Exploring halide anion affinities to native cyclodextrins by mass spectrometry and molecular modelling. Issue 3 (June 2018)

• Record Type: Journal Article
• Authors: Xu, Chongsheng; He, Nan; Li, Zhenhua; Chu, Yanqiu; Ding, Chuan-Fan
• Is Part Of: European journal of mass spectrometry. Volume 24:Issue 3(2018)
• Page Start: 268
• Page End: 278
• Publication Date: 2018-06
• Subjects: Cyclodextrins -- density functional calculation -- halide anions -- inclusion complexes -- mass spectrometry; Mass spectrometry -- Periodicals; Mass Spectrometry; Mass spectrometry; Periodicals; Periodicals; 543.6505
• DOI: 10.1177/1469066717748658
• Languages: English
• ISSNs: 1469-0667

Abstract

The binding affinities of cyclodextrins complexation with chlorine (Cl − ), bromine (Br − ) and iodine (I − ), were measured by mass spectrometric titrimetry, and the fitting of the binding constants was based on the concentration measurement of the cyclodextrin equilibrium. The binding constants (lg Ka ) for α-, β- or γ-cyclodextrin with Cl − were 3.99, 4.03 and 4.11, respectively. The gas-phase binding affinity of halide anions for native cyclodextrins was probed by collision-induced dissociation. In collision-induced dissociation, the centre-of-mass frame energy results revealed that in the gas phase, for the same type of cyclodextrin, the stability of the complexes decreased in order: Cl > Br > I, and for the same halide anion, the binding stability of the complex with α-, β- or γ-cyclodextrin decreased in the order: γ-cyclodextrin >β-cyclodextrin > α-cyclodextrin. The density functional theory calculations showed that halide anion binding on the primary face had a lower energy than the secondary face and hydrogen bonding was the main driving force for complex formation. The higher stability of the γ-cyclodextrin complex with the Cl anion can be attributed to the higher charge density of the Cl anion and better flexibility of γ-cyclodextrin.