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1. Synthesis and Chiroptical Properties of a Chiral Isotopologue of syn-Cryptophane-B

Author: Thierry Brotin, Nicolas Daugey, Josef Kapitan, Nicolas Vanthuyne, Marion Jean, Erwann Jeanneau, and Thierry Buffeteau
Subjects: Organic Chemistry
Published: 2023
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2. Subtle Stereochemical Effects Influence Binding and Purification Abilities of an FeII4L4 Cage

Author: Weichao Xue, Luca Pesce, Adinarayana Bellamkonda, Tanya K. Ronson, Kai Wu, Dawei Zhang, Nicolas Vanthuyne, Thierry Brotin, Alexandre Martinez, Giovanni M. Pavan, and Jonathan R. Nitschke
Subjects: Colloid and Surface Chemistry, General Chemistry, Biochemistry, Catalysis
Published: 2023
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3. Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

Author: Thierry Brotin, Patrick Berthault, Kévin Chighine, and Erwann Jeanneau
Subjects: General Chemical Engineering, General Chemistry
Published: 2022
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4. Allosterically Regulated Guest Binding Determines Framework Symmetry for an Fe II 4 L 4 Cage

Author: Weichao Xue, Kai Wu, Nianfeng Ouyang, Thierry Brotin, and Jonathan R. Nitschke
Subjects: General Medicine, General Chemistry, Catalysis
Published: 2023
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5. syn-Cryptophanes: macrocyclic compounds with optimized characteristics for the design of 129Xe NMR-based biosensors

Author: Estelle Léonce, Thierry Brotin, and Patrick Berthault
Subjects: General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract: A new water-soluble syn-cryptophane shows remarkable xenon binding properties and thereby constitutes an essential platform for 129Xe NMR-based biosensors.
Published: 2022
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6. Impact of the

Author: Thierry, Brotin, Patrick, Berthault, Kévin, Chighine, and Erwann, Jeanneau
Abstract: We report in this article the synthesis, the X-ray crystal structure of compound
Published: 2022

7. Access to the Syn diastereomers of cryptophane cages using HFIP

Author: Oriane Della-Negra, Yoann Cirillo, Thierry Brotin, Jean-Pierre Dutasta, Pierre-Loic Saaidi, Bastien Chatelet, Alexandre Martinez, 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), 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), Génomique métabolique (UMR 8030), Genoscope - Centre national de séquençage [Evry] (GENOSCOPE), 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)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: The use of the HFIP/bisulfate salt combination provides convenient and fast access to syn-cryptophanes.
Published: 2022
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8. Etude de xénon-cryptophane complexes syn et ani portant des groupements amines. plateformes chimiques pour accéder à de nouveaux cryptopahnes

Author: Martin Doll, Patrick Berthault, Estelle Léonce, Céline Boutin, Erwann Jeanneau, Thierry Brotin, Nicolas De Rycke, 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), Centre de diffractométrie Henri Longchambon, Institut de Chimie de Lyon, Université de Lyon-Université de Lyon-École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon
Subjects: Organic Chemistry, [CHIM]Chemical Sciences, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract: International audience; We report the synthesis of C3-symmetric cryptophanes decorated with three aromatic amine groups on the same CTB cap and their interaction with xenon. The relative stereochemistry of these two stereoisomers syn and anti was assessed thanks to the determination of the X-ray structure of an intermediate compound. As previously observed with the tris-aza-cryptophanes analogs anti-1 and syn-2 (J. Org. Chem. 2021, 86, 11, 7648–7658), both compounds anti-5 and syn-6 show a slow in–out exchange dynamics of xenon at 11.7 T. Our work supports the idea that the presence of nitrogen atoms grafted directly onto the cryptophane backbone has a strong impact on the in–out exchange dynamics of xenon whatever their stereochemistry. This result contrasts with the case of other cryptophanes decorated solely with methoxy substituents. Finally, we demonstrate that these new derivatives can be used to design new anti/syn cryptophanes bearing suitable ligands in order to constitute potent 129Xe NMR-based sensors. An example is reported here with the synthesis of the tris-iodo derivatives anti-13 and syn-14 from compounds anti-5 and syn-6.
Published: 2022
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9. Access to the

Author: Oriane, Della-Negra, Yoann, Cirillo, Thierry, Brotin, Jean-Pierre, Dutasta, Pierre-Loic, Saaidi, Bastien, Chatelet, and Alexandre, Martinez
Abstract: Cryptophane cages can adopt either an
Published: 2022

10. Study of

Author: Martin, Doll, Patrick, Berthault, Estelle, Léonce, Céline, Boutin, Erwann, Jeanneau, Thierry, Brotin, and Nicolas, De Rycke
Subjects: Magnetic Resonance Spectroscopy, Xenon, Stereoisomerism, Amines, Magnetic Resonance Imaging
Abstract: We report the synthesis of
Published: 2022

11. Chiroptical and Potential In Vitro Anti-Inflammatory Properties of Viniferin Stereoisomers from Grapevine (Vitis vinifera L)

Author: Guillaume Buffeteau, Ruth Hornedo-Ortega, Julien Gabaston, Nicolas Daugey, Antonio Palos-Pinto, Anne Thienpont, Thierry Brotin, Jean-Michel Mérillon, Thierry Buffeteau, Pierre Waffo-Teguo, Unité de Recherche Œnologie [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), 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), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Anti-Inflammatory Agents, chirality, Stereoisomerism, Wine, General Medicine, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Analytical Chemistry, stilbene, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Stilbenes, stereoisomers, Vitis, vine, viniferins, Food Science, anti-inflammatory
Abstract: International audience; Determination of stereochemistry and enantiomeric excess in chiral natural molecules is a research of great interest because enantiomers can exhibit different biological activities. Viniferin stilbene dimers are natural molecules present in grape berries and wine but also, in larger amount, in stalks of grapevine. Four stereoisomers of viniferin stilbene dimers (7aS,8aS)-E-ε-viniferin (1a), (7aR,8aR)-E-ε-viniferin (1b), (7aS,8aR)-Eε-viniferin (2a), and (7aR,8aS)-E-ω-viniferin (2b) were isolated from grapevine stalks of Cabernet Sauvignon, Merlot and Sauvignon Blanc, using a combination of centrifugal partition chromatography (CPC), preparative and chiral HPLC. The structure elucidation of these molecules was achieved by NMR whereas the absolute configurations of the four stereoisomers were investigated by vibrational circular dichroism spectroscopy in combination with density functional theory (DFT) calculations. This study unambiguously established the (+)-(7aS,8aS) and (+)-(7aR,8aS) configurations for E-ε-viniferin and E-ω-viniferin, respectively. Finally, we show that Cabernet Sauvignon provided the quasi enantiopure (+)-(7aS,8aS)-E-εviniferin compound which presents the best anti-inflammatory and anti-oxidant activities.
Published: 2022
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12. 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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13. 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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14. Are the Physical Properties of Xe@Cryptophane Complexes Easily Predictable? The Case of

Author: Martin, Doll, Patrick, Berthault, Estelle, Léonce, Céline, Boutin, Thierry, Buffeteau, Nicolas, Daugey, Nicolas, Vanthuyne, Marion, Jean, Thierry, Brotin, and Nicolas, De Rycke
Abstract: We report the synthesis and optical resolution of
Published: 2021

15. 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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16. 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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17. 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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18. 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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19. 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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20. 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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21. 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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22. 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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23. Enantiopure [Cs

Author: Dawei, Zhang, Tanya K, Ronson, Jake L, Greenfield, Thierry, Brotin, Patrick, Berthault, Estelle, Léonce, Jun-Long, Zhu, Lin, Xu, and Jonathan R, Nitschke
Abstract: Hierarchically nested hosts offer new opportunities to control the guest binding of the inner host, functionalize the cavity of the outer host, and investigate communication between different layers. Here we report a self-assembled triazatruxene-based Fe
Published: 2019

24. 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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25. 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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26. Bimodal Detection of Proteins by

Author: Emilie, Mari, Yasmina, Bousmah, Céline, Boutin, Estelle, Léonce, Gaelle, Milanole, Thierry, Brotin, Patrick, Berthault, and Marie, Erard
Subjects: Luminescent Proteins, Magnetic Resonance Spectroscopy, Spectrometry, Fluorescence, Xenon, Organometallic Compounds, Biosensing Techniques, Cysteine
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
Published: 2018

27. 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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28. 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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29. Accurate pH Sensing using Hyperpolarized

Author: Estelle, Léonce, Jean-Pierre, Dognon, Delphine, Pitrat, Jean-Christophe, Mulatier, Thierry, Brotin, and Patrick, Berthault
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
Published: 2018

30. 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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31. 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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32. Bimodal fluorescence

Author: Gaëlle, Milanole, Bo, Gao, Audrey, Paoletti, Grégory, Pieters, Christophe, Dugave, Eric, Deutsch, Sofia, Rivera, Frédéric, Law, Jean-Luc, Perfettini, Emilie, Mari, Estelle, Léonce, Céline, Boutin, Patrick, Berthault, Hervé, Volland, François, Fenaille, Thierry, Brotin, and Bernard, Rousseau
Subjects: Lung Neoplasms, Magnetic Resonance Spectroscopy, Dose-Response Relationship, Drug, Molecular Structure, Cell Survival, Antineoplastic Agents, Fluorescence, Molecular Imaging, ErbB Receptors, Structure-Activity Relationship, Carcinoma, Non-Small-Cell Lung, Tumor Cells, Cultured, Humans, Xenon Isotopes, Drug Screening Assays, Antitumor, Protein Kinase Inhibitors, Fluorescent Dyes
Abstract: 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/
Published: 2017

33. 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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34. Role of the Methoxy Groups in Cryptophanes for Complexation of Xenon: Conformational Selection Evidence from

Author: Patrick, Berthault, Céline, Boutin, Estelle, Léonce, Erwann, Jeanneau, and Thierry, Brotin
Abstract: We report the laser-polarized
Published: 2017

35. Experimental Measure of Solvation Energy from Model Cryptophane-Rubidium Binding Reaction

Author: Dominic V. Ngo, Daryl K. Eggers, Sherry Fu, Elizabeth H. Vuomg, and Thierry Brotin
Subjects: chemistry, Chemical physics, Biophysics, Solvation, Measure (physics), chemistry.chemical_element, Cryptophane, Rubidium
Published: 2020
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36. 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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37. Tetraarylcyclobutadienecyclopentadienylcobalt Complexes: Synthesis, Electronic Spectra, Magnetic Circular Dichroism, Linear Dichroism, and TD DFT Calculations

Author: Thierry Brotin, Gregg Kottas, Kamal Gala, John R. Miller, Zdeněk Havlas, Peter F. H. Schwab, James P. Kirby, and Josef Michl
Subjects: Circular dichroism, Absorption spectroscopy, Chemistry, Magnetic circular dichroism, Organic Chemistry, Analytical chemistry, Linear dichroism, Spectral line, Inorganic Chemistry, Crystallography, X-ray magnetic circular dichroism, Vibrational circular dichroism, Density functional theory, Physical and Theoretical Chemistry
Abstract: The known (tetraphenyl-η4-cyclobutadiene)-η5-cyclopentadienylcobalt (1) and a series of its new substituted derivatives have been prepared. The electronic states of a few representatives have been characterized by absorption and magnetic circular dichroism. Time-dependent density functional theory has been used to arrive at spectral assignments for several prominent low-energy bands. The absorption spectra of the radical ions of 1 have also been recorded.
Published: 2014
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38. Cover Feature: Bimodal Detection of Proteins by 129 Xe NMR and Fluorescence Spectroscopy (ChemBioChem 11/2019)

Author: Thierry Brotin, Marie Erard, Emilie Mari, Yasmina Bousmah, Céline Boutin, Patrick Berthault, Gaëlle Milanole, and Estelle Léonce
Subjects: Materials science, Organic Chemistry, Analytical chemistry, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Biochemistry, Fluorescence, Fluorescence spectroscopy, Xenon, chemistry, Feature (computer vision), Molecular Medicine, Cover (algebra), Molecular Biology, Biosensor
Published: 2019
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39. NMR Investigation of Chloromethane Complexes of Cryptophane-A and Its Analogue with Butoxy Groups

Author: Thierry Brotin, Emelie Steiner, Josef Kowalewski, Zoltan Takacs, 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: Chloroform, Chloromethane, Carbon-13 NMR, Spectral line, Cryptophane, Article, 3. Good health, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Materials Chemistry, Physical chemistry, Physical and Theoretical Chemistry, Spectroscopy, Two-dimensional nuclear magnetic resonance spectroscopy, ComputingMilieux_MISCELLANEOUS, Dichloromethane
Abstract: Host-guest complexes between cryptophane-A as host and dichloromethane and chloroform as guests are investigated using (1)H and (13)C NMR spectroscopy. Moreover, a related cryptophane, with the methoxy groups replaced by butoxy units (cryptophane-But), and its complexes with the same guests were also studied. Variable temperature spectra showed effects of chemical exchange between the free and bound guests, as well as of conformational exchange of the host. The guest exchange was studied quantitatively by exchange spectroscopy or line shape analysis. Extraction of kinetic and thermodynamic parameters led to the characterization of the affinity between guests and hosts. On the other hand, the host exchange was investigated by means of (13)C Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion which aims at the determination of the transverse relaxation rate R2, the inverse of the transverse relaxation time T2, as a function of the repetition of the π pulses in a CPMG train. The variation of the measured transverse relaxation rate with the repetition rate νCPMG indicated conformational exchange occurring on the microsecond-millisecond time scale. Structural information was obtained through measurements of cross-relaxation rates, both within the host and between the host and the guest protons. The NMR results were supported by DFT calculations.
Published: 2014
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40. 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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41. 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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42. 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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43. 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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44. 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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45. High Affinity of Water-Soluble Cryptophanes for Cesium Cations

Author: Aude Bouchet, Thierry Buffeteau, Dominique Cavagnat, Roland Montserret, Thierry Brotin, and Mathieu Linares
Subjects: Magnetic Resonance Spectroscopy, Aqueous solution, Circular Dichroism, Organic Chemistry, Inorganic chemistry, Cesium, Water, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Calorimetry, Rubidium, Chemistry Techniques, Analytical, Cryptophane, Solutions, Enantiopure drug, Water soluble, Solubility, chemistry, Cations, Caesium, Organic chemistry, Polycyclic Compounds
Abstract: Exceptionally high affinity for cesium cations was achieved in aqueous solution using two enantiopure cryptophanes. Complexation of cesium was evidenced by (133)Cs NMR spectroscopy and by electronic circular dichroism (ECD). Binding constants as high as 6 × 10(9) M(-1) have been measured by isothermal titration calorimetry (ITC). Very strong complexation of rubidium cations (K ~10(6) M(-1)) has also been measured. Chiral hosts allowed the detection of the two cations at low concentrations (μM) using ECD.
Published: 2012
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46. 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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47. 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

48. Enantiodifferentiation of polyethers by the dirhodium method. Part 2: Cyclotriveratrylenes and cryptophanes

Author: Edison Díaz Gómez, Helmut Duddeck, and Thierry Brotin
Subjects: chemistry.chemical_classification, Olefin fiber, Sulfide, Organic Chemistry, Catalysis, Cryptophane, Inorganic Chemistry, chemistry.chemical_compound, 13c nmr spectroscopy, chemistry, Standard protocol, Phenol, Organic chemistry, Physical and Theoretical Chemistry, Enantiomer
Abstract: Cycloveratrylenes and cryptophanes 1–12 are chiral compounds and were studied in their racemic form. Although most of them are non-polar oligocyclic ethers, their enantiomers can be easily differentiated by 1H and 13C NMR spectroscopy in the presence of an equimolar amount of Rh2[(R)-(+)-MTPA]4 (the standard protocol for the dirhodium method). Coordination mechanisms were studied. Various functionalities (sulfide, various ethers, olefin and phenol) were also sequenced according to their donor properties.
Published: 2007
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49. Vibrational Absorption and Circular Dichroism Studies of (−)-Camphanic Acid

Author: and Aude Bouchet, Dominique Cavagnat, Thierry Buffeteau, and Thierry Brotin
Subjects: Bridged-Ring Compounds, education.field_of_study, Circular dichroism, Circular Dichroism, Dimer, Population, Intermolecular force, Molecular Conformation, Hydrogen Bonding, Stereoisomerism, Photochemistry, Sensitivity and Specificity, Vibration, Lactones, chemistry.chemical_compound, Crystallography, Monomer, chemistry, Spectroscopy, Fourier Transform Infrared, Density functional theory, Physical and Theoretical Chemistry, Absorption (chemistry), education, Conformational isomerism
Abstract: Vibrational absorption and circular dichroism (VCD) spectra of (-)-(1S,3R)-camphanic acid have been measured in deuterated chloroform solutions at different concentrations (0.005, 0.045, and 0.200 M) in the mid-infrared spectral range. Experimental spectra have been compared with the density functional theory (DFT) absorption and VCD spectra, calculated using the B3PW91 functional and cc-pVTZ basis set for three conformers of both the monomer and the dimer forms of (-)-(1S,3R)-camphanic acid. These calculations indicate that, in the dilute solution, the conformer with intramolecular hydrogen-bonding between the hydroxyl and lactone groups is of lowest energy and represents 70% of the different monomer conformers at room temperature, whereas, in concentrated solution, the dimer formed by intermolecular hydrogen-bonding of carboxyl groups of the two distinct monomer conformations is stabilized. The vibrational absorption and circular dichroism spectra calculated from the Boltzmann population of the individual monomer and dimer conformers are in very good overall agreement with the corresponding experimental spectra, allowing the absolute conformation and configuration of (-)-(1S,3R)-camphanic acid in dilute and concentrated solution, respectively. Experiments were also performed on (-)-(1S,3R)-camphanic chloride for which the populations predicted by DFT calculations are found to be in disagreement with those deduced from experimental spectra.
Published: 2007
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50. Chiroptical Properties of Nona and Dodecamethoxy Cryptophanes

Author: Laurent Ducasse, Dominique Cavagnat, Thierry Buffeteau, Thierry Brotin, 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 (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)-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), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-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 Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Circular dichroism, Chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Absolute configuration, Aromaticity, Time-dependent density functional theory, Cryptophane, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Vibrational circular dichroism, Density functional theory, Ethylenedioxy, ComputingMilieux_MISCELLANEOUS
Abstract: Enantiopure cryptophane derivatives bearing nine (2, 3) and 12 (4) methoxy substituents attached on the six aromatic rings were separated by HPLC using chiral stationary phases. The chiroptical properties of compounds 2-4 were determined from polarimetry, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD) experiments and were compared to those of cryptophane-A (1) derivative. ECD spectra of 1 and 4 were calculated by time-dependent density functional theory (TDDFT) to determine the absolute configuration (AC) of cryptophane derivatives. The (+)-PP absolute configuration was thus established for the anti-cryptophane-A (1) and its congeners 2 and 4. VCD experiments associated with DFT calculations confirmed the (+)-PP configuration of anti-compounds 2 and 4 and established the (+)-PM configuration of the syn-3 compound as well. This study revealed the preferential all-trans (TTT) conformation of the three ethylenedioxy linkers for the CHCl3@1, CHCl3@3, and CHCl3@4 complexes, whereas the GTT conformation was found the most favorable for the CHCl3@2 complex.
Published: 2015
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