A Designed Cavity for Zwitterionic Species: Selective Recognition of Taurine in Aqueous Media

Perraud, Olivier; Robert, Vincent; Martinez, Alexandre; Dutasta, Jean‐Pierre

doi:10.1002/chem.201101522

Cited by 40 publications

(32 citation statements)

References 46 publications

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“…Various hosts have been investigated for ion‐pair recognition, such as uranyl‐salophen compounds, or calixarene‐based, resorcinarene‐based, or pillararene‐based receptors. Studies of hemicryptophanes have revealed that they are also an appealing type of receptor for this purpose . Hemicryptophanes are chiral molecular containers that include a cyclotriveratrylene (CTV) moiety bonded to a C 3 ‐symmetrical organic group using three linkers whose identity and length can be varied .…”

Section: Introductionmentioning

confidence: 99%

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

et al. 2019

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A low‐energy collision induced dissociation (CID) (low‐energy CID) approach that can determine both activation energy and activation entropy has been used to evaluate gas‐phase binding energies of host‐guest (H‐G) complexes of a heteroditopic hemicryptophane cage host (Zn (II)@1) with a series of biologically relevant guests. In order to use this approach, preliminary calibration of the effective temperature of ions undergoing resonance excitation is required. This was accomplished by employing blackbody infrared radiative dissociation (BIRD) which allows direct measurement of activation parameters. Activation energies and pre‐exponential factors were evaluated for more than 10 H‐G complexes via the use of low‐energy CID. The relatively long residence time of the ions inside the linear ion trap (maximum of 60 s) allowed the study of dissociations with rates below 1 s−1. This possibility, along with the large size of the investigated ions, ensures the fulfilment of rapid energy exchange (REX) conditions and, as a consequence, accurate application of the Arrhenius equation. Compared with the BIRD technique, low‐energy CID allows access to higher effective temperatures, thereby permitting one to probe more endothermic decomposition pathways. Based on the measured activation parameters, guests bearing a phosphate (―OPO32−) functional group were found to bind more strongly with the encapsulating cage than those having a sulfonate (―SO3−) group; however, the latter ones make stronger bonds than those with a carboxylate (―CO2−) group. In addition, it was observed that the presence of trimethylammonium (―N(CH3)3+) or phenyl groups in the guest's structure improves the strength of H‐G interactions. The use of this technique is very straightforward, and it does not require any instrumental modifications. Thus, it can be applied to other H‐G chemistry studies where comparison of bond dissociation energies is of paramount importance.

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Section: Introductionmentioning

confidence: 99%

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

et al. 2019

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“…[8][9][10] They were found to be a novel class of efficient supramolecular catalysts, 11,12 ion pair, 13 or zwitterions receptors 14,15 and led to the design of novel molecular mechanical components as propeller or gyroscope. Their syntheses mainly afford racemic mixtures, and their optical resolution is a common and challenging issue in the research of optically pure molecular hosts.…”

Section: Introductionmentioning

confidence: 99%

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

et al. 2012

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The hemicryptophane racemate (±)-1 was optically resolved by semipreparative HPLC on Chiralpak IC column. The absolute configuration of each isolated enantiomer was established from the analysis of their electronic circular dichroism spectra. Enantiodifferentiation of the chiral cationic cage (±)-1 was evidenced in solution using Δ-TRISPHAT as chiral solvating agent, and the diastereomeric associations were observed in (1)H and (31)P NMR spectra.

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“…It is also noteworthy that, among the reported zwitterion receptors,7, 9–11 only a few examples describe the selective complexation of betaines,9, 11 with most of the systems being devoted to the binding of amino acids 7. 10a,c…”

Section: Resultsmentioning

confidence: 99%

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

Cornut

Moerkerke

Bruylants

et al. 2014

Chemistry An Asian Journal

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The efficient synthesis of calix[6]cryptothiourea 6 was achieved through a two-step sequence that involves a key [1+1] macrocyclization step. It was shown by NMR spectroscopy that this heteroditopic receptor can bind zwitterions in protic media with an outstanding selectivity for β-alanine betaine G5, which is likely due to a high complementarity between the two partners. This result constitutes a rare example of cavity complexation of a zwitterion by a calix[6]arene. In comparison with the parent urea-based receptors, 6 behaves as a much more efficient host for betaines. This strengthening of the binding properties is due to the better preorganization of the tripodal hydrogen-bonding cap as well as to the higher acidity of the thiourea groups and their poor ability to self-associate. Remarkably, host 6 is able to perform solid-liquid as well as liquid-liquid extraction of G5. Finally, 6 provides an excellent structural model for the binding site of glycine betaine G4 encountered in natural systems.

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A Designed Cavity for Zwitterionic Species: Selective Recognition of Taurine in Aqueous Media

Cited by 40 publications

References 46 publications

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

Investigation of activation energies for dissociation of host‐guest complexes in the gas phase using low‐energy collision induced dissociation

Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

A Biomimetic Heteroditopic Receptor for Zwitterions in Protic Media

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