This dissertation focuses on the investigation of gas-phase characteristics of cucurbituril host-guest systems using ion mobility spectrometry (IMS) and related techniques. Collision cross-sections (CCS) of alkylammonium complexes of cucurbit[n]uril (CB[n]) are measured to understand the allosteric interactions that induce conformational changes in the complex in the presence of metal cations on one of the portals of the cucurbituril (CB) host. Cationic species on one CB rim sterically force longer linear alkylammonium guests out of the cucurbituril cavity during complex formation. Similarly, rigid cucurbituril-metal complexes were studied using IMS to demonstrate the effect of long-range ion-neutral interactions on the gas phase mobility of ions. The contributions of charge state and charge distribution to the ion mobility CCS measured using a drift tube ion mobility spectrometer (DTIMS) were studied. This IMS method characterization will help in the study of biomolecules and may answer some of the questions regarding CCS measurements in protein structures, that are still being debated. While most of the studies were done using an IMS system, this dissertation also includes gas phase characterization studies done using Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. A novel gas-phase CCS measurement technique - cross sectional areas using Fourier transform ion cyclotron resonance mass spectrometry (CRAFTI) was attempted on bigger systems like the [cucurbituril-n-alkylammonium]+ complexes. Infrared multi-photon dissociation (IRMPD), collision induced dissociation (CID), and sustained off-resonance irradiation (SORI) studies were done on many CB[n] systems, which helped to extract useful structural information about the complexes.
College and Department
Physical and Mathematical Sciences; Chemistry and Biochemistry
BYU ScholarsArchive Citation
Shrestha, Jamir, "Gas Phase Structure Characterization of Host-Guest Systems Using Ion Mobility Spectrometry" (2022). Theses and Dissertations. 9405.
Cucurbit[n]uril, IMS, DTIMS, FTICR, IRMPD, CRAFTI, SORI, CID