Synthesis of Deuterium-Labeled Cryptophane-A and Investigation of Xe@Cryptophane Complexation Dynamics by 1D-EXSY NMR Experiments

Devic, Thomas; Lesage, Anne; Emsley, Lyndon; Collet, André

doi:10.1002/1521-3765(20010401)7:7<1561::aid-chem1561>3.3.co;2-0

Cited by 4 publications

(6 citation statements)

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“…To demonstrate this, Brotin et al studied the encapsulation of xenon in a series of deuterium-labeled cryptophanes-A. 50,121 Cryptophane-A (1) and one of its labeled analogues were mixed together with xenon, and 129 Xe NMR spectra were recorded. For example, when cryptophane-A-d 30 (81) was mixed with 1, at low temperature, two well-resolved resonances were observed at low frequency, corresponding to xenon encapsulated in the cavity of each cryptophane (Figure 37).…”

Section: Xe Nmr Spectroscopy Of Xe@cryptophane Complexesmentioning

confidence: 99%

“…Using 129 Figure 40). 50 From these experiments, it was possible to determine the whole set of kinetic constants and to conclude that the process involving the direct exchange of xenon by collision between cryptophanes was negligible and that the main mechanism involved the capture and the release of xenon from the solution and into it. Similar conclusions were obtained from 2D-EXSY experiments.…”

Section: Dynamics Of Xenon Encapsulationmentioning

confidence: 99%

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Cryptophanes and Their Complexes—Present and Future

2008

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Contents 98 4.2. Monofunctionalized Cryptophanes: Cryptophanol 98 4.3. Cryptophanes as Biosensors 99 4.4. Bis-cryptophanes 100 5. Structural Aspects and Characterization of Cryptophanes 100 5.1. Some Peculiarities in the Characterization of Cryptophane Hosts 101 5.2. Inverted and Imploded Cryptophanes 102 5.3. Molecular Structures of Cryptophane-A 1 and Related Ones 103 5.4. Some Aspects of Cryptophanes in the Crystalline State 104

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Section: Xe Nmr Spectroscopy Of Xe@cryptophane Complexesmentioning

confidence: 99%

Section: Dynamics Of Xenon Encapsulationmentioning

confidence: 99%

Cryptophanes and Their Complexes—Present and Future

2008

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“…The MAD-STEAM experiment can be viewed as an extension of a 2D exchange spectroscopy (EXSY) NMR experiment (18,32). The exchange spectroscopy experiment also uses a stimulated echo from three 90 pulses, in which the time between the first two 90 pulses, t 1 , is incremented to sample a entire 2D spectrum (18).…”

Section: The Mad-steam Experimentsmentioning

confidence: 99%

Quantitative measurement of cancer metabolism using stimulated echo hyperpolarized carbon‐13 MRS

Swisher

Larson

Kruttwig

et al. 2013

Magnetic Resonance in Med

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Purpose Magnetic resonance spectroscopy (MRS) of hyperpolarized substrates allows for the observation of label exchange catalyzed by enzymes providing a powerful tool to investigate tissue metabolism and potentially kinetics in vivo. However, the accuracy of current methods to calculate kinetic parameters have been limited by T1 relaxation effects, extracellular signal contributions, and reduced precision at lower SNR. Theory and Methods To address these challenges, we investigated a new modeling technique using Metabolic Activity Decomposition-Stimulated Echo Acquisition Mode (MAD-STEAM). The MAD-STEAM technique separates exchanging from non-exchanging metabolites providing twice the information as conventional techniques. Results This allowed for accurate measurements of rates of conversion and of multiple T1 values simultaneously using a single acquisition. Conclusion The additional measurement of T1 values for the reaction metabolites provides further biological information about the cellular environment of the metabolites. The new technique was investigated through simulations and in vivo studies of transgenic mouse models of cancer demonstrating improved assessments of kinetic rate constants and new T1 relaxation value measurements for hyperpolarized 13C-pyruvate, 13C-lactate and 13C -alanine.

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“…A roughly spherical cavity is left between the CTB caps in which guest atoms or molecules can reside. The affinity (free energy of Xe binding) between the Cr cage and Xe guest is experimentally measured to be 4–9 kcal/mol, − depending on the temperature and particular choice of the Cr cage and solvent. For comparison, computational values of 4–21 kcal/mol have been reported. − Crs have six substitution sites, R 1 –R 6 in Figure , that can be furnished with, e.g., targeting antennas or water-solubility enhancing moieties, with the latter needed particularly in biomedical use of XBSs.…”

Section: Introductionmentioning

confidence: 99%

Water Molecules Confined in Cryptophane Nanocages: Structures and Dynamics Driven by Hydrogen Bonding and Water Chains

Hilla,

Vaara

2024

J. Phys. Chem. B

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Cryptophanes (Crs) are roughly spherical organic nanocages used as vehicles for hosting xenon atoms in 129 Xe NMR biosensor (XBS) structures. Crs also bind other guests, importantly water, which is abundant in biological systems. In other host cages, it has been found that the release of "high-energy" water from confinement constitutes an important contribution to the binding affinity of nonwater guests. Despite that, the role of water has received little attention in the XBS field. Based on molecular dynamics simulations in explicit water solvent, we here study the properties of confined water in three different CrA cages that have an identical interior but are functionalized with 0, 3, or 6 water solubility-enhancing, hydrophilic CH 2 COOH moieties. The number of the solubility groups is found to be a decisive factor for the structures and dynamics of the confined water. Formation of stable water-molecule chains is predicted within the cage with six hydrophilic groups, starting with the anchoring of one water molecule at the portal between the cage and the bulk solution. We find that the experimentally measured differences in the Xe-binding affinities of the cages can be related to the average number of hydrogen bonds per confined water molecule. The rotational dynamics of the confined water is significantly slower than that in the bulk, suggesting NMR relaxation measurements to study the intracavity water. The present findings reveal new details about the microscopic cryptophane−H 2 O host−guest chemistry, which will become important in the design of improved XBS devices.

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Synthesis of Deuterium-Labeled Cryptophane-A and Investigation of Xe@Cryptophane Complexation Dynamics by 1D-EXSY NMR Experiments

Cited by 4 publications

References 4 publications

Cryptophanes and Their Complexes—Present and Future

Cryptophanes and Their Complexes—Present and Future

Quantitative measurement of cancer metabolism using stimulated echo hyperpolarized carbon‐13 MRS

Water Molecules Confined in Cryptophane Nanocages: Structures and Dynamics Driven by Hydrogen Bonding and Water Chains

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