What happens to hydrophobic interactions during transfer from the solution to the gas phase?: The case of electrospray-based soft ionization methodsстатья

Статья опубликована в высокорейтинговом журнале

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Дата последнего поиска статьи во внешних источниках: 6 декабря 2018 г.

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[1] What happens to hydrophobic interactions during transfer from the solution to the gas phase?: The case of electrospray-based soft ionization methods / K. Barylyuk, R. M. Balabin, D. Grünstein et al. // Journal of the American Society for Mass Spectrometry. — 2011. — Vol. 22, no. 7. — P. 1167–1177. The disappearance of the hydrophobic effect in the gas phase due to the absence of an aqueous surrounding raises a long-standing question: can noncovalent complexes that are exclusively bound by hydrophobic interactions in solution be preserved in the gas phase? Some reports of successful detection by mass spectrometry of complexes largely stabilized by hydrophobic effect are questionable by the presence of electrostatic forces that hold them together in the gas phase. Here, we report on the MS-based analysis of model supramolecular complexes with a purely hydrophobic association in solution, β-cyclodextrin, and synthetic adamantyl-containing ligands with several binding sites. The stability of these complexes in the gas phase is investigated by quantum chemical methods (DFT-M06). Compared with the free interaction partners, the inclusion complex between β-cyclodextrin and adamantyl-containing ligand is shown to be stabilized in the gas phase by ΔG = 9.6 kcal mol -1. The host-guest association is mainly enthalpy-driven due to strong dispersion interactions causedbya large nonpolar interface and a high steric complementarity of the binding partners. Interference from other types of noncovalent binding forces is virtually absent. The complexes are successfully detected via electrospray ionization mass spectrometry, althougha high dissociation yieldisalso observed. We attribute this pronounced dissociationof the complexes tothe collisional activation of ions in the atmospheric interface of mass spectrometer. The comparison of several electrospray-based ionization methods reveals that cold spray ionization provides the softest ion generation conditions for these complexes. [ DOI ]

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