Enantiopure [Cs+/Xe⊂Cryptophane]⊂FeII4L4 Hierarchical Superstructures.

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 FeII4L4 capsule, which was able to encapsulate a covalent cage, cryptophane-111 (CRY). The resulting cage-in-cage complex was capable of accommodating a cesium cation or xenon atom with altered guest binding behavior compared to the CRY alone. A crystal structure of the Russian doll complex [Cs+⊂CRY]⊂FeII4L4 unambiguously demonstrated the unusual encapsulation of a cation within a capsule bearing a 8+ charge. Moreover, the binding of enantiopure CRY occurred with high enantioselectivity (530-fold) between the two enantiomers of the tetrahedron. This discrimination resulted in stereochemical information transfer from the inner covalent cage to the outer self-assembled capsule, leading to the formation of enantiopure [guest⊂cage]⊂cage complexes. The stereochemistry of the tetrahedron persisted even after displacement of CRY with an achiral guest.European Research Council (695009), the UK Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1

A doubly responsive probe for the detection of Cys4-tagged proteins

International audienceRecombinant proteins bearing a tag are crucial tools for assessing protein location or function. Small tags such as Cys4 tag (tetracysteine; Cys–Cys–X–X–Cys–Cys) are less likely disrupt protein function in the living cell than green fluorescent protein. Herein we report the first example of the design and synthesis of a dual fluorescence and hyperpolarized 129Xe NMR-based sensor of Cys4-tagged proteins. This sensor becomes fluorescent when bound to such Cys4-tagged peptides, and the 129Xe NMR spectrum exhibits a specific signal, characteristic of the biosensor-peptide association

Conformational Changes in Cryptophane Having C 1 -Symmetry Studied by Vibrational Circular Dichroism

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Synthesis and Chiroptical Properties of Cryptophanes Having C 1 -Symmetry

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Cryptophanes

International audienceCryptophanes are organic molecular receptors known for their complexation properties toward neutral and cationic species in organic or aqueous media. Small halogenomethanes and alkanes, monoatomic xenon, as well as ammonium and metal cations are reversibly entrapped into the molecular cavity of the cryptophanes. Different synthetic routes have been developed to construct cryptophanes with peculiar functionalities that are key compounds for biological applications. Throughout this contribution, a brief survey of their structures and complexation properties are reviewed, that enlighten the possible applications of these organic hosts in molecular recognition, chiral recognition, and biosensing

Cryptophanes and Their Complexes—Present and Future

International audience1. Introduction 2. Syntheses of Cryptophanes 2.1. The “Direct (Two-Step) Method” 2.2. The “Template Method” 2.3. Coupling of CTVs 3. Syntheses of New Cryptophanes Using the Template Method 3.1. Deuterium Labeled Cryptophanes 3.2. Methylthio Containing Crytophanes 3.3. Amphipathic Cryptophanes 3.4. Syntheses of C2-Symmetrical Cryptophanes 4. Transformation and Functionalization of Cryptophanes 4.1. Water-Soluble Cryptophanes: Hexacarboxylic Acid Cryptophanes 4.2. Monofunctionalized Cryptophanes: Cryptophanol 4.3. Cryptophanes as Biosensors 4.4. Bis-cryptophanes 5. Structural Aspects and Characterization of Cryptophanes 5.1. Some Peculiarities in the Characterization of Cryptophane Hosts 5.2. Inverted and Imploded Cryptophanes 5.3. Molecular Structures of Cryptophane-A 1 and Related Ones 5.4. Some Aspects of Cryptophanes in the Crystalline State 6. Binding Properties of Cryptophanes 6.1. Complexation of Small Neutral Molecules 6.2. Complexation of Ammonium Guests 6.3. Complexation of Metal Cations 6.4. Complexation of Anion Guests 7. Dynamics of the Guest in the Cryptophane Cavity 7.1. Investigations by NMR Spectroscopy 7.2. Computational Investigations 7.3. Host−Guest Complexes in the Solid: Raman Microspectrometry 7.4. Studies in Mesophases 8. Chiral Discrimination 8.1. CHFClBr 8.2. CHFClI 9. Xenon in the Cryptophane Cavity 9.1. Xe@cryptophane Complexes 9.2. 129Xe NMR Spectroscopy of Xe@Cryptophane Complexes 9.3. Dynamics of Xenon Encapsulation 9.4. Laser-Polarized Xenon and Cryptophanes 9.4.1. Laser-Polarized Xenon in Cryptophane Complexes 9.4.2. Probing the Molecular Cavity of Cryptophane 9.4.3. “Functionalized” Xenon 10. Syntheses and Chiroptical Properties of Optically Pure Cryptophanes 10.1. Optical Resolution of CTVs and Cryptophanes 10.1.1. Optical Resolution Using Chiral HPLC 10.1.2. Resolution of CTVs 10.2. Syntheses of Optically Pure Cryptophanes 10.2.1. From Enantiopure CTVs 10.2.2. From Cryptophanol 10.3. Electronic Circular Dichroism (ECD) Spectra of Resolved Cryptophanes 10.3.1. ECD of CTVs 10.3.2. ECD of D3-Symmetrical Cryptophanes 10.3.3. ECD of C1-Symmetrical Cryptophanes 10.4. VCD of Cryptophane Hosts 11. Conclusion—The Future of Cryptophanes 12. Dedicatio

Induced Chiroptical Changes of a Water-Soluble Cryptophane by Encapsulation of Guest Molecules and Counterion Effects

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Synthesis of Highly Substituted Cryptophane Derivatives

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Syn-cryptophanes: macrocyclic compounds with optimized characteristics for the design of 129 Xe NMR-based biosensors

International audienceA new water-soluble xenon host system with great promise for the 129 Xe NMR-based biosensing approach is presented: the syn-cryptophane-222-hexacarboxylate. It compares favorably with its already known anti diastereomer, on the one hand, and with cucurbit[6]uril, on the other hand, in particular in terms of xenon binding constant and xenon in-out exchange, a key parameter for the efficiency of the most sensitive HyperCEST method