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1. Enantiopure cryptophane derivatives: Synthesis and chiroptical properties

Author

Thierry Brotin, Thierry Buffeteau, Orsola Baydoun, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Large range, 010402 general chemistry, 01 natural sciences, Catalysis, Cryptophane, Analytical Chemistry, Computational chemistry, Drug Discovery, Molecule, ECD, Spectroscopy, ROA, Pharmacology, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Absolute configuration, VCD, 0104 chemical sciences, 3. Good health, absolute configuration, Enantiopure drug, Vibrational circular dichroism, macrocyclic compounds, Raman optical activity
Abstract

International audience; This review addresses the synthesis of enantiopure cryptophane and the study of their chiroptical properties. Cryptophane derivatives represent an important class of macrocyclic compounds that can bind a large range of species in solution under different conditions. The overwhelming majority of these host molecules is chiral and their chiroptical properties have been thoroughly investigated. The first part of this review is dedicated to the optical resolution and the synthesis of enantiopure cryptophane derivatives. In a second part, the study of the chiroptical properties of these molecular hosts by different techniques such as electronic and vibrational circular dichroism and Raman optical activity is detailed. These techniques allow the determination of the absolute configuration of cryptophane derivatives and provide useful information about their conformation in different conditions.

Published
2021
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2. Are the physical properties of Xe@cryptophane complexes easily predictable? the case of $syn$ and $anti$ tris-$aza$-cryptophanes

Author

Patrick Berthault, Nicolas Daugey, Marion Jean, Nicolas de Rycke, Thierry Brotin, Estelle Léonce, Martin Doll, Nicolas Vanthuyne, Thierry Buffeteau, Céline Boutin, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-19-CE19-0024,PHOENIX,Mesure du pH extracellulaire par RMN du Xenon-129(2019), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC)

Subjects
Tris, 010405 organic chemistry, Chemistry, Organic Chemistry, Resolution (electron density), Combined use, Diastereomer, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, Xenon, Computational chemistry, Vibrational circular dichroism, Quantum
Abstract

International audience; We report the synthesis and the optical resolution of C3-symmetrical tris-azacryptophanes anti-3 and syn-4, as well as the study of their interaction with xenon via hyperpolarized 129 Xe NMR. These molecular cages are close structural analogs of the two wellknown cryptophane-A (1; chiral) and cryptophane-B (2; achiral) diastereomers since these new 2 compounds differ only by the presence of three nitrogen atoms grafted on the same cyclotribenzylene unit. The assignment of their relative (syn vs anti) and absolute configurations was made possible thanks to the combined use of quantum calculation at the DFT level and vibrational circular dichroism (VCD). More importantly, our results show that despite the large structural similarities with cryptophane-A (1) and-B (2), these two new compounds show very different behavior in the presence of xenon in organic solution. These results demonstrate that a prediction of the physical properties of the xenon@cryptophane complexes, only based on structural parameters, remains extremely difficult.

Published
2021
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3. Selective Capture of Thallium and Cesium by a Cryptophane Soluble at Neutral pH

Author

Patrick Berthault, Delphine Pitrat, Thierry Brotin, Jean-Christophe Mulatier, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Carboxylic acid, Organic Chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Caesium, Polymer chemistry, Thallium, Phenol, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Neutral ph, Derivative (chemistry)
Abstract

International audience; We report in this article the synthesis of a asymmetrical cryptophane derivative (possessing only C3-symmetry) bearing three phenol groups and three other carboxylic acid functions, each of these groups on the aromatic rings. Thanks to isothermal titration calorimetry experiments, we show that this compound binds large monovalent cations, such as Cs+ and Tl+ with a binding constant significantly lower than its congeners bearing a larger number of phenol groups grafted on the benzene rings. However, higher selectivity for Cs+ and Tl+ was observed with this compound since it does not show any affinity for other alkali cations. More importantly, due to the greater solubility of this derivative in pure water, we show for the first time that effective thallium(I) complexation takes place at neutral pH. This result demonstrates that cryptophane derivatives decorated with a higher number of phenol groups are promising host molecules for removing traces of thallium(I) from aqueous phases at neutral pH or above.

Published
2020
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4. Synthesis of Cryptophane-B: Crystal Structure and Study of Its Complex with Xenon

Author

Delphine Pitrat, Patrick Berthault, Estelle Léonce, Thierry Brotin, Erwann Jeanneau, Jean-Christophe Mulatier, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Diastereomer, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, Cryptophane, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Xenon, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Yield (chemistry), Molecule, Derivative (chemistry)
Abstract

International audience; Whereas the synthesis of the $anti$-cryptophane-A (1) derivative is known for nearly 40 years, the preparation of its diastereomer (cryptophane-B according to Collet's nomenclature) has never been reported. Thus, the synthesis of the cryptophane-B derivative represents a real challenge for chemists interested in the preparation of these hollow molecules. Herein, we describe a synthetic route that allows us to prepare cryptophane-B (2), however in low yield. The X-ray crystallographic structure of this compound is described and it reveals the presence of an ethanol molecule inside the cavity of the host. Finally, the ability of cryptophane-B to bind xenon in 1,1,2,2-tetrachloroethane-$d_2$ is also studied via hyperpolarized $^{129}$Xe NMR

Published
2018
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5. Accurate pH Sensing using Hyperpolarized 129 Xe NMR Spectroscopy

Author

Jean-Pierre Dognon, Patrick Berthault, Delphine Pitrat, Thierry Brotin, Estelle Léonce, and Jean-Christophe Mulatier

Subjects
010405 organic chemistry, Chemistry, Chemical shift, Organic Chemistry, Analytical chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, Ph measurement, 010402 general chemistry, 01 natural sciences, Quantum chemistry, Catalysis, Cryptophane, 3. Good health, 0104 chemical sciences, Hyperpolarized xenon, Ph sensing
Abstract

In the search for powerful non-invasive methods for pH measurement, NMR usually suffers from biases, especially for heterogeneous samples or tissues. In this Communication, using the signals of hyperpolarized $^{129}$Xe encapsulated in a pair of water-soluble cryptophanes, we show that a differential pH measurement can be achieved, free from most of these biases, by monitoring the difference between their chemical shifts.

Published
2018
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6. Enantioselective Complexation of Chiral Oxirane Derivatives by an Enantiopure Cryptophane in Water

Author

Thierry Buffeteau, Nicolas Vanthuyne, Nicolas de Rycke, Thierry Brotin, and Marion Jean

Subjects
Circular dichroism, 010405 organic chemistry, Chemistry, Organic Chemistry, Binding properties, Supramolecular chemistry, Enantioselective synthesis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Cryptophane, 0104 chemical sciences, Enantiopure drug, Molecular recognition, Physical and Theoretical Chemistry
Published
2018
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7. Diastereomeric stilbenoid glucoside dimers from the rhizomes of Gnetum africanum

Author

Jonathan Bisson, Jean-Michel Mérillon, Caroline Rouger, Julien Gabaston, Thierry Buffeteau, Pierre Waffo-Teguo, Thierry Brotin, Institut des Sciences de la Vigne et du Vin [Villenave d'Ornon] (ISVV), Université de Bordeaux (UB), Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Unité de Recherche Oenologie [Villenave d'Ornon] (OENO), Université de Bordeaux (UB)-Institut des Sciences de la Vigne et du Vin (ISVV)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, Stereochemistry, Plant Science, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Stilbenoid, 01 natural sciences, Biochemistry, chemistry.chemical_compound, Glucoside, Stilbenoids, Gnetum africanum, Chelation, Absolute configuration, [CHIM.COOR]Chemical Sciences/Coordination chemistry, biology, 010405 organic chemistry, Diastereomer, Polyphenols, biology.organism_classification, 0104 chemical sciences, 3. Good health, Rhizome, 010404 medicinal & biomolecular chemistry, chemistry, Gnetaceae, Vibrational circular dichroism, Iron chelation, Agronomy and Crop Science, Biotechnology
Abstract

International audience; In a continuing search for neuroprotective stilbenoids, two uncommon diastereomeric stilbenoid glucosides, africanoside A (1) and B (2) as well as fifteen known stilbenes, E-resveratrol, E-gnetifolin E, E-piceid, E-resveratroloside, E-gnetifolin K, E-gnetol, E-isorhapontigenin, E-isorhapontin, E-isorhapontigenin-4′-O-glucopyranoside, E-gnetin C, E-bisisorhapontigenin B, E-gnemonoside A, E-gnemonoside C, E-gnemonoside D, and E-gnetin E, were isolated from rhizomes of Gnetum africanum, using a combination of centrifugal partition chromatography and preparative HPLC. The structure of these two stilbenoids was investigated by NMR, vibrational circular dichroism (VCD), and electronic circular dichroism (ECD) experiments. The absolute configurations of 1, and 2 were established by VCD as (7aS,8aS) and (7aR,8aR), respectively. Compound 1 significantly chelated Fe(II) at 100, 250 and 500 μM. The ability of stilbenoids to chelate ferrous ions which are implicated in physiopathological hallmark of Alzheimer’s disease provides useful data for potential treatment.

Published
2020
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8. Synthesis of Cryptophane-223-Type Derivatives with Dual Functionalization

Author

Estelle Léonce, Nicolas de Rycke, Thierry Brotin, Erwann Jeanneau, Orsola Baydoun, Céline Boutin, Patrick Berthault, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Xenon, Aqueous medium, chemistry, 010405 organic chemistry, Organic Chemistry, Surface modification, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Cryptophane, 0104 chemical sciences
Abstract

International audience; In this article, we present the synthesis of new cryptophane-type hosts capable of binding xenon in aqueous media and that may be useful for the development of xenon-based magnetic resonance imaging derivatives. The synthetic route proposed was chosen to facilitate both the introduction of water-solubilizing substituents and the functionalization of the host with a single arm showing recognition properties that constitute two crucial steps. This was made possible by preparing new cryptophane-223 derivatives bearing two different chemical functions that can be easily modified at a later stage. Thus, subsequent reactions allowed the design of a new cryptophane host able to bind zinc or nickel cations. The ability of this molecule to bind cationic species was assessed by calorimetric titration experiments and hyperpolarized 129Xe NMR. The advantages and disadvantages of this approach are discussed.

Published
2019
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9. Chiroptical study of cryptophanes subjected to self‐encapsulation

Author

Laure-Lise Chapellet, Nicolas de Rycke, Thierry Brotin, Orsola Baydoun, Thierry Buffeteau, Nicolas Vanthuyne, Marion Jean, Nicolas Daugey, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Pharmacology, Circular dichroism, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Absolute configuration, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Catalysis, Cryptophane, 0104 chemical sciences, 3. Good health, Analytical Chemistry, Crystallography, Drug Discovery, Proton NMR, Optical rotation, Enantiomer, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

In 1,1,2,2-tetrachloroethane-d2 , the 129 Xe NMR spectrum of the Xe@cryptophane-223 complex bearing seven acetate groups (Xe@1 complex) shows an unusually broad signal compared with that of its congeners (Chapellet, LL. et al. J. Org. Chem. 2015;80:6143-6151). To interpret this unexpected behaviour, a 1 H NMR analysis and a thorough study of the chiroptical properties of 1 as a function of the nature of the solvent have been performed. The 1 H NMR spectra of 1 reveal that a self-encapsulation phenomenon takes place in DMSO-d6 and 1,1,2,2-tetrachloroethane-d2 solvents. Thanks to the separation of the two enantiomers of 1 by HPLC on chiral stationary phase, the two enantiomers of 1 have been studied in detail by polarimetry, electronic (ECD), and vibrational (VCD) circular dichroism spectroscopies. Except for ECD spectroscopy, these chiroptical techniques reveal spectroscopic changes as a function of the nature of the solvent. For instance, in DMSO and 1,1,2,2-tetrachloroethane, in which the self-encapsulation phenomenon takes place, the sign of the specific optical rotation of [CD(-)254 ]-1 and [CD(+)254 ]-1 is changed. These results have then been compared with those obtained with cryptophane-223 bearing only one acetate group on the propylenedioxy linker (compound 2) and with cryptophane-223 bearing six acetate groups (compound 3). A self-encapsulation phenomenon is also observed with compound 2. Finally, compounds 2 and 3 show different chiroptical properties compared with those obtained with the two enantiomers of compound 1.

Published
2019
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10. Bioinspired Oxidation of Methane in the Confined Spaces of Molecular Cages

Author

Thierry Brotin, Alexander B. Sorokin, Jean-Pierre Dutasta, Sk Asif Ikbal, Dawei Zhang, Cédric Colomban, Magalie Delecluse, Alexandre Martinez, Véronique Dufaud, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Catalyse Hétérogène pour la Transition Energétique (CATREN), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-Energies, carburants, intermédiaires pour le développement durable (ECI2D), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
010405 organic chemistry, Chemistry, Supramolecular chemistry, chemistry.chemical_element, Vanadium, 010402 general chemistry, Photochemistry, 01 natural sciences, Copper, Methane, 0104 chemical sciences, Catalysis, Turnover number, Inorganic Chemistry, chemistry.chemical_compound, Anaerobic oxidation of methane, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Selectivity, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Non-heme iron, vanadium, and copper complexes bearing hemicryptophane cavities were evaluated in the oxidation of methane in water by hydrogen peroxide. According to 1H nuclear magnetic resonance studies, a hydrophobic hemicryptophane cage accommodates a methane molecule in the proximity of the oxidizing site, leading to an improvement in the efficiency and selectivity for CH3OH and CH3OOH compared to those of the analogous complexes devoid of a hemicryptophane cage. While copper complexes showed low catalytic efficiency, their vanadium and iron counterparts exhibited higher turnover numbers, ≤13.2 and ≤9.2, respectively, providing target primary oxidation products (CH3OH and CH3OOH) as well as over-oxidation products (HCHO and HCOOH). In the case of caged vanadium complexes, the confinement effect was found to improve either the selectivity for CH3OH and CH3OOH (≤15%) or the catalytic efficiency. The confined space of the hydrophobic pocket of iron-based supramolecular complexes plays a significant role in the improvement of both the selectivity (≤27% for CH3OH and CH3OOH) and the turnover number of methane oxidation. These results indicate that the supramolecular approach is a promising strategy for the development of efficient and selective bioinspired catalysts for the mild oxidation of methane to methanol.

Published
2019
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11. Immobilization of Cryptophane Derivatives onto γ-Fe2O3 Core–Shell Magnetic Nanoparticles

Author

Luc Vellutini, Thierry Brotin, Elise Siurdyban, Karine Heuzé, David Talaga, Thierry Buffeteau, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS)

Subjects
Chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Grafting, 01 natural sciences, Nanoshell, Cryptophane, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Core shell, General Energy, Transmission electron microscopy, Polymer chemistry, Molecule, Magnetic nanoparticles, Organic chemistry, Diffuse reflection, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Three immobilization strategies of cryptophane derivatives onto core–shell γ-Fe2O3/silica magnetic nanoparticles (MNPs) are reported. Immobilization of a cryptophane bearing five methoxy substituents and an alkanethiol chain, 1, was performed onto MNPs coated with a gold nanoshell. Likewise, immobilization of a cryptophane molecule bearing five methoxy substituents and one acid function, 2, onto MNPs coated with APTES was also performed via amide bonds. Finally, the cysteamine coupling agent was used to modify 2, giving 3, before its immobilization onto MNPs coated with a gold nanoshell. Diffuse reflectance infrared transform Fourier spectroscopy (DRIFTS) and transmission electron microscopy (TEM) were used to characterize the chemical modifications of the MNPs for the three immobilization strategies. A very efficient grafting of 1 onto MNPs coated with gold was found whereas the immobilization of 2 and 3 was unsuccessful.

Published
2016
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12. Bimodal detection of proteins by $^{129}$Xe NMR and fluorescence spectroscopy

Author

Estelle Léonce, Gaëlle Milanole, Patrick Berthault, Céline Boutin, Marie Erard, Thierry Brotin, Emilie Mari, Yasmina Bousmah, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Physique (ICP), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_element, 010402 general chemistry, biosensor, 01 natural sciences, Biochemistry, Fluorescence spectroscopy, Cryptophane, Xenon, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Moiety, Molecule, fluorescent protein, cryptophane, Molecular Biology, 010405 organic chemistry, Chemistry, Organic Chemistry, Nuclear magnetic resonance spectroscopy, Combinatorial chemistry, Fluorescence, tetracyteine-tag, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, $^{129}$Xe NMR, Molecular Medicine, fluorescence, Biosensor
Abstract

A full understanding of biological phenomena involves sensitive and noninvasive detection. Herein, we report the optimization of a probe for intracellular proteins that combines the advantages of fluorescence and hyperpolarized 129 Xe NMR spectroscopy detection. The fluorescence detection part is composed of six residues containing a tetracysteine tag (-CCXXCC-) genetically incorporated into the protein of interest and of a small organic molecule, CrAsH. CrAsH becomes fluorescent if it binds to the tetracysteine tag. The part of the biosensor that enables detection by means of 129 Xe NMR spectroscopy, which is linked to the CrAsH moiety by a spacer, is based on a cryptophane core that is fully suited to reversibly host xenon. Three different peptides, containing the tetracysteine tag and four organic biosensors of different stereochemistry, are benchmarked to propose the best couple that is fully suited for the in vitro detection of proteins.

Published
2019
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13. Optimized Continuous Application of Hyperpolarized Xenon to Liquids

Author

Peter Blümler, B. Niederländer, Hans-Joachim Krause, D. van Dusschoten, Andreas Offenhäusser, Werner Heil, Thierry Brotin, Institute of Physics, University of Mainz, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Jülich Supercomputing Centre Forschungszentrum Jülich GmbH Jülich, Germany, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_element, hollow fiber membranes, 010402 general chemistry, Residence time (fluid dynamics), 01 natural sciences, Cryptophane, 030218 nuclear medicine & medical imaging, 03 medical and health sciences, 0302 clinical medicine, Xenon, magnetic resonance imaging, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Polarization (electrochemistry), Dissolution, Aqueous solution, 129Xe, NMR, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, nuclear magnetic resonance, Membrane, chemistry, Chemical physics, compressor, Gas compressor, transfer
Abstract

International audience; In recent years, NMR with hyperpolarized (HP) xenon inside functionalized host structures (e.g. cryptophanes) have become a potential candidate for the direct observation of metabolic processes (i.e. molecular imaging). A critical issue for real applications is the dissolution of the HP-gas in the liquid which contains the host. In this work, we present recent developments for an improved and controlled dissolution of HP-Xe in liquids using hollow fiber membranes and different compressor systems. The designed apparatus consists of a compressor and a membrane unit. The compressor provides HP-129 Xe continuously at small adjustable pressures and in a polarization-preserving way. The membrane unit enables a molecular solution of the HP-gas in aqueous liquids, avoiding the formation of bubbles or even foams. Two different types of compressors were tested in terms of function and useful materials. Special emphasis was put on a systematic reduction of transfer losses in the gas and liquid phase. In order to optimize the system parameters, several physical models were developed to describe the transport and the losses of nuclear polarization. Finally, the successful implementation was demonstrated in several experiments. HP-Xe was dissolved in an aqueous cryptophane-A-(OCH 2 COOH) 6 solution, and stable Xe signals could be measured over 35 min, only limited by the size of the gas reservoir. Such long and stable Version 6 21.10.2019 BN experimental conditions enabled the study of chemical exchange of xenon between cryptophane and water environments even for a time-consuming 2D NMR-experiment. The good signal stability over the measurement time allowed an exact determination of the residence time of the Xe-atom inside the cryptophane, resulting in an average residence time of 42.9 ± 3.3 ms.

Published
2018
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14. Chiroptical properties of 2,2’-bioxirane

Author

Thierry Brotin, Thierry Buffeteau, Nicolas Daugey, N. De Rycke, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Population, 010402 general chemistry, DFT calculations, 01 natural sciences, Polarizable continuum model, Catalysis, Analytical Chemistry, 0103 physical sciences, Drug Discovery, Molecule, Optical rotation, education, Conformational isomerism, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Bioxirane, Pharmacology, education.field_of_study, 010304 chemical physics, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, conformational analysis, vibrational circular dichroism, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Vibrational circular dichroism, Physical chemistry, Raman optical activity, Density functional theory
Abstract

The two enantiomers of 2,2'-bioxirane were synthesized, and their chiroptical properties were thoroughly investigated in various solvents by polarimetry, vibrational circular dichroism (VCD), and Raman optical activity (ROA). Density functional theory (DFT) calculations at the B3LYP/aug-cc-pVTZ level revealed the presence of three conformers (G+ , G- , and cis) with Gibbs populations of 51, 44, and 5% for the isolated molecule, respectively. The population ratios of the two main conformers were modified for solvents exhibiting higher dielectric constants (G- form decreases whereas G+ form increases). The behavior of the specific optical rotation values with the different solvents was correctly reproduced by time-dependent DFT calculations using the polarizable continuum model (PCM), except for the benzene for which explicit solvent model should be necessary. Finally, VCD and ROA spectra were perfectly reproduced by the DFT/PCM calculations for the Boltzmann-averaged G+ and G- conformers.

Published
2018
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15. Unsaturated cryptophanes: toward dual PHIP/hyperpolarised xenon sensors

Author

Estelle Léonce, Thierry Brotin, Nicolas de Rycke, Orsola Baydoun, Patrick Berthault, Gaspard Huber, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) ( LSDRM ), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) ( NIMBE UMR 3685 ), Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie - UMR5182 ( LC ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Cryptophane, Spectral line, 0104 chemical sciences, 3. Good health, Catalysis, Xenon, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, [ CHIM.MATE ] Chemical Sciences/Material chemistry, Proton NMR, Dual probe, General Materials Science, Biosensor
Abstract

Accepted Manuscript; International audience; Cryptophanes, cage-molecules constituted of aromatic bowls, are now well recognized as powerful xenon hosts in $^{129}$Xe NMR-based biosensing. In the quest of a dual probe that can be addressed only by NMR we have studied three cryptophanes bearing a tether with an unsaturated bond. The idea behind this is to build probes that can be detected both via hyperpolarised $^{129}$Xe NMR and Para-Hydrogen Induced Polarisation (PHIP) $^1$H NMR. Only two of the three cryptophanes experience a sufficiently fast hydrogenation enabling the PHIP effect. While the in-out xenon exchange properties are maintained after hydrogenation, the chemical shift of xenon encaged in these two cryptophanes is not strikingly modified, which impedes safe discrimination of the native and hydrogenated states via $^{129}$Xe NMR. However, a thorough examination of the hyperpolarised $^1$H spectra reveals some interesting features for the catalytic process and gives us clues for the design of doubly smart $^1$H/$^{129}$Xe NMR-based biosensors.

Published
2017
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16. Bimodal Fluorescence/{129}Xe NMR Probe for Molecular Imaging and Biological Inhibition of EGFR in Non-Small Cell Lung Cancer

Author

Sofia Rivera, Grégory Pieters, Hervé Volland, Gaëlle Milanole, Christophe Dugave, Bo Gao, Frédéric Law, Estelle Léonce, Bernard Rousseau, Céline Boutin, Audrey Paoletti, Jean-Luc Perfettini, Patrick Berthault, Eric Deutsch, Emilie Mari, François Fenaille, Thierry Brotin, Service de Chimie Bio-Organique et de Marquage ( SCBM ), Département Médicaments et Technologies pour la Santé ( DMTS ), Direction de Recherche Fondamentale (CEA) ( DRF (CEA) ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) ( DRF (CEA) ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay, Unité de radiothérapie moléculaire ( UMR 1030 ), Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Institut Gustave Roussy ( IGR ) -Université Paris-Sud - Paris 11 ( UP11 ), Département de radiothérapie [Gustave Roussy], Institut Gustave Roussy ( IGR ), Université Paris-Sud 11 - Faculté de médecine ( UP11 UFR Médecine ), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) ( LSDRM ), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) ( NIMBE UMR 3685 ), Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Institut de Biologie et de Technologies de Saclay ( IBITECS ), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), Laboratoire de Chimie - UMR5182 ( LC ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), ITMO Cancer AVIESAN (French Alliance for Life Sciences and Health), ANR-11-IDEX-0003-02/10-LABX-0035,Nano-Saclay,Paris-Saclay multidisciplinary Nano-Lab ( 2011 ), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Radiothérapie moléculaire (UMR 1030), Université Paris-Sud - Paris 11 (UP11)-Institut Gustave Roussy (IGR)-Institut National de la Santé et de la Recherche Médicale (INSERM), Institut Gustave Roussy (IGR), Université Paris-Sud - Paris 11 - Faculté de médecine (UP11 UFR Médecine), Université Paris-Sud - Paris 11 (UP11), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Biologie et de Technologies de Saclay (IBITECS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut Gustave Roussy (IGR)-Université Paris-Sud - Paris 11 (UP11)

Subjects
[SDV]Life Sciences [q-bio], EGFR, Clinical Biochemistry, Analytical chemistry, Pharmaceutical Science, Cetuximab, 010402 general chemistry, 01 natural sciences, Biochemistry, Epidermal growth factor, Drug Discovery, medicine, Receptor, Lung cancer, Molecular Biology, [ SDV ] Life Sciences [q-bio], 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Nuclear magnetic resonance spectroscopy, medicine.disease, Fluorescence, NMR, 0104 chemical sciences, 3. Good health, [ CHIM.MATE ] Chemical Sciences/Material chemistry, Cancer cell, Cancer research, Molecular Medicine, Molecular imaging, Hyperpolarized Xenon, Biosensor, medicine.drug
Abstract

International audience; Although Non-Small Cell Lung Cancer (NSCLC) is one of the main causes of cancer death, very little improvement has been made in the last decades regarding diagnosis and outcomes. In this study, a bimodal fluorescence/$^{129}$Xe NMR probe containing a xenon host, a fluorescent moiety and a therapeutic antibody has been designed to target the Epidermal Growth Factor Receptors (EGFR) overexpressed in cancer cells. This biosensor shows high selectivity for the EGFR, and a biological activity similar to that of the antibody. It is detected with high specificity and high sensitivity (sub-nanomolar range) through hyperpolarized $^{129}$Xe NMR. This promising system should find important applications for theranostic use.

Published
2017
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17. Role of the Methoxy Groups in Cryptophanes for Complexation of Xenon. Conformational Selection Evidenced by 129 Xe-1 H NMR SPINOE Experiments

Author

Estelle Léonce, Patrick Berthault, Céline Boutin, Erwann Jeanneau, Thierry Brotin, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-12-BSV5-0003,MAX4US,Miniaturization And hyperpolarized Xenon NMR for Ultrahigh Sensitivity(2012), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Stereochemistry, chemistry.chemical_element, 010402 general chemistry, Cryptophanes, 01 natural sciences, Spectral line, Cryptophane, chemistry.chemical_compound, Molecular recognition, Degree of substitution, Xenon, Physical and Theoretical Chemistry, Benzene, SPINOE, 010405 organic chemistry, hyperpolarized xenon, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, Atomic and Molecular Physics, and Optics, NMR, 0104 chemical sciences, 3. Good health, Crystallography, chemistry, Proton NMR, molecular recognition
Abstract

International audience; We report the laser-polarized 129 Xe and 1 H NMR spectra of a series of cryptophane derivatives that differ only by the number of methoxy groups attached on their benzene rings and the arrangement syn or anti of the linkers (compounds 6a-s, 9a-s, 12a-s). All these compounds bind xenon even though the characteristic signal of the gas encapsulated in the cavity of the cage-molecule cannot be always detected. Interestingly, the exchange dynamics of xenon strongly depends on the degree of substitution and is different from that of the cryptophane derivatives studied previously. In solution, the 1 H NMR spectra of these derivatives show the presence of different conformations in a slow exchange regime that can be explained by a decrease of the flexibility of their skeleton. Thanks to 129 Xe-1 H dipolar cross-relaxation (SPINOE) spectra we demonstrate that a single conformation present in solution can bind xenon.

Published
2017
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18. Immobilization of Cryptophane Derivatives onto SiO2/Au and Au Substrates

Author

Elise Siurdyban, Karine Heuzé, Luc Vellutini, Thierry Brotin, Thierry Buffeteau, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université Sciences et Technologies - Bordeaux 1

Subjects
Chemistry, Infrared, Polarization modulation, 02 engineering and technology, Surfaces and Interfaces, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Photochemistry, Grafting, 01 natural sciences, Cryptophane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Monolayer, Electrochemistry, Molecule, General Materials Science, Gold surface, 0210 nano-technology, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

The synthesis of a cryptophane molecule bearing five methoxy substituents and an alkanethiol chain, 4, as well as its subsequent grafting onto a gold surface, is reported. Immobilization of cryptophane derivatives onto silica (SiO2/Au) surfaces was also performed by reacting a cryptophane molecule bearing one or six acid functions, 5 or 6, respectively, with an amino-terminated self-assembled monolayer (SAM). Polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) was used to characterize the two types of cryptophane monolayers. Surface coverage of cryptophane monolayers was estimated by comparing the PM-IRRAS intensity of cryptophane bands with that calculated from the optical constants of pentamethoxy-cryptophane for a compact monolayer. A very efficient grafting of 4 onto a gold surface was found, with a surface coverage close to 100%. On the other hand, the reaction of mono-acid, 5, or hexa-acid, 6, cryptophanes with amino-terminated SAM was less efficient, since the surface coverage did not exceed 15%. Finally, a good surface coverage (75%) was also obtained by using a cysteamine coupling agent to modify 5 before its grafting onto a gold surface.

Published
2014
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19. Influence of the Cavity Size of Water-Soluble Cryptophanes on Their Binding Properties for Cesium and Thallium Cations

Author

Patrick Berthault, Sylvie Goncalves, Thierry Brotin, Thierry Buffeteau, Dominique Cavagnat, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-09-BLAN-0182,GHOST,Reconnaissance de gaz par des molécules cages en solution(2009), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC)

Subjects
Circular dichroism, 010405 organic chemistry, chemistry.chemical_element, Isothermal titration calorimetry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Enantiopure drug, chemistry, Caesium, Basic solution, Materials Chemistry, Thallium, Physical and Theoretical Chemistry
Abstract

International audience; The binding properties of water-soluble cryptophane 1 toward cesium and thallium cations, in basic solution, have recently been reported. In this Article, we show that water-soluble cryptophane-222 (2), cryptophane-223 (3), and cryptophane-233 (4), bearing zero, one, and two propylenedioxy linkers, respectively, also efficiently bind these two cations under similar experimental conditions. Their binding properties are thoroughly studied by 133Cs and 205Tl NMR spectroscopy, while the binding constants are determined by isothermal titration calorimetry (ITC) experiments under various experimental conditions. Complexation of cesium and thallium is also evidenced by electronic circular dichroism (ECD) using the enantiopure MM-2 compound. This study reveals that the cavity size of the cryptophane is not the main parameter to observe efficient binding. In contrast, the number of phenolate moieties surrounding the cryptophane backbone seems to be pivotal for the complexation of these two cations. These results are important in the field of detoxification.

Published
2013
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20. Chiroptical properties of cryptophane-111

Author

Marion Jean, Nicolas Daugey, Nicolas Vanthuyne, Thierry Buffeteau, Laurent Ducasse, Delphine Pitrat, Frank Wien, Nathalie Calin, Thierry Brotin, Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
Circular dichroism, 010405 organic chemistry, Chemistry, Analytical chemistry, General Physics and Astronomy, Time-dependent density functional theory, 010402 general chemistry, 01 natural sciences, Binding constant, Cryptophane, 0104 chemical sciences, Excited state, Vibrational circular dichroism, Physical chemistry, [CHIM]Chemical Sciences, Density functional theory, Raman optical activity, Physical and Theoretical Chemistry
Abstract

International audience; The two enantiomers of cryptophane-111 (1), which possesses the most simplified chemical structure of cryptophane derivatives and exhibits the highest binding constant for xenon encapsulation in organic solution, were separated by HPLC using chiral stationary phases. The chiroptical properties of [CD(+) 254 ]-1 and [CD(À) 254 ]-1 were determined in CH 2 Cl 2 and CHCl 3 solutions by polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) experiments and were compared to those of cryptophane-222 (2) derivative. Synchroton Radiation Circular Dichroism (SRCD) spectra were also recorded for the two enantiomers of 1 to investigate low-lying excited states in the 1 B b region. Time-dependent density functional theory (TDDFT) calculations of the ECD and SRCD as well as DFT calculations of the VCD and ROA allowed the [CD(À) 254 ]-PP-1 and [CD(+) 254 ]-MM-1 absolute configurations for 1 in CH 2 Cl 2 and CHCl 3 solutions. Similar configurations were found in the solid state from X-ray crystals of the two enantiomers but the chemical structures are significantly different from the one calculated in solution. In addition, the chiroptical properties of the two enantiomers of 1 were independent of the nature of the solvent, which is significantly different to that observed for cryptophane-222 compound. The lack of solvent molecule (CH 2 Cl 2 or CHCl 3) within the cavity of 1 can explain this different behaviour between 1 and 2. Finally, we show in this article that the encapsulation of xenon by 1 can be evidenced by ROA following the symmetric breathing mode of the cryptophane-111 skeleton at 150 cm À1 .

Published
2017
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21. Unusual Chiroptical Properties of the Cryptophane-222 Skeleton

Author

Marion Jean, Nicolas Daugey, Delphine Pitrat, Nathalie Calin, Frank Wien, Laurent Ducasse, Thierry Brotin, Thierry Buffeteau, Nicolas Vanthuyne, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Analytical chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, Spectral line, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Crystallography, chemistry.chemical_compound, Enantiopure drug, chemistry, Vibrational circular dichroism, Materials Chemistry, [CHIM.CRIS]Chemical Sciences/Cristallography, Raman optical activity, Physical and Theoretical Chemistry, Optical rotation, Derivative (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract

Enantiopure cryptophane-222 derivative (1) devoid of substituents was obtained via high-performance liquid chromatography (HPLC) using chiral stationary phases. The chiroptical properties of 1 were determined from polarimetry, electronic circular dichroism (ECD), synchrotron radiation circular dichroism (SRCD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) experiments and were compared to those of the cryptophane-A (2) derivative. Unusual polarimetric results were obtained for 1 in CHCl3 solvent as the sign of the optical rotation (OR) values changes in the nonresonance region above 365 nm, whereas no change was observed in the CH2Cl2 solvent. ECD spectra in the 1La and 1Lb regions were very similar for the two solutions and could not explain these unusual polarimetric properties. In contrast, SRCD spectra in the 1Bb region revealed spectral differences for the two solutions, which have been associated with conformational changes of the three linkers by time-dependent density func...

Published
2016
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22. Host-guest complexes between cryptophane-C and chloromethanes revisited

Author

Zoltan Takacs, Mária Šoltésová, Thierry Brotin, Jan Lang, Jozef Kowalewski, and Jean-Pierre Dutasta

Subjects
Chloroform, Proton, 010405 organic chemistry, Stereochemistry, Relaxation (NMR), General Chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Molecular recognition, chemistry, General Materials Science, Density functional theory, Two-dimensional nuclear magnetic resonance spectroscopy, Dichloromethane
Abstract

Cryptophane-C is composed of two nonequivalent cyclotribenzylene caps, one of which contains methoxy group substituents on the phenyl rings. The two caps are connected by three OCH2CH2O linkers in an anti arrangement. Host–guest complexes of cryptophane-C with dichloromethane and chloroform in solution were investigated in detail by nuclear magnetic resonance techniques and density functional theory (DFT) calculations. Variable temperature proton and carbon-13 spectra show a variety of dynamic processes, such as guest exchange and host conformational transitions. The guest exchange was studied quantitatively by exchange spectroscopy measurements or by line-shape analysis. The conformational preferences of the guest-containing host were interpreted through cross-relaxation measurements, providing evidence of the gauche+2 and gauche−2 conformations of the linkers. In addition, the mobility of the chloroform guest inside the cavity was studied by carbon-13 relaxation experiments. Combining different types of evidence led to a detailed picture of molecular recognition, interpreted in terms of conformational selection. Copyright © 2012 John Wiley & Sons, Ltd.

Published
2012
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23. A Sensitive Zinc-Activated129Xe MRI Probe

Author

Sylvie Coudert, Patrick Berthault, Estelle Léonce, Céline Boutin, Léa Delacour, Nawal Tassali, Bernard Rousseau, Naoko Kotera, David-Alexandre Buisson, Frédéric Taran, Thierry Brotin, Ténin Traoré, Jean-Pierre Dutasta, Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre de résonance magnétique des systèmes biologiques (CRMSB), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
inorganic chemicals, Gadolinium, chemistry.chemical_element, Zinc, 010402 general chemistry, 01 natural sciences, Catalysis, Cryptophane, Ion, Nuclear magnetic resonance, Xenon, medicine, Humans, Moiety, Polycyclic Compounds, Chelation, cardiovascular diseases, medicine.diagnostic_test, integumentary system, 010405 organic chemistry, Magnetic resonance imaging, General Chemistry, General Medicine, Magnetic Resonance Imaging, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Molecular Probes, Xenon Isotopes, circulatory and respiratory physiology
Abstract

International audience; Xenon capsule: A smart 129Xe NMR-based sensor of Zn2+ ions for magnetic resonance imaging (MRI) is proposed. The resonance frequency of xenon encapsulated in a cryptophane that bears a nitrilotriacetic ligand moiety varies when Zn2+ ions are present in solution (see picture). With hyper-polarized gas, such a construct enables detection of 100 nM zinc in one xenon batch, a threshold 300 times lower than achieved with gadolinium chelates.

Published
2012
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24. Encapsulation of Small Gas Molecules by Cryptophane-111 in Organic Solution. 1. Size- and Shape-Selective Complexation of Simple Hydrocarbons

Author

Thierry Brotin, Boyd M. Goodson, Kathleen E. Chaffee, Heather A. Fogarty, Jean-Pierre Dutasta, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, 010405 organic chemistry, Chloromethane, Analytical chemistry, chemistry.chemical_element, Trapping, 010402 general chemistry, Kinetic energy, 01 natural sciences, Cryptophane, Methane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Xenon, chemistry, 13. Climate action, Molecule, Physical and Theoretical Chemistry
Abstract

The reversible trapping of small hydrocarbons and other gases by cryptophane-111 (1) in organic solution was characterized with variable-temperature (1)H NMR spectroscopy. Characteristic spectral changes observed upon guest binding allowed kinetic and thermodynamic data to be readily extracted, permitting quantification and comparison of different host-guest interactions. Previous work (J. Am. Chem. Soc. 2007, 129, 10332) demonstrated that 1, the smallest cryptophane to date, forms a complex with xenon with remarkably high affinity. Presently, it is shown that 1 also exhibits slow exchange dynamics with methane at reduced temperatures (delta(bound) = -5.2 ppm) with an association constant K(a) = 148 M(-1) at 298 K. In contrast, ethane and ethylene are poorly recognized by 1 with K(a) values of only 2 M(-1) and 22 M(-1), respectively; moreover, chloromethane (whose molecular volume is similar to that of xenon, approximately 42 A(3)) is not observed to bind to 1. Separately, molecular hydrogen (H(2)) gas is observed to bind 1, but in contrast to other ligands presently studied, H(2) complexation is spectrally manifested by fast exchange throughout virtually the entire range of available conditions, as well as by a complex dependence of the guest (1)H resonance frequency upon temperature and host concentration. Taken together, these results establish 1 as a selective host for small gases, with implications for the design of size- and geometry-selective sensors targeted for various gas molecules.

Published
2009
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25. Water-soluble cryptophanes: design and properties

Author

Alexandre Martinez, Jean-Pierre Dutasta, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Brotin, thierry

Subjects
Green chemistry, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Supramolecular chemistry, Nanotechnology, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, Inherent chirality, 01 natural sciences, Cryptophane, 0104 chemical sciences, Molecular recognition, Molecule, Host–guest chemistry, Supramolecular catalysis, ComputingMilieux_MISCELLANEOUS
Abstract

The molecular cages, or host molecules, still play an important role in supramolecular chemistry, where they are at the origin of the most spectacular advances in the field of molecular recognition. In this review we focus on the most significant results developed in recent years in the field of the chemistry of water-soluble host molecules belonging to the family of cryptohanes and hemicryptophanes. Indeed, some recent progress towards biosciences and new approaches in supramolecular catalysis contributed significantly to the development of the domain. The need to work in aqueous media appears evident for biological or biomedical applications and for the design of new catalytic systems to address critical issues of green chemistry, where environmental considerations may require the use of water as solvent. We thus report the new synthetic strategies that have been developed to produce hydrosoluble cages and we discuss their recognition properties toward small neutral molecules, ammonium cations and metal ions. We also describe more specifically the design of water-soluble xenon-cryptophane biosensors potentially usable for biomedical imaging. The inherent chirality of these molecules makes them very selective receptors for chiral substrates and this aspect is also underlined. The potential of hemicryptophanes in supramolecular catalysis in aqueous media has resulted in important and innovative recent results that are reported in this chapter.

Published
2016

26. Chiroptical Properties of Cryptophane-223 and -233 Investigated by ECD, VCD, and ROA Spectroscopy

Author

Nicolas Daugey, Erwann Jeanneau, Thierry Buffeteau, Nicolas Vanthuyne, Thierry Brotin, Laurent Ducasse, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, 010405 organic chemistry, Chemistry, Analytical chemistry, Absolute configuration, Time-dependent density functional theory, 010402 general chemistry, 01 natural sciences, Cryptophane, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Enantiopure drug, Vibrational circular dichroism, Materials Chemistry, Density functional theory, Raman optical activity, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Enantiopure cryptophane derivatives 1 and 2, possessing linkers of different nature (ethylenedioxy and propylenedioxy) connecting the two cyclotribenzylenes (CTB) units, were separated by HPLC using chiral stationary phases. X-ray crystallographic structures of the four enantiomers (+)-1, (-)-1, (+)-2, and (-)-2 have been obtained, allowing the unambiguous determination of their absolute configuration (AC) in the solid state. The chiroptical properties of compounds 1 and 2 were determined from polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) experiments and were compared to those of cryptophane-A (3) derivative. VCD, ROA and ECD spectra of 1 and 2 were calculated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, respectively, to confirm the AC of the cryptophane derivatives in solution. The (+)-PP and (-)-MM configurations were established for compounds 1 and 2 in chloroform solution, as already reported for the two enantiomers of 3. This result is in agreement with the X-ray structures of the two enantiomers of 1 and 2.

Published
2015
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27. Raman optical activity of enantiopure cryptophanes

Author

Dominique Cavagnat, Thierry Buffeteau, Nicolas Daugey, Thierry Brotin, Nicolas Vanthuyne, Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, Chemistry, Absolute configuration, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Enantiopure drug, Materials Chemistry, Molecule, Density functional theory, Raman optical activity, Physical and Theoretical Chemistry, Enantiomer, ComputingMilieux_MISCELLANEOUS, Ethylenedioxy
Abstract

Raman optical activity (ROA) and density functional theory (DFT) calculations were used to determine the absolute configuration of enantiopure cryptophane molecules and to obtain conformational information about their three ethylenedioxy linkers. ROA spectra recorded in chloroform solution for the two resolved enantiomers of cryptophanes derivatives bearing five (2), six (1), nine (3 and 4), and 12 (5) methoxy substituents are presented for the first time. The number of methoxy substituents (cryptophanes 1, 3, and 5) and the arrangement of the three linkers (anti for 3 and syn for 4) are two important parameters that significantly affect the ROA spectra. DFT calculations, at the B3PW91/6-31G** level, for cryptophane bearing six methoxy substituents establish, besides the absolute configuration, the preferential all-trans conformation of the ethylenedioxy linkers of the chloroform-cryptophane complex. This study shows that the ROA/DFT approach exhibits a higher selectivity for the conformation of the linkers than vibrational circular dichroism (VCD) associated with theoretical calculations.

Published
2014
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28. Ultrafast Z-Spectroscopy for 129 Xe NMR-Based Sensors

Author

Céline Boutin, Patrick Berthault, Estelle Léonce, Alexej Jerschow, Thierry Brotin, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Department of Chemistry [New York], Columbia University [New York], École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, chemistry.chemical_element, Nanotechnology, 010402 general chemistry, 01 natural sciences, Article, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Magnetization, Xenon, Reaction rate constant, chemistry, Chemical physics, Saturation transfer, General Materials Science, Hyperpolarization (physics), Physical and Theoretical Chemistry, Spectroscopy, Ultrashort pulse, Biosensor, ComputingMilieux_MISCELLANEOUS
Abstract

When working with hyperpolarized species, it is often difficult to maintain a stable level of magnetization over consecutive experiments, which renders their detection at the trace level cumbersome, even when combined with chemical exchange saturation transfer (CEST). We report herein the use of ultra-fast Z-spectroscopy as a powerful means to detect low concentrations of 129Xe NMR-based sensors and to measure the in-out xenon exchange. Modifications of the original sequence enable a multiplexed detection of several sensors, as well as the extraction of the exchange buildup rate constant in a single-shot fashion.

Published
2013
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29. Synthesis of highly substituted cryptophane derivatives

Author

Dominique Cavagnat, Erwann Jeanneau, Thierry Buffeteau, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, Organic Chemistry, chemistry.chemical_element, Alcohol, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, 3. Good health, Catalysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Yield (chemistry), Proton NMR, Scandium, Benzene, Trifluoromethanesulfonate, ComputingMilieux_MISCELLANEOUS
Abstract

We report the synthesis of new cryptophane derivatives 1-4 bearing nine (1, 2) and twelve (3, 4) methoxy substituents. These compounds represent the first examples of cryptophane derivatives bearing more than six substituents attached on the benzene rings. The preparation of these highly substituted cryptophanes was achieved due to the synthesis of a new cyclotrisyringyl derivative obtained from the reaction of a protected syringyl alcohol in the presence of a catalytic amount of scandium triflate Sc(OTf)3. This reaction also provides the protected cyclotetrasyringyl derivative in low yield (7%), which was fully characterized by (1)H NMR, IR, and X-ray crystallography. In contrast to what is observed for the cryptophane-A congener, the synthesis of these highly substituted cryptophanes gives rise to the two anti- and syn-diastereomers. These compounds have been fully characterized, and their X-ray structures have been obtained to ascertain the stereochemistry of these new cryptophane derivatives.

Published
2013
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30. [n]-Polyenovanillins (n = 1−6) as New Push−Pull Polyenes for Nonlinear Optics: Synthesis, Structural Studies, and Experimental and Theoretical Investigation of Their Spectroscopic Properties, Electronic Structures, and Quadratic Hyperpolarizabilities

Author

Thierry Brotin, Joseph Zyss, Chantal Andraud, Monique Perrin, Sophie Brasselet, Isabelle Ledoux, André Collet, and Alain Thozet, Stéréochimie et Interactions Moléculaires (STIM), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), France Telecom, Centre National d'Etudes de Télécommunications, Laboratoire de Bagneux (CNET Bagneux), CNET, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Absorption spectroscopy, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, General Chemical Engineering, Solvatochromism, Nonlinear optics, Hyperpolarizability, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Electronic structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, NMR spectra database, CNDO/2, Dipole, Computational chemistry, Materials Chemistry, Physical chemistry
Abstract

International audience; We describe the synthesis and quadratic hyperpolarizability properties of [n]-polyenovanillins, a new family of push−pull polyenes deriving from vanillin, thiovanillin, and isothiovanillin. Twenty-five [n]-polyenovanillins of structure 3,4-(RO;R‘S)C6H4(CHCH)nCHO [with n = 1−6 and R, R‘ = Me or n-Bu] were synthesized by using a Wittig−Horner polyvinylogation methodology, and the structure of one of these was established by single-crystal X-ray crystallography. The UV−vis absorption and fluorescence spectra of these polyenovanillins were recorded and interpreted in light of CNDO/S calculations that allowed the identification of the different transitions. EFISH measurements provided up to 350 × 10-30 esu (for 14, n = 6) with an exponential increase of the quadratic hyperpolarizability with the conjugation length. These data were satisfactorily interpreted by means of a CNDO/S/NLO method which provided information as to the relative orientation of the dipole moment μ and βvec, the vector part of the hyperpolarizability tensor. In the sulfur-substituted series, there is a significant divergence between the orientation of μ and βvec, which in turn leads to an underestimation of β in the EFISH method. The calculation also revealed that when the length of the polyenic chain increases, the charge transfer from the donor toward the acceptor actually tends to concentrate on the polyenic chain rather than on the aldehyde group.

Published
1996
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31. Enantiopure Supramolecular Cages: Synthesis and Chiral Recognition Properties

Author

Alexandre Martinez, Laure Guy, Jean-Pierre Dutasta, and Thierry Brotin

Subjects
010405 organic chemistry, Chemistry, Supramolecular chemistry, Nanotechnology, Stereoisomerism, 010402 general chemistry, Inherent chirality, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Stereocenter, Molecular recognition, Enantiopure drug, Molecule, Enantiomer
Abstract

Enantiopure compounds are ubiquitous in the chemical sciences and present a particular interest in the field of molecular recognition and host-guest systems. Indeed, chiral molecular receptors are at the basis of numerous biological recognition processes and have important implications in biochemistry or pharmacology. Chemists have been investigating this field for several decades, which has led to the development of the synthesis of chiral hosts, their enantiomeric differentiation, and the studies of their recognition properties towards important and bio-relevant chiral guest substrates. The design of molecular cages is a rather difficult task that is even more demanding when enantiopure molecules are required. In this review we chose to present the main families of synthetic organic supramolecular cages that have been developed, whose structures contain stereogenic centers or present an inherent chirality, giving rise to chiral supramolecular cages. Particular attention is given to obtaining enantiopure compounds. Their recognition properties are also underlined. A last important aspect of the review is to present how chiroptical spectroscopies can be used to characterize the recognition phenomena displayed by supramolecular cages.

Published
2013
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32. Water-soluble molecular capsule for the complexation of cesium and thallium cations

Author

Thierry Brotin, Patrick Berthault, Thierry Buffeteau, Roland Montserret, Dominique Cavagnat, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie et chimie des protéines [Lyon] (IBCP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), ANR-09-BLAN-0182,GHOST,Reconnaissance de gaz par des molécules cages en solution(2009), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Inorganic chemistry, chemistry.chemical_element, Cesium, Calorimetry, 010402 general chemistry, 01 natural sciences, Cryptophane, chemistry.chemical_compound, Coordination Complexes, Cations, Materials Chemistry, Polycyclic Compounds, cardiovascular diseases, Physical and Theoretical Chemistry, Thallium, 010405 organic chemistry, Circular Dichroism, Binding properties, Capsule, Water, Stereoisomerism, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Enantiopure drug, Water soluble, chemistry, Caesium, cardiovascular system, Derivative (chemistry)
Abstract

Binding properties of cesium and thallium cations by an enantiopure cryptophane derivative PP-1 have been investigated in water under basic conditions. The binding process has been evidenced using electronic circular dichroism (ECD), and binding constants of the Cs(+)@PP-1 and Tl(+)@PP-1 complexes have been determined from isothermal titration calorimetry (ITC) experiments in LiOH/H(2)O, NaOH/H(2)O, and KOH/H(2)O solutions. In addition, Tl(+)@PP-1 complex has been characterized for the first time by (205)Tl NMR spectroscopy. Cryptophane 1 exhibits an exceptionally high affinity for thallium and cesium cations in a large range of experimental conditions (nature, concentration of the counterion, and temperature). For example, binding constants as high as 2.9 × 10(9) M(-1) and 5.3 × 10(8) M(-1) have been measured by ITC at 298 K in NaOH/H(2)O (0.1 M) solution, for the Tl(+)@PP-1 and Cs(+)@PP-1 complexes, respectively. The high affinity of cryptophane 1 for Cs(+) and Tl(+) cations is preserved at higher LiOH, NaOH, and KOH concentrations and under extreme basic conditions, revealing the stability and the great selectivity of this supramolecular system toward Li(+), Na(+), and K(+) cations.

Published
2012
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33. Inclusion of Chloromethane Guests Affects Conformation and Internal Dynamics of Cryptophane-D Host

Author

Jean-Pierre Dutasta, Jozef Kowalewski, Jan Lang, Zoltan Takacs, Guido Todde, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Faculty of Mathematics and Physics [Praha/Prague], Charles University [Prague] (CU), Collège de France (CdF (institution)), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Models, Molecular, Magnetic Resonance Spectroscopy, Chloroform, 010405 organic chemistry, Stereochemistry, Chloromethane, Molecular Conformation, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Kinetics, chemistry.chemical_compound, chemistry, Methyl Chloride, Materials Chemistry, Quantum Theory, Polycyclic Compounds, Cryptophane-D, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Dichloromethane
Abstract

Cryptophane-D is composed of two nonequivalent cyclotribenzylene caps bound together by three OCH2CH2O bridges in a syn arrangement. Host-guest complexes with chloroform and dichloromethane were investigated in solution by NMR spectroscopy. Variable temperature NMR (1)H and (13)C spectra showed effects of chemical exchange between the free and bound guest and of conformational exchange for the host, strongly and specifically affected by guest binding. We found in particular that the carbon-13 chemical shifts for the linkers connecting the two cyclotribenzylene units are very informative. The NMR results were supported by DFT calculations. The guest exchange was also studied quantitatively, either by EXSY measurements (for chloroform as guest) or by line-shape analysis (for dichloromethane as guest). In the case of chloroform guest, we also investigated cross-relaxation between the guest and host protons, as well as carbon-13 longitudinal relaxation and heteronuclear NOE at three different fields. The results were interpreted in terms of orientation and dynamics of the guest inside the host cavity. Putting together various types of evidence resulted in remarkably detailed insight into the process of molecular recognition of the two guests by cryptophane-D host.

Published
2012
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34. Influence of the Chemical Structure of Water-Soluble Cryptophanes on Their Overall Chiroptical and Binding Properties

Author

Dominique Cavagnat, Thierry Brotin, Mathieu Linares, Thierry Buffeteau, Aude Bouchet, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chirotechnologies : Catalyse et Biocatalyse (CCB), Université Paul Cézanne - Aix-Marseille 3-Centre National de la Recherche Scientifique (CNRS), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, 010405 organic chemistry, Chemistry, Stereochemistry, Chemical structure, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Molecular recognition, Vibrational circular dichroism, Proton NMR, Enantiomer, Spectroscopy, ComputingMilieux_MISCELLANEOUS
Abstract

The synthesis and the chiroptical properties of the two enantiomers of the hexacarboxylic acid cryptophane-A derivative, 1, are described in this article. The chiroptical and binding properties of 1 toward achiral and chiral guests have been investigated in water under basic conditions by polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and (1)H NMR spectroscopy. These experiments reveal that the (1)H NMR spectra of 1 are very sensitive to the nature of the guest trapped in its cavity whereas ECD and VCD spectra remain unchanged. We also show that the two enantiomers of 1 are able to distinguish between the two enantiomers of a series of small chiral epoxides. The enantiodiscrimination increases with the size of the chiral guest whereas the corresponding binding constants decrease. In contrast to what was observed for other water-soluble cryptophanes, the molecular recognition process is found independent of the nature of the counterions surrounding host 1, shedding light on the importance of the chemical structure of cryptophanes on their binding and chiroptical properties.

Published
2011
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35. Cell uptake of a biosensor detected by hyperpolarized 129Xe NMR: The transferrin case

Author

Nadège Jamin, Thierry Brotin, Nawal Tassali, Patrick Berthault, Céline Boutin, Yves Boulard, Gaspard Huber, Fatimazohra Lenda, Marie Carrière, Aurore Bogaert-Buchmann, Alain Sanson, Jean-Pierre Dutasta, François Leteurtre, Antoine Stopin, Hervé Desvaux, Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Système membranaires, photobiologie, stress et détoxication (SMPSD), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), CNR-ISTEC, National Research Council of Italy, Service de Biologie Intégrative et Génétique Moléculaire (SBIGeM), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre de résonance magnétique des systèmes biologiques (CRMSB), Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB), Service de Chimie Inorganique et Biologique (SCIB - UMR E3), Institut Nanosciences et Cryogénie (INAC), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay, Laboratoire de Chimie - UMR5182 ( LC ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] ( IBMM ), Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Système membranaires, photobiologie, stress et détoxication ( SMPSD ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS ), Service de Biologie Intégrative et Génétique Moléculaire ( SBIGeM ), Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Résonance magnétique des systèmes biologiques ( RMSB ), Université Bordeaux Segalen - Bordeaux 2-Centre National de la Recherche Scientifique ( CNRS ), Service de Chimie Inorganique et Biologique ( SCIB - UMR E3 ), Institut Nanosciences et Cryogénie ( INAC ), and Université Grenoble Alpes ( UGA ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Grenoble Alpes ( UGA ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Centre National de la Recherche Scientifique ( CNRS )

Subjects
Magnetic Resonance Spectroscopy, Clinical Biochemistry, Pharmaceutical Science, Transferrin receptor, Biosensing Techniques, macromolecular substances, 010402 general chemistry, Endocytosis, 01 natural sciences, Biochemistry, Cryptophane, Cell membrane, Cell Line, Tumor, Drug Discovery, Fluorescence microscope, medicine, Humans, Hyperpolarization (physics), Molecular Biology, chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Transferrin, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, medicine.anatomical_structure, chemistry, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, Biophysics, Xenon Isotopes, Molecular Medicine, Biosensor, Protein Binding
Abstract

International audience; For detection of biological events in vitro, sensors using hyperpolarized 129Xe NMR can become a powerful tool, provided the approach can bridge the gap in sensitivity. Here we propose constructs based on the non-selective grafting of cryptophane precursors on holo-transferrin. This biological system was chosen because there are many receptors on the cell surface, and endocytosis further increases this density. The study of these biosensors with K562 cell suspensions via fluorescence microscopy and 129Xe NMR indicates a strong interaction, as well as interesting features such as the capacity of xenon to enter the cryptophane even when the biosensor is endocytosed, while keeping a high level of polarization. Despite a lack of specificity for transferrin receptors, undoubtedly due to the hydrophobic character of the cryptophane moiety that attracts the biosensor into the cell membrane, these biosensors allow the first in-cell probing of biological events using hyperpolarized xenon.

Published
2011
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36. Enantioselective Complexation of Chiral Propylene Oxide by an Enantiopure Water-Soluble Cryptophane

Author

Dominique Cavagnat, Mathieu Linares, Aude Bouchet, Hans Ågren, Thierry Brotin, Thierry Buffeteau, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chirotechnologies : Catalyse et Biocatalyse (CCB), Université Paul Cézanne - Aix-Marseille 3-Centre National de la Recherche Scientifique (CNRS), Royal Institute of Technology [Stockholm] (KTH ), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Epoxide, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Cryptophane, Substrate Specificity, chemistry.chemical_compound, Ab initio quantum chemistry methods, Organic chemistry, Polycyclic Compounds, Propylene oxide, ComputingMilieux_MISCELLANEOUS, Aqueous solution, 010405 organic chemistry, Chemistry, Organic Chemistry, Diastereomer, Enantioselective synthesis, Water, Stereoisomerism, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Enantiopure drug, Solubility, Epoxy Compounds, Thermodynamics
Abstract

ECD and NMR experiments show that the complexation of propylene oxide (PrO) within the cavity of an enantiopure water-soluble cryptophane 1 in NaOH solution is enantioselective and that the (R)-PrO@PP-1 diastereomer is more stable than the (S)-PrO@PP-1 diastereomer with a free energy difference of 1.7 kJ/mol. This result has been confirmed by molecular dynamics (MD) and ab initio calculations. The enantioselectivity is preserved in LiOH and KOH solutions even though the binding constants decrease, whereas PrO is not complexed in CsOH solution.

Published
2011
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37. Conformational Effects Induced by Guest Encapsulation in an Enantiopure Water-Soluble Cryptophane

Author

Dominique Cavagnat, Hans Ågren, Aude Bouchet, Mathieu Linares, Thierry Buffeteau, Thierry Brotin, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Science and Technology [Linköping], Linköping University (LIU), Theoretical Chemistry, Royal Institute of Technology [Stockholm] (KTH ), Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC)

Subjects
Circular dichroism, Inorganic chemistry, Molecular Conformation, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Cryptophane, Inclusion compound, chemistry.chemical_compound, Theoretical chemistry, [CHIM]Chemical Sciences, Polycyclic Compounds, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Aqueous solution, 010405 organic chemistry, Chemistry, Circular Dichroism, Organic Chemistry, Water, Stereoisomerism, 0104 chemical sciences, 3. Good health, Crystallography, Enantiopure drug, Solubility, Vibrational circular dichroism, Quantum Theory, Counterion
Abstract

A new water-soluble cryptophane 1 derivative (penta-hydroxyl cryptophane-A) has been synthesized from cryptophanol-A and the chiroptical properties of its two enantiomers MM-1 and PP-1 have been studied by polarimetry, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD). Cryptophane 1 shows specific circular dichroism responses upon complexation that depend on the size of the guest and on the nature of the counterion (Li(+), Na(+), K(+), Cs(+)) present in the solution. In LiOH and NaOH solutions, chiroptical changes induced by the encapsulation of guests and by the presence of cations in the vicinity of hosts can be interpreted from molecular dynamics (MD) and ab initio calculations by subtle conformational changes of the bridges. In KOH solution, the exchange dynamics is dependent on the size of the guest molecules, whereas in CsOH solution no encapsulation effect is observed whatever the size of the guest molecule. This last behavior comes from the fact that host 1 exhibits a very high affinity for cesium cations.

Published
2011
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38. A Water-Soluble Xe@cryptophane-111 Complex Exhibits Very High Thermodynamic Stability and a Peculiar 129Xe NMR Chemical Shift

Author

K. Travis Holman, Akil I. Joseph, Thierry Brotin, Robert Fairchild, Céline Boutin, Patrick Berthault, Jean-Pierre Dutasta, Gaspard Huber, Heather A. Fogarty, National Centre for Biological Sciences [TIFR] (NCBS), Tata Institute for Fundamental Research (TIFR), Marfan Research Group, Westmead Hospital [Sydney], Department of Molecular Genetics, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Aqueous solution, 010405 organic chemistry, Chemistry, Stereochemistry, Chemical shift, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Biochemistry, Binding constant, Catalysis, Cryptophane, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, Yield (chemistry), Chemical stability, Derivative (chemistry)
Abstract

The known xenon-binding (±)-cryptophane-111 (1) has been functionalized with six [(η(5)-C(5)Me(5))Ru(II)](+) ([Cp*Ru](+)) moieties to give, in 89% yield, the first water-soluble cryptophane-111 derivative, namely [(Cp*Ru)(6)1]Cl(6) ([2]Cl(6)). [2]Cl(6) exhibits a very high affinity for xenon in water, with a binding constant of 2.9(2) × 10(4) M(-1) as measured by hyperpolarized (129)Xe NMR spectroscopy. The (129)Xe NMR chemical shift of the aqueous Xe@[2](6+) species (308 ppm) resonates over 275 ppm downfield of the parent Xe@1 species in (CDCl(2))(2) and greatly broadens the practical (129)Xe NMR chemical shift range made available by xenon-binding molecular hosts. Single crystal structures of [2][CF(3)SO(3)](6)·xsolvent and 0.75H(2)O@1·2CHCl(3) reveal the ability of the cryptophane-111 core to adapt its conformation to guests.

Published
2010
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39. Effect of pH and Counterions on the Encapsulation Properties of Xenon in Water-Soluble Cryptophanes

Author

Patrick Berthault, Yves Boulard, Hervé Desvaux, Jean-Pierre Dutasta, Antoine Stopin, Thierry Brotin, Thierry Wendlinger, Marina Gyejacquot, Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Biologie Intégrative et Génétique Moléculaire (SBIGeM), Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut Rayonnement Matière de Saclay ( IRAMIS ), Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay, Laboratoire de Chimie - UMR5182 ( LC ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Service de Biologie Intégrative et Génétique Moléculaire ( SBIGeM ), Institut de Biologie Intégrative de la Cellule ( I2BC ), Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ) -Université Paris-Sud - Paris 11 ( UP11 ) -Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ) -Université Paris-Saclay-Centre National de la Recherche Scientifique ( CNRS ), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Magnetic Resonance Spectroscopy, Xenon, Analytical chemistry, Ionic bonding, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Cryptophane, Molecule, Polycyclic Compounds, chemistry.chemical_classification, Molecular Structure, 010405 organic chemistry, Organic Chemistry, Water, General Chemistry, Nuclear magnetic resonance spectroscopy, Hydrogen-Ion Concentration, Triazoles, Binding constant, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Solubility, chemistry, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, Xenon Isotopes, Counterion, Biosensor, Algorithms
Abstract

International audience; In the 129Xe NMR-based biosensing approach in which the hyperpolarized noble gas is transported to biological receptors for a sensitive molecular imaging, cryptophanes are excellent xenon host systems. However to avoid formation of self-organized systems, these hydrophobic cage molecules can be rendered water soluble by introduction of ionic groups. We show that the sensitivity of xenon to its local environment and the presence of these ionic functions can lead to interesting properties. For a first water-soluble cryptophane derivative, we show that a precise monitoring of the local pH can be performed. For a second cryptophane, the presence of ionic groups close to the cryptophane cavity modifies the xenon binding constant and in–out exchange rate. The latter allows the tuning of physical properties of xenon–cryptophane interactions without resorting to a change of the cavity size. These results open new perspectives on the influence of chemical modifications of cryptophanes for optimizing the biosensor properties.

Published
2010
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40. NMR investigation of guest-host complex between chloroform and cryptophane C

Author

Dmytro Kotsyubynskyy, Thierry Brotin, Mária Šoltésová, Zoltan Takacs, Jean-Pierre Dutasta, Jan Lang, Jozef Kowalewski, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Bridged-Ring Compounds, Models, Molecular, Magnetic Resonance Spectroscopy, Guest host, Kinetics, 010402 general chemistry, 01 natural sciences, Cryptophane, chemistry.chemical_compound, Computational chemistry, Molecule, Organic chemistry, General Materials Science, Chloroform, Molecular Structure, 010405 organic chemistry, Phenyl Ethers, General Chemistry, Nuclear magnetic resonance spectroscopy, Reference Standards, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Proton NMR, Quantum Theory, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

International audience; Guest–host complex between cryptophane C, possessing two non-equivalent caps, and chloroform is investigated by NMR spectroscopy. The kinetics of the chloroform exchange between the bound and free sites is determined by 1H exchange spectroscopy. Moreover, the preferential orientation of chloroform molecule with respect to the cryptophane C frame is examined by the NOESY and ROESY experiments. The experimental findings are compared to the results of quantum chemical calculations. Copyright © 2010 John Wiley & Sons, Ltd.

Published
2010
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41. Cryptophanes and Their Complexes—Present and Future

Author

Jean-Pierre Dutasta, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, 010405 organic chemistry, Computational chemistry, Cyclotriveratrylene, General Chemistry, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences
Abstract

International audience; 1. Introduction 2. Syntheses of Cryptophanes 2.1. The “Direct (Two-Step) Method” 2.2. The “Template Method” 2.3. Coupling of CTVs 3. Syntheses of New Cryptophanes Using the Template Method 3.1. Deuterium Labeled Cryptophanes 3.2. Methylthio Containing Crytophanes 3.3. Amphipathic Cryptophanes 3.4. Syntheses of C2-Symmetrical Cryptophanes 4. Transformation and Functionalization of Cryptophanes 4.1. Water-Soluble Cryptophanes: Hexacarboxylic Acid Cryptophanes 4.2. Monofunctionalized Cryptophanes: Cryptophanol 4.3. Cryptophanes as Biosensors 4.4. Bis-cryptophanes 5. Structural Aspects and Characterization of Cryptophanes 5.1. Some Peculiarities in the Characterization of Cryptophane Hosts 5.2. Inverted and Imploded Cryptophanes 5.3. Molecular Structures of Cryptophane-A 1 and Related Ones 5.4. Some Aspects of Cryptophanes in the Crystalline State 6. Binding Properties of Cryptophanes 6.1. Complexation of Small Neutral Molecules 6.2. Complexation of Ammonium Guests 6.3. Complexation of Metal Cations 6.4. Complexation of Anion Guests 7. Dynamics of the Guest in the Cryptophane Cavity 7.1. Investigations by NMR Spectroscopy 7.2. Computational Investigations 7.3. Host−Guest Complexes in the Solid: Raman Microspectrometry 7.4. Studies in Mesophases 8. Chiral Discrimination 8.1. CHFClBr 8.2. CHFClI 9. Xenon in the Cryptophane Cavity 9.1. Xe@cryptophane Complexes 9.2. 129Xe NMR Spectroscopy of Xe@Cryptophane Complexes 9.3. Dynamics of Xenon Encapsulation 9.4. Laser-Polarized Xenon and Cryptophanes 9.4.1. Laser-Polarized Xenon in Cryptophane Complexes 9.4.2. Probing the Molecular Cavity of Cryptophane 9.4.3. “Functionalized” Xenon 10. Syntheses and Chiroptical Properties of Optically Pure Cryptophanes 10.1. Optical Resolution of CTVs and Cryptophanes 10.1.1. Optical Resolution Using Chiral HPLC 10.1.2. Resolution of CTVs 10.2. Syntheses of Optically Pure Cryptophanes 10.2.1. From Enantiopure CTVs 10.2.2. From Cryptophanol 10.3. Electronic Circular Dichroism (ECD) Spectra of Resolved Cryptophanes 10.3.1. ECD of CTVs 10.3.2. ECD of D3-Symmetrical Cryptophanes 10.3.3. ECD of C1-Symmetrical Cryptophanes 10.4. VCD of Cryptophane Hosts 11. Conclusion—The Future of Cryptophanes 12. Dedication

Published
2009
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42. Conformational changes in cryptophane having C1-symmetry studied by vibrational circular dichroism

Author

Dominique Cavagnat, Thierry Brotin, Thierry Buffeteau, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Absolute configuration, 010402 general chemistry, Photochemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Vibrational circular dichroism, Molecule, Density functional theory, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Vibrational circular dichroism (VCD) measurements and density functional theory (DFT) calculations were used to obtain the absolute configuration of a cryptophane molecule having C1-symmetry (labeled cryptophane-H). This molecule exhibits chiroptical properties different from those published for cryptophane-A having D3-symmetry [Brotin et al. J. Am. Chem. Soc. 2006, 128, 5533−5540]. In particular, we have shown that the conformation of the aliphatic linkers is very dependent on the solvent used and its ability to enter (CDCl3 solution) or not (C2D2Cl4 solution) in the cryptophane cavity. Calculations performed at the DFT (B3PW91/6-31G*) level establish, besides the absolute configuration, the preferential anti and gauche conformations of the aliphatic linkers of the chloroform@cryptophane-H complex and the empty cryptophane-H molecule, respectively. Polarimetric measurements performed in several solvents reflect also the change of conformation of the bridges upon guest encapsulation.

Published
2008
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43. Studies of Inclusion Complexes of Dichloromethane in Cryptophanes by Exchange Kinetics and 13 C NMR in Solution and the Solid State

Author

Jean-Pierre Dutasta, A. Y. H. Lo, Thierry Brotin, S. Nikkhou Aski, M. Edén, J. Kowalewski, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Proton, 010405 organic chemistry, Chemistry, Relaxation (NMR), Carbon-13 NMR, 010402 general chemistry, 01 natural sciences, Cryptophane, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Dipole, General Energy, Computational chemistry, Magic angle spinning, Molecule, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Dichloromethane
Abstract

Cryptophanes are molecular hosts having high binding affinities for small, neutral molecules in weakly polar solvents. We have previously studied dichloromethane as a guest inside the cavity of cryptophane-E (cryptophane-333), in solution as well as in the solid state. Here, we present a solution 13C relaxation study of dichloromethane as the guest molecule complexed in the cavity of two smaller hosts: cryptophane-A (cryptophane-222) and cryptophane-223. 13C relaxation measurements were performed for both guest and host molecules. Exchange kinetics have to be explicitly taken into consideration in order to derive 13C relaxation properties of the bound guest. Rate coefficients were measured using proton 1D-exchange experiments. We have also investigated dichloromethane complexed in the cavity of cryptophane-233 in the solid state, by estimating the motionally averaged 13C−1H dipolar interactions from recoupling experiments under magic angle spinning (MAS) conditions. The measurements for the three cryptoph...

Published
2008
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44. Synthesis and chiroptical properties of cryptophanes having C1-symmetry

Author

Dominique Cavagnat, Thierry Brotin, Thierry Buffeteau, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, Circular dichroism, Macrocyclic Compounds, Stereochemistry, Macromolecular Substances, Molecular Conformation, 010402 general chemistry, 01 natural sciences, Vibration, Cryptophane, Computational chemistry, Polycyclic Compounds, Spectroscopy, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, Circular Dichroism, Organic Chemistry, Absolute configuration, Stereoisomerism, Triazoles, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Models, Chemical, Vibrational circular dichroism, Solvent effects, Cotton effect
Abstract

New enantiopure cryptophanes 3-7 having C(1)-symmetry have been synthesized. Electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) have been used to investigate their chiroptical properties, and the results are compared to those obtained for cryptophane-A (1) having D(3)-symmetry. The ECD spectra of compounds 3-7 show Cotton effects that differ from those of cryptophane-A. However, our results suggest that a confident determination of the absolute configuration of the monofunctionalized cryptophanes can be made using ECD spectroscopy. Interestingly, we have found that the ECD spectra of cryptophanes, especially the (1)L(b) transition, are very sensitive to the nature of the solvent. These spectral modifications are essentially due to bulk solvent properties rather than the ability of a particular solvent to insert into the cavity of cryptophanes. On the other hand, VCD spectra of the monofunctionalized cryptophanes have not revealed significant spectral modifications with respect to the VCD spectrum of the CHCl(3) at cryptophane-A complex, except for CHCl(3) at 7 and to a smaller extent for CHCl(3) at 6. These spectral modifications, which essentially consist in lower intensities of VCD bands associated with the cryptophane backbone, were perfectly reproduced by ab initio calculations performed at DFT (B3PW91/6-31G*) level. These results clearly demonstrate that VCD measurements associated with DFT calculations allow an easy determination of the absolute configuration of cryptophane-A derivatives.

Published
2007
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45. Water soluble cryptophanes showing unprecedented affinity for xenon: candidates as NMR-based biosensors

Author

Gaspard Huber, Thierry Brotin, Lionel Dubois, Patrick Berthault, Jean-Pierre Dutasta, Hervé Desvaux, Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Macrocyclic Compounds, Magnetic Resonance Spectroscopy, Xenon, Stereochemistry, chemistry.chemical_element, Biosensing Techniques, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Cryptophane, Molecular dynamics, Colloid and Surface Chemistry, Computational chemistry, Chemical affinity, Molecule, Aqueous solution, 010405 organic chemistry, Chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, Magnetic Resonance Imaging, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Proton NMR
Abstract

International audience; Cryptophanes bearing OCH2COOH groups in place of the methoxy groups represent a new class of xenon-carrier molecules soluble in water at biological pH. By using 1H and 129Xe NMR (thermally- and laser-polarized dissolved gas), the structural and dynamical behaviors of these host molecules as well as their interaction with xenon are studied. They are shown to exist in aqueous solution under different conformations in very slow exchange. A saddle form present for one of these conformations could explain the 1H NMR spectra. Whereas the cryptophanes in such a conformation are unable to complex xenon, unprecedented high binding constants are found for cryptophanes in the other canonical crown−crown conformation. These host molecules could therefore be valuable candidates for biosensing using 129Xe MRI.

Published
2006
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46. Optimization of Xenon Biosensors for Detection of Protein Interactions

Author

Jean-Pierre Dutasta, Sandra Garcia, Lana Chavez, E. Janette Ruiz, Alexander Pines, Peter G. Schultz, Tom Y.-H. Wu, David E. Wemmer, Thierry Brotin, Thomas J. Lowery, David S. King, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Models, Molecular, Analyte, Magnetic Resonance Spectroscopy, Xenon, Protein Conformation, Analytical chemistry, chemistry.chemical_element, Biosensing Techniques, 010402 general chemistry, Sensitivity and Specificity, 01 natural sciences, Biochemistry, Cryptophane, Structure-Activity Relationship, Isotopes of xenon, Molecule, [CHIM]Chemical Sciences, Biosensors Hyperpolarized Xenon Imaging Agents Nuclear Magnetic Resonance Avidin-biotin binding, Molecular Biology, ComputingMilieux_MISCELLANEOUS, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Life Sciences, Stereoisomerism, Nuclear magnetic resonance spectroscopy, Reference Standards, Avidin, Deuterium, 0104 chemical sciences, Xenon Isotopes, Molecular Medicine, Linker, Biosensor, Protein Binding
Abstract

Hyperpolarized 129Xe NMR spectroscopy can detect the presence of specific low-concentration biomolecular analytes by means of a xenon biosensor that consists of a water-soluble, targeted cryptophane-A cage that encapsulates the xenon. In this work, we use the prototypical biotinylated xenon biosensor to determine the relationship between the molecular composition of the xenon biosensor and the characteristics of protein-bound resonances. The effects of diastereomer overlap, dipole-dipole coupling, chemical-shift anisotropy, xenon exchange, and biosensor conformational exchange on the protein-bound biosensor signal were assessed. It was found that an optimal protein-bound biosensor signal can be obtained by minimizing the number of biosensor diastereomers and using a flexible linker of appropriate length. Both the line width and sensitivity of chemical shift to protein binding of the xenon biosensor were found to be inversely proportional to linker length.

Published
2006
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47. Vibrational circular dichroism study of optically pure cryptophane-A

Author

Thierry Buffeteau, Jean-Pierre Dutasta, Thierry Brotin, Dominique Cavagnat, Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Absolute configuration, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Spectral line, Cryptophane, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Colloid and Surface Chemistry, Computational chemistry, Alkane stereochemistry, Vibrational circular dichroism, Molecule, Density functional theory, Enantiomer
Abstract

Vibrational circular dichroism (VCD) measurements and density functional theory (DFT) calculations were used to obtain the absolute configuration of optically pure cryptophane-A molecule. This large molecule (120 atoms) that possess a globular shape, but no chiral centers, exceeds the molecular size of published structures for which VCD has been used to determine the absolute configuration. VCD spectra recorded in CDCl(3) solution for the two resolved enantiomers are near mirror images, and very good agreement between the observed IR and VCD spectra and intensity calculations performed at the DFT (B3PW91/6-31G) level establish, besides the absolute configuration, the preferential anti conformation of the aliphatic linkers of the chloroform-cryptophane-A complex. Experiments performed in CD(2)Cl(2) and C(2)D(2)Cl(4) solutions show no significant modifications in the IR and VCD spectra, indicating that the conformation of the aliphatic linkers is similar for empty (C(2)D(2)Cl(4) solution) and encaged (CDCl(3) and CD(2)Cl(2) solutions) cryptophane-A molecules.

Published
2006
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48. Improved Synthesis of Functional CTVs and Cryptophanes Using Sc(OTf) 3 as Catalyst

Author

Jean-Pierre Dutasta, Vincent Roy, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Cyclotriveratrylene, 010402 general chemistry, 01 natural sciences, Chemical synthesis, Cryptophane, 0104 chemical sciences, 3. Good health, Catalysis, Inclusion compound, chemistry.chemical_compound, chemistry, Organic chemistry, [CHIM]Chemical Sciences, Scandium, Trifluoromethanesulfonate, ComputingMilieux_MISCELLANEOUS
Abstract

Functional cyclotriveratrylene (CTV) and cryptophane derivatives are synthesized in the presence of scandium triflate [Sc(OTf)3]. This route allows the preparation of new derivatives that could not be prepared or easily obtained by using the previously reported experimental procedures. With a catalytic amount of scandium triflate (1% mol), CTVs were obtained with yields similar to or higher than those reported previously in reactions run under strong acidic conditions. Cryptophanes were also synthesized in fairly good yields by performing the ring-closure step in the presence of a stoichiometric amount of Sc(OTf)3. Interestingly, this novel approach strongly reduces the formation of side products and gives rise to novel functionalized molecules for the construction of supramolecular host-guest systems.

Published
2005
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49. Raman Microspectrometry as a New Approach to the Investigation of Molecular Recognition in Solids: Chloroform−Cryptophane Complexes

Author

Thierry Brotin, Alain Thozet, François Guillaume, Monique Perrin, Dominique Cavagnat, Jean-Luc Bruneel, Jean-Pierre Dutasta, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Laboratoire de Physico-Chimie Moléculaire (LPCM), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Reconnaissance et Organisation Moléculaire et Biomoléculaire, Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
host-guest interactions, Cyclotriveratrylene, 010402 general chemistry, 01 natural sciences, Spectral line, Cryptophane, chemistry.chemical_compound, symbols.namesake, Raman microspectrometry, Molecular recognition, Ab initio quantum chemistry methods, Computational chemistry, Materials Chemistry, Molecule, [CHIM]Chemical Sciences, cryptophane, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Chloroform, 010405 organic chemistry, ab initio calculations, 0104 chemical sciences, Surfaces, Coatings and Films, Crystallography, chemistry, symbols, Raman spectroscopy
Abstract

Information about the orientation and dynamics of a chloroform molecule encaged in cryptophane-A and cryptophane-E is obtained by means of Raman microspectrometry. The microscopy technique allows us to study the two observed crystalline structures of the CDCl 3 -cryptophane-A complexes separately. The spectra, recorded under different polarization conditions, are compared with those of CHCl 3 -D 3 0 -cryptophane-A and analyzed in light of the crystalline structures determined by X-ray diffraction. The spectral analysis is improved by ab initio calculations performed for the isolated guest and host molecules. The orientation of the encaged chloroform with the C-H bond pointing toward the center of the cyclotriveratrylene structures is confirmed. The vCD (or vCH) stretching wavenumber of chloroform is red shifted upon complexation as compared to the wavenumber of the gaseous isolated state. This red shift, larger for the CDCl 3 -cryptophane-E complex than for the CDCl 3 -cryptophane-A complex, is the signature of stronger binding host-guest interactions with cryptophane-E. In addition, the analysis of the band shape of the vCD stretching vibration of chloroform suggests different rotational dynamics for the guest molecule encaged in cryptophane-A or in cryptophane-E. This work illustrates the capability of the Raman microspectrometry technique to investigate molecular recognition phenomena in solids.

Published
2004
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50. Synthesis and application of cryptophanol hosts: 129Xe NMR spectroscopy of a deuterium-labeled (Xe)2@bis-cryptophane complex

Author

Denis Bouchu, Magali Darzac, Laurence Rousset-Arzel, Jean-Pierre Dutasta, Thierry Brotin, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Supramolecular chemistry, Analytical chemistry, chemistry.chemical_element, General Chemistry, Activation energy, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Catalysis, Cryptophane, 0104 chemical sciences, Xenon, Materials Chemistry, Physical chemistry, [CHIM]Chemical Sciences, Deuterium labeled, ComputingMilieux_MISCELLANEOUS
Abstract

The new bis-cryptophanes 7–9 were prepared from cryptophanols 1–3 and illustrate the synthetic possibilities offered by the latter for the design of new host systems featuring the preparation of large supramolecular receptors and new polycryptophane bio-sensors for NMR imaging. Hosts 1–3 were obtained from the monoprotected cryptophanes 4–6 following a multi-step strategy. The complexation of xenon by the dissymmetrical bis-cryptophane 8 was studied by 129Xe NMR spectroscopy. At low temperature, a strong discrimination (Δδ = 1.16 ppm) of the encapsulated xenon guests inside the two cryptophane cavities was observed. The kinetic parameters for the complexation process were determined from 1D-EXSY 129Xe NMR experiments. The activation energy Ea = 39.0 ± 3 kJ mol−1 and associated parameters ΔH≠ = 37.0 ± 3 kJ mol−1 and ΔS≠ = −46.0 ± 10 kJ mol−1 K−1 are in agreement with the values determined for cryptophane-A and [D27]-cryptophane-A.

Published
2004
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