<i>syn</i>-Cryptophanes: macrocyclic compounds with optimized characteristics for the design of <sup>129</sup>Xe NMR-based biosensors

Léonce, Estelle; Berthault, Patrick

doi:10.1039/d2cp03714a

Cited by 8 publications

(12 citation statements)

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“…This compound can be recrystallized from a hot acetone solution. Compound syn-2 was fully characterized by 1 H and 13 C NMR spectroscopy and HRMS. The 1 H NMR spectrum (3.0−9.0 ppm; DMSO-d 6 ) of 2 is shown Figure 1 and compared to the known hexa-phenol derivative anti-1.…”

Section: ■ Resultsmentioning

confidence: 99%

“…The two spectra look very similar, with the exception of the diastereotopic protons of compound syn-2, which appear as two sets of signals instead of one for its congener. 1 H and 13 C NMR spectra of compound syn-2 are reported in Figures S1 and S2.…”

Section: ■ Resultsmentioning

confidence: 99%

“…The intermediate syn - 3 appears to be a useful derivative to prepare a wide range of C 3 -symmetric derivatives with the syn configuration due to the presence of three unprotected phenol groups and three other protected phenol functions that allow us to easily modify its structure. For example, recent studies have suggested that cryptophanes with the syn configuration possess superior characteristics for the design of 129 Xe NMR-based biosensors compared to their anti -congeners . Therefore, the interest for the syn -compounds should rapidly grow in the future.…”

Section: Discussionmentioning

confidence: 99%

“…For example, recent studies have suggested that cryptophanes with the syn configuration possess superior characteristics for the design of 129 Xe NMR-based biosensors compared to their anti -congeners. 13 Therefore, the interest for the syn -compounds should rapidly grow in the future. Interestingly, compound syn - 3 allows us to give access to the syn - 2 derivative in good yield and in a single step.…”

Section: Discussionmentioning

confidence: 99%

“…Before each acquisition batch, external of the instrument was performed with a sodium formate clusters solution. 1 H and13 C NMR spectra were recorded at 300 and 75.5 MHz, respectively. Chemical shifts were referenced to Me 4 Si ( 1 H and 13 C).…”

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confidence: 99%

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Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

2022

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We report in this article the synthesis, the X-ray crystal structure of compound syn-2, and its binding properties with cesium and thallium in aqueous solution under basic conditions. Compound syn-2 is the diastereomeric compound of anti-1 that shows very high affinity for cesium and thallium in aqueous solution under the same conditions. Despite the close structural similarities that exist between the syn-2 and anti-1 compounds, they show large discrepancy in their ability to bind cesium and thallium cations in the same conditions. Indeed, the syn-2 derivative has a lower affinity for these two cationic species and the binding constants are several orders of magnitude lower than those found for its congener. The large differences in affinity observed with these two compounds can be explained by the relative position of the six hydroxyl groups to each other.

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Section: ■ Resultsmentioning

confidence: 99%

Section: ■ Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

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Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

2022

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Isomer‐Dependent Escape Rate of Xenon from a Water‐Soluble Cryptophane Cage Studied by Ab Initio Molecular Dynamics

Pollet,

Dognon,

Berthault

2023

ChemPhysChem

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The escape of xenon from the anti and syn diastereomers of hexacarboxylic‐cryptophane‐222 in water has been studied by ab initio molecular dynamics simulations. The structures of both complexes, when the xenon atom is trapped inside their cages, have been compared and show no major differences. In addition, the free‐energy profiles corresponding to the escape reaction have been calculated with the Blue Moon ensemble method using the distance between Xe and the center of mass of the cage as the reaction coordinate. The resulting free‐energy barriers are very different; the escape rate is much faster in the case of the syn diastereomer, in agreement with experimental data obtained in hyperpolarized 129Xe NMR. Our simulations reveal the mechanistic details for each diastereomer and provide an explanation for the different in‐out xenon rates based on the solvation structure around the cages.

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Organoplatinum‐Bridged Cyclotribenzylene Dimers

et al. 2023

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Cyclotribenzylenes (CTBs) combining carbonitrile (−CN) and alkyne (−C2H) substituents were synthesized as racemic mixtures and resolved by HPLC on chiral stationary phases. Two of these compounds were used to prepare platinum‐bridged CTB dimers, in which PtII is bound to the CTBs via Pt−alkynyl bonds in cis configuration. The organometallic complexes were examined by mass spectrometry and NMR spectroscopy, which indicated that they were obtained as mixtures of diastereoisomers (a meso or syn form and a pair of chiral or anti forms) when racemic CTBs were used. Enantiomerically pure complexes were prepared from resolved CTBs, which allowed us to distinguish the NMR signals of the chiral and meso forms in the diastereoisomeric mixtures. In certain conditions, the platinum complexes played the role of a pincer π‐alkynyl ligand for Cu(I) coming from the copper iodide used as a synthetic auxiliary. The Cu+ cations could be easily removed by treatment with NaCN, affording the mononuclear bis‐cyclotribenzylene complexes. These compounds failed to lead to metallo‐cryptophanes by coordination of two [M(dppp)]2+ complex subunits (M=Pd, Pt; dppp=1,3‐bis(diphenylphosphino)propane), each to two carbonitrile substituents belonging to different CTBs, pointing to the superiority of the one pot self‐assembly processes for the preparation of metallo‐cryptophanes.

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

Abstract: A new water-soluble xenon host system with great promise for the 129Xe NMR-based biosensing approach is presented: the syn-cryptophane-222-hexacarboxylate. It compares favorably with its already known anti diastereomer, on the...

Cited by 8 publications

References 40 publications

Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

Isomer‐Dependent Escape Rate of Xenon from a Water‐Soluble Cryptophane Cage Studied by Ab Initio Molecular Dynamics

Organoplatinum‐Bridged Cyclotribenzylene Dimers

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

Abstract: A new water-soluble xenon host system with great promise for the 129Xe NMR-based biosensing approach is presented: the syn-cryptophane-222-hexacarboxylate. It compares favorably with its already known anti diastereomer, on the...

Cited by 8 publications

References 40 publications

Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

Impact of the Syn/Anti Relative Configuration of Cryptophane-222 on the Binding Affinity of Cesium and Thallium

Isomer‐Dependent Escape Rate of Xenon from a Water‐Soluble Cryptophane Cage Studied by Ab Initio Molecular Dynamics

Organoplatinum‐Bridged Cyclotribenzylene Dimers

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