What Happens to Hydrophobic Interactions during Transfer from the Solution to the Gas Phase?

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Author(s) Barylyuk, Konstantin, Balabin, Roman M., Grünstein, Dan, Kikkeri, Raghavendra, Frankevich, Vladimir, Seeberger, Peter H., Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title What Happens to Hydrophobic Interactions during Transfer from the Solution to the Gas Phase?
Subtitle The Case of Electrospray-Based Soft Ionization Methods
Author(s) Barylyuk, Konstantin
Balabin, Roman M.
Grünstein, Dan
Kikkeri, Raghavendra
Frankevich, Vladimir
Seeberger, Peter H.
Zenobi, Renato
Journal or Series Title Journal of the American Society for Mass Spectrometry
Volume Number 22
Issue Number 7
Start Page 1167
End Page 1177
ISSN 1044-0305
Publisher Springer
Publication Place New York
Publication Date 2011-07
Keyword(s) Electrospray ionization mass spectrometry
Non-covalent complexes
Hydrophobic interactions
Van der Waals-London dispersion interactions
Gas phase
Abstract 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, beta-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 beta-cyclodextrin and adamantyl-containing ligand is shown to be stabilized in the gas phase by Delta G = 9.6 kcal mol(-1). The host-guest association is mainly enthalpy-driven due to strong dispersion interactions caused by a 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, although a high dissociation yield is also observed. We attribute this pronounced dissociation of the complexes to the 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 10.1007/s13361-011-0118-8
Additional Notes Received 15 November 2010, Revised 11 February 2011, Accepted 28 February 2011, Published online 26 April 2011
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
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NEBIS System Number 000541631
Source Database ID WOS-000291257400007
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  author = "Barylyuk, Konstantin and Balabin, Roman M. and Gr{\"{u}}nstein, Dan and Kikkeri, Raghavendra and Frankevich, Vladimir and Seeberger, Peter H. and Zenobi, Renato",
  title = "{W}hat {H}appens to {H}ydrophobic {I}nteractions during {T}ransfer from the {S}olution to the {G}as {P}hase?: {T}he {C}ase of {E}lectrospray-{B}ased {S}oft {I}onization {M}ethods",
  journal = "Journal of the American Society for Mass Spectrometry",
  year = 2011,
  volume = "22",
  number = "7",
  pages = "1167--1177",
  month = jul,

E-Citations record created: Mon, 04 Jul 2011, 13:03:26 CET