Quantifying non‐covalent binding affinity using mass spectrometry: A systematic study on complexes of cyclodextrins with alkali metal cations

Wei, Wanghui; Chu, Yanqiu; Wang, Rizhi; He, Xiaodan; Ding, Chuan‐Fan

doi:10.1002/rcm.7181

Cited by 18 publications

(19 citation statements)

References 36 publications

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“…27 The gas phase complexation between various b-CDs and alkali metals was also studied by DFT calculations (see the Experimental section). Moreover, such cation preference for b-CDs is quite similar to those obtained by ESI titration 65 and for a-CD using vibrational spectroscopy. 6.…”

Section: View Article Onlinesupporting

confidence: 79%

Probing the common alkali metal affinity of native and variously methylated β-cyclodextrins by combining electrospray-tandem mass spectrometry and molecular modeling

Przybylski

Bonnet

Cézard

2015

Phys. Chem. Chem. Phys.

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In the study herein, we investigated the solution and gas phase affinity of native and variously methylated β-cyclodextrins (CDs) as hosts towards three common alkali metals as guests namely lithium, sodium and potassium. For this purpose, two complementary approaches have been employed: electrospray-tandem mass spectrometry (ESI-MS/MS) with two energetic regimes: Collision Induced Dissociation (CID) and Higher Collision Dissociation (HCD), respectively, and DFT molecular modeling. These approaches have been achieved by taking into account the interaction of either one or two alkali metals with the host molecules. The results showed a good agreement between experimental and theoretical data. It was demonstrated that increasing the methylation degree strengthened the gas phase affinity towards all studied alkali metals. Furthermore, it was established that the cation selectivity was Na(+) > Li(+) > K(+) and Li(+) > Na(+) > K(+) for the solution and gas phase, respectively.

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Section: View Article Onlinesupporting

confidence: 79%

Probing the common alkali metal affinity of native and variously methylated β-cyclodextrins by combining electrospray-tandem mass spectrometry and molecular modeling

Przybylski

Bonnet

Cézard

2015

Phys. Chem. Chem. Phys.

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“…H‐G complexes have been subjected to various mass spectrometry‐based studies with a variety of purposes such as measurement of the energetics of H‐G binding using blackbody infrared radiative dissociation (BIRD) or threshold collision induced dissociation (TCID), obtaining a relative ranking of the stabilities of H‐G complexes by comparing fragmentation efficiency (or survival yield [SY]) curves, studying the role of proton affinities of guest molecules on the characteristics of fragmentation spectra of H‐G complexes, exploring the structure of H‐G complexes and the interactions between the two partners using the Förster resonance energy transfer (FRET) technique, quantifying binding affinities by mass spectrometric titration, and exploring the influence of solvent on H‐G affinities . These kinds of gas‐phase studies, however, have been never employed for the study of hemicryptophane H‐G complexes.…”

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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“…Investigations of host-guest complexes in the gas-phase [33][34][35][36][37], however, are not so common.…”

Section: Introductionmentioning

confidence: 99%

“…When utilizing tandem mass spectrometry techniques for comparison purposes, commonly survival yield (SY) is plotted as a function of energy in the center of mass frame. The so-called "SY curves" generated in this manner have sigmoidal shapes, and their inflection points are usually used to compare the relative stabilities of a series of H-G complexes [33][34][35][36][37]55]. There are various parameters influencing the position of the SY curves such as: the number of collisions (which depends on the size of the ion and the target gas pressure), critical energy, entropy of activation, and available time for decomposition that all combine to determine the "kinetic shift" [56,57] (i.e., the excess energy that needs to be applied to the precursor ion, relative to its critical energy of dissociation, in order to observe fragmentation in the time scale of mass spectrometric detection).…”

Section: Introductionmentioning

confidence: 99%

Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

Bayat

Gatineau

Lesage

et al. 2018

J. Am. Soc. Mass Spectrom.

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In advancing host-guest (H-G) chemistry, considerable effort has been spent to synthesize host molecules with specific and well-defined molecular recognition characteristics including selectivity and adjustable affinity. An important step in the process is the characterization of binding strengths of the H-G complexes that is typically performed in solution using NMR or fluorescence. Here, we present a mass spectrometry-based multimodal approach to obtain critical energies of dissociation for two hemicryptophane cages with three biologically-relevant guest molecules. A combination of blackbody infrared radiative dissociation (BIRD) and high-pressure collision induced dissociation (high-pressure CID), along with RRKM modeling, were employed for this purpose. For the two tested hemicryptophane hosts, the cage containing naphthyl linkages exhibited stronger interactions than the cage bearing phenyl linkages. For both cages, the order of guest stability is: choline > acetylcholine > betaine.The information obtained by these types of mass spectrometric studies can provide new insight into the structural features that most influence the stability of H-G pairs, thereby providing guidance for future syntheses.

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Quantifying non‐covalent binding affinity using mass spectrometry: A systematic study on complexes of cyclodextrins with alkali metal cations

Cited by 18 publications

References 36 publications

Probing the common alkali metal affinity of native and variously methylated β-cyclodextrins by combining electrospray-tandem mass spectrometry and molecular modeling

Probing the common alkali metal affinity of native and variously methylated β-cyclodextrins by combining electrospray-tandem mass spectrometry and molecular modeling

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

Investigation of Hemicryptophane Host-Guest Binding Energies Using High-Pressure Collision-Induced Dissociation in Combination with RRKM Modeling

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