Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichlo...

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Published in:Journal of the American Society for Mass Spectrometry 2012-10, Vol.23 (10), p.1786-1793
Main Authors: Choi, Tae Su, Ko, Jae Yoon, Heo, Sung Woo, Ko, Young Ho, Kim, Kimoon, Kim, Hugh I.
Format: Article
Language:English
Subjects:
Analytical Chemistry
Anions
Binding energy
Bioinformatics
Biotechnology
Bridged-Ring Compounds - chemistry
Chemical bonds
Chemistry
Chemistry and Materials Science
Chloroacetates - chemistry
Complex formation
Computer Simulation
Density functional theory
Electrospraying
Energy consumption
Exact sciences and technology
Gases - chemistry
Imidazoles - chemistry
Ionic mobility
Ionization
Ions
Mass spectra
Mass spectrometry
Models, Molecular
Organic Chemistry
Proteomics
Reactivity and mechanisms
Research Article
Spectrometry, Mass, Electrospray Ionization
Thermodynamics
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Summary:Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular S N 2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular S N 2 reaction of haloacetate, which correlate well with the experimental observation.
ISSN:1044-0305
1879-1123
DOI:10.1007/s13361-012-0443-6