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Full-Text Articles in Physical Sciences and Mathematics
Determination Of A Catalytic Mechanism By Time Resolved Fourier Transform Infrared Spectroscopy And Time Domain Analysis Of Data From Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Jacob T. Davis
Theses and Dissertations
Heterobimetallic catalysts offer large potential for efficient and selective catalysis of a wide range of reactions. Better understanding of these catalytic mechanisms could yield further improvement in their catalytic abilities. Cp(CO)2Fe-Cu(IPr) (IPr = N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is a catalyst that has been reported to catalyze arene borylation. The catalytic mechanism of this catalyst that had been previously proposed had the initial step being a metal-metal cleavage. However, computational modeling suggested an alternate mechanism that could be more energetically favorable. Rather than a metal-metal cleavage as the initial step, we proposed a photoactivated carbonyl dissociation. To support this proposition, we performed time resolved …
Ion Structure Characterization And Energetics In The Gas Phase Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry And Ion Mobility Spectrometry, Tina Heravi
Theses and Dissertations
In this dissertation, I used Fourier transform ion cyclotron resonance mass spectrometry (FTICR) and ion mobility spectrometry (IMS) to study the structure and energetics of supramolecular complex ions in the gas phase. Using the CRAFTI (cross sectional areas by Fourier transform ion cyclotron resonance) technique developed by Dearden’s lab we observed that complexes with alkali cations capping the portals of cucurbit[5]uril (CB[5]) bind halide anions size-selectively in the gas phase. Our data suggest that Cl– binds inside the CB[5] cavity, Br– binds both inside (with Na+ions capping the portals of CB[5]) and outside (when K+caps CB[5]), and I– binds weakly …
Gas Phase Techniques For The Study Of Biomolecular And Supramolecular Structures And Chemistry, Andrew J. Arslanian
Gas Phase Techniques For The Study Of Biomolecular And Supramolecular Structures And Chemistry, Andrew J. Arslanian
Theses and Dissertations
This dissertation expounds on the investigations of the structure and chemistry of peptides and supramolecular host-guest systems in the gas phase. These investigations used two different kinds of analytical instrument: Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and ion mobility mass spectrometry (IM-MS, IMS). These investigations were complemented by chemical modeling. The FTICR was used to radially trap ions with its 4.7 T magnet, which allowed the ions to undergo sustained off-resonance irradiation collision-induced dissociation (SORI-CID). A subsequent event then measured the collision cross sections (σ) of the targeted precursor ion and one of the selected product ions. These …
Gas Phase Structure Characterization Of Host-Guest Systems Using Ion Mobility Spectrometry, Jamir Shrestha
Gas Phase Structure Characterization Of Host-Guest Systems Using Ion Mobility Spectrometry, Jamir Shrestha
Theses and Dissertations
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 cucurbit[6]uril (CB[6]) host. Cationic species on one CB[6] 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 …