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Inclusion Complexes of Ionic Liquids and Cyclodextrins: Are They Formed in the Gas Phase?

  • Ana M. Fernandes
  • Bernd Schröder
  • Tânia Barata
  • Mara G. Freire
  • João A. P. Coutinho
Research Article

Abstract

The interaction of imidazolium-based ionic liquids with α- and β-cyclodextrins was investigated by electrospray ionization mass spectrometry with variable collision induced dissociation energy and quantum chemical gas-phase calculations. The center-of-mass energy at which 50 % of a precursor ion decomposes (Ecm,1/2) was determined for the isolated [cyclodextrin + cation]+ or [cyclodextrin + anion] adduct ions of imidazolium-based ionic liquids with different alkyl chain lengths combined with a large set of anions, such as chloride, bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methanesulfonate, dicyanamide, and hydrogensulfate. Moreover, both symmetric and asymmetric imidazolium cationic cores were evaluated. The relative interaction energies in the adduct ions were interpreted in terms of the influence of cation/anion structures and their inherent properties, such as hydrophobicity and hydrogen bond accepting ability, in the complexation process with the cyclodextrins. The trends observed in the mass spectral data together with quantum-chemical calculations suggest that in the gas phase, cations and anions will preferentially interact with the lower or upper rim of the cyclodextrin, respectively, as opposed to what has been reported in condensed phase where the formation of an inclusion complex between ionic liquid and cyclodextrin is assumed.

Keywords

Ionic liquids Cyclodextrin Inclusion Electrospray-ionization Collision-induced-dissociation Electronic-structure calculations 

Notes

Acknowledgments

Thanks are due to Fundação para a Ciência e a Tecnologia (FCT, Portugal) and European Union, QREN, FEDER, and COMPETE for funding the QOPNA research unit (project PEst-C/QUI/UI0062/2011) and CICECO (Pest-C/CTM/LA0011/2011). B.S. acknowledges the award of a FCT post-doctoral grant (SFRH/BPD/38637/2007) and the FCT project (PTDC/AAC-AMB/121161/2010). T.B. acknowledges a FCT BII grant, M.G.F. acknowledges a FCT post-doctoral grant SFRH/BPD/41781/2007.

Supplementary material

13361_2013_820_MOESM1_ESM.docx (1.1 mb)
ESM 1 (DOCX 1.13 MB)

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Copyright information

© American Society for Mass Spectrometry 2014

Authors and Affiliations

  • Ana M. Fernandes
    • 1
  • Bernd Schröder
    • 2
  • Tânia Barata
    • 1
  • Mara G. Freire
    • 2
  • João A. P. Coutinho
    • 2
  1. 1.Departamento de Química, QOPNAUniversidade de AveiroAveiroPortugal
  2. 2.Departamento de Química, CICECOUniversidade de AveiroAveiroPortugal

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