relates to enzyme-sensitive biosensors and methods and kits using the same. Specifically, the invention relates to methods, systems and kits for the detection of enzymes using the chemical shift observed in an isotope complexed to the biose
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Page/Page column 27; 3/28
(2010/11/30)
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- Designing 129Xe NMR biosensors for matrix metalloproteinase detection
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Xenon-129 biosensors offer an attractive alternative to conventional MRI contrast agents due to the chemical shift sensitivity and large nuclear magnetic signal of hyperpolarized 129Xe. Here, we report the first enzyme-responsive 129
- Wei, Qian,Seward, Garry K.,Hill, P. Aru,Patton, Brian,Dimitrov, Ivan E.,Kuzma, Nicholas N.,Dmochowski, Ivan J.
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p. 13274 - 13283
(2008/03/11)
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- Synthesis of deuterium-labeled cryptophane-A and investigation of Xe@cryptophane complexation dynamics by 1D-EXSY NMR experiments
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We present the synthesis of a series of deuterated cryptophanes 2-6 by a slightly modified procedure used for cryptophane-A. We show that for [Xe@cryptophane] complexes the use of variable-temperature one-dimensional 129Xe magnetization transfe
- Brotin, Thierry,Devic, Thomas,Lesage, Anne,Emsley, Lyndon,Collet, Andre
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p. 1561 - 1573
(2007/10/03)
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- Cryptocalix[6]arenes; Molecules with a large cavity
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A new type of cavitand molecules with large cavities (4a-g) has been synthesized by the covalent three-point linking of a p-tert- butylcalix[6]arene to a cyclotriveratrylene (CTV) and their dynamic behavior has been studied by 1H NMR spectrosco
- Janssen, Rob G.,Verboom, Willem,Van Duynhoven, John P. M.,Van Velzen, Ewoud J. J.,Reinhoudt, David N.
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p. 6555 - 6558
(2007/10/02)
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- Analytical Optical Resolution of Bromochlorofluoromethane by Enantioselective Inclusion into a Tailor-Made "Cryptophane" and Determination of Its Maximum Rotation
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Analytical optical resolution of bromochlorofluoromethane (1) has been achieved by 1H NMR spectroscopy by inclusion of the haloform within the cavity of a chiral host molecule (5) (cryptophane-C) designed to fit substrates of this size.The diastereometric
- Canceill, Josette,Lacombe, Liliane,Collet, Andre
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p. 6993 - 6996
(2007/10/02)
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