A Water-Soluble Xe@cryptophane-111 Complex Exhibits Very High Thermodynamic Stability and a Peculiar <sup>129</sup>Xe NMR Chemical Shift

Fairchild, Robert; Joseph, Akil I.; Holman, K. Travis; Fogarty, Heather A.; Brotin, Thierry; Dutasta, Jean‐Pierre; Boutin, Céline; Huber, Gaspard; Berthault, Patrick

doi:10.1021/ja1071515

Cited by 80 publications

(101 citation statements)

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“…The development of high-affinity Xe-binding cages is an area of active investigation and is critical to the burgeoning field of xenon biosensing (16,37,38). Synthetic host molecules designed to bind xenon in cells or in vivo must compete against a wide variety of biological substrates.…”

Section: Resultsmentioning

confidence: 99%

“…Recent X-ray crystallographic studies have shown that the internal volume of trisubstituted cryptophane-A derivatives can vary by more than 20%, depending on the size of the encapsulated guest (12). Several cryptophane-A derivatives have been synthesized and shown by isothermal titration calorimetry (ITC), fluorescence quenching, and NMR studies to exhibit xenon association constants as high as 33;000 AE 3;000 M −1 at 293 K in phosphate-buffered water (13)(14)(15)(16). Herein, we report a previously unsynthesized cryptophane-A derivative, tris-(triazole ethylamine) cryptophane (TTEC), with superior xenon-binding characteristics.…”

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confidence: 99%

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Measurement of radon and xenon binding to a cryptophane molecular host

Jacobson

Khan²,

Collé³

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Xenon and radon have many similar properties, a difference being that all 35 isotopes of radon ( 195 Rn– 229 Rn) are radioactive. Radon is a pervasive indoor air pollutant believed to cause significant incidence of lung cancer in many geographic regions, yet radon affinity for a discrete molecular species has never been determined. By comparison, the chemistry of xenon has been widely studied and applied in science and technology. Here, both noble gases were found to bind with exceptional affinity to tris-(triazole ethylamine) cryptophane, a previously unsynthesized water-soluble organic host molecule. The cryptophane–xenon association constant, K a = 42,000 ± 2,000 M -1 at 293 K, was determined by isothermal titration calorimetry. This value represents the highest measured xenon affinity for a host molecule. The partitioning of radon between air and aqueous cryptophane solutions of varying concentration was determined radiometrically to give the cryptophane–radon association constant K a = 49,000 ± 12,000 M -1 at 293 K.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Measurement of radon and xenon binding to a cryptophane molecular host

Jacobson

Khan²,

Collé³

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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“…12 Another strategy was the metalation of the six arene rings of cryptophane-111 by [Cp*Ru] + moieties leading to cryptophane salts which exhibit a very high water solubility at physiological pH and the highest xenon affinity ever reported. 10 More recently, a new cryptophane skeleton has been developed : cryptophane with two ethylenedioxy linkers and the third linker of the propylenedioxy type bearing a unique secondary alcohol. 13 A second solubilizing or functional group can therefore be selectively introduced, facilitating the synthesis of new molecular platforms with reduced risks of creation of diastereomers.…”

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confidence: 99%

“…An important concern can also be the ability of the biosensor to cross the cell membrane. Considering all these requirements, various host structures have been synthesized during the recent years: cryptophanes, 10 cucurbiturils, 14 cucurbituril-based rotaxanes, 15 pillararenes, 16 Fe 4 L 6 cages 14 (respectively 1 to 5 in Fig. 3 been conceived following two strategies.…”

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confidence: 99%

¹²⁹Xe NMR-based sensors: biological applications and recent methods

Mari

Berthault

2017

Analyst

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aXenon is a first-rate sensor of biological events, due to its large polarizable electron cloud inducing significant modification of NMR parameters through slight changes in its local environment. The use of xenon as a sensor is of increasing interest for sensitive magnetic resonance imaging, since its signal can be enhanced by several orders of magnitude, mainly by spinexchange optical pumping. Furthermore xenon can be vectorized toward targets of interest by using functionalized host systems, enabling their detection at subnanomolar concentrations. Associated with a new generation of detection methods this gives rise to a powerful molecular imaging approach, where xenon can be delivered on purpose several times after introduction of the functionalized host system. IntroductionFrom simple photograph of the inside of the human body providing information on bone structure or form and abnormalities of various organs, molecular imaging now offers a dynamic view of biological processes occurring locally, witnessing for instance the presence of infectious cells or metabolic deregulations. The development of powerful imaging techniques is the key to early diagnosis of disease, best follow-up treatments and also biomedical research tools. These techniques developed particularly in the 21th century form part of the molecular imaging concept. Magnetic resonance imaging (MRI) is a good compromise to achieve molecular imaging in vivo in real time without any perturbative radiation. The major advantages of MRI are its potential high spatial resolution (25-100 µm), its low invasiveness, its harmlessness and the excellent tissue contrast it can provide. In this context, MRI complements and sometimes overruns other molecular imaging approaches by enabling monitoring of events at the cellular or even subcellular level. However, classical implementation of this technique suffers from low sensitivity due to the very low population differences between nuclear spin energy levels at Boltzmann equilibrium. Hyperpolarization techniques 1 that transiently increase the nuclear spin polarization of a very dilute agent by several orders of magnitude circumvent the MRI sensitivity problem. Among the species that can be spinhyperpolarized, xenon is of high interest, due to its exogenous nature (leading to the absence of background signal) and the fact that it can act as a spy of biological events without interfering with them. Moreover, it can be endlessly reloaded and simply removed from the sample since it is a gas at ambient temperature and pressure. Finally, owing to the high deformability of its large electron cloud xenon is deeply sensitive to its local environment and constitutes a perfect probe for various biological interactions. Soluble in most biological fluids, xenon can cross the plasma membrane in a few tens of milliseconds without losing its hyperpolarization. 2The initial applications of hyperpolarized xenon in biology were the anatomical imaging of the lung 3 and the investigation of hydrophobic binding pockets in proteins ...

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“…Indeed, the boronic acid function is an electron-withdrawing group, whereas the phenol group is an electron-donating group. The cryptophane-111 structure was chosen, as 1) it displays the highest affinity for xenon both in organic solvents [10] and water, [11] 2) tiny chemical modifications on the aromatic rings are expected to strongly influence the chemical shift of caged xenon, and 3) since it is the smallest cryptophane representative, although far from simple, theoretical calculations should be more straightforward. Moreover, several boronic functionalities can be grafted on a cryptophane-111 core to form, after oxidation, different molecular cages.…”

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confidence: 99%

Understanding a Host–Guest Model System through ¹²⁹Xe NMR Spectroscopic Experiments and Theoretical Studies

Dubost¹,

Dognon²,

Rousseau³

et al. 2014

Angewandte Chemie

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Gaining an understanding of the nature of hostguest interactions in supramolecular complexes involving heavy atoms is a difficult task. Described herein is a robust simulation method applied to complexes between xenon and members of a cryptophane family. The calculated chemical shift of xenon caged in a H 2 O 2 probe, as modeled by quantum chemistry with complementary-orbital, topological, and energy-decomposition analyses, is in excellent agreement with that observed in hyperpolarized 129 Xe NMR spectra. This approach can be extended to other van der Waals complexes involving heavy atoms.

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

Cited by 80 publications

References 31 publications

Measurement of radon and xenon binding to a cryptophane molecular host

Measurement of radon and xenon binding to a cryptophane molecular host

¹²⁹Xe NMR-based sensors: biological applications and recent methods

Understanding a Host–Guest Model System through ¹²⁹Xe NMR Spectroscopic Experiments and Theoretical Studies

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

Cited by 80 publications

References 31 publications

Measurement of radon and xenon binding to a cryptophane molecular host

Measurement of radon and xenon binding to a cryptophane molecular host

129Xe NMR-based sensors: biological applications and recent methods

Understanding a Host–Guest Model System through 129Xe NMR Spectroscopic Experiments and Theoretical Studies

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

¹²⁹Xe NMR-based sensors: biological applications and recent methods

Understanding a Host–Guest Model System through ¹²⁹Xe NMR Spectroscopic Experiments and Theoretical Studies