Document Type
Dissertation
Degree
Doctor of Philosophy (PhD)
Major/Program
Chemistry
First Advisor's Name
Francisco Fernandez-Lima
First Advisor's Committee Title
Committee chair
Second Advisor's Name
Piero Gardinali
Second Advisor's Committee Title
Committee member
Third Advisor's Name
J. Martin E. Quirke
Third Advisor's Committee Title
Committee member
Fourth Advisor's Name
Berrin Tansel
Fourth Advisor's Committee Title
Committee member
Fifth Advisor's Name
John Berry
Fifth Advisor's Committee Title
Committee member
Keywords
TIMS, FT-ICR MS, Complex mixtures, High resolution ion mobility spectrometry, endocrine disruptors, crude oil, petroleum, polyaromatic hydrocarbons, PAHs, APLI, Atmospheric pressure laser ionization, molecular modeling, isomer separations
Date of Defense
9-18-2017
Abstract
Analytical Characterization of complex mixtures, such as crude oil, environmental samples, and biological mixtures, is challenging because of the large diversity of molecular components. Mass spectrometry based techniques are among the most powerful tools for the separation of molecules based on their molecular composition, and the coupling of ion mobility spectrometry has enabled the separation and structural elucidation using the tridimensional structure of the molecule. The present work expands the ability of analytical chemists by furthering the development of IMS-MS instrumentation by coupling Trapped Ion Mobility Spectrometry to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (TIMS-FT-ICR MS). The TIMS-FT-ICR MS platform combines the high-resolution separation of TIMS, which has mobility resolving powers up to 400, and ultra-high mass resolution of FT-ICR MS, with mass resolving power over 1,000,000. This instrumentation allows the assignment of exact chemical composition for compounds in a complex mixture, as well as measurement of the collision cross-section of the molecule. Herein, the principles of the TIMS separation and its coupling to FT-ICR MS are described, as well as how the platform can be applied to targeted analysis of molecules, and untargeted characterization of complex mixtures.
Molecular standards were analyzed by TIMS-MS in order to develop a computational workflow that can be utilized to elucidate molecular structure, using the measured collision cross-section of the ion. This workflow enabled identification of structural, cis/trans isomers, and chelated molecules and provides the basis for unsupervised structural elucidation of a complex mixture, and in particular for the elucidation of hydrocarbons from fossil fuels. In summary, this work presents the coupling of TIMS-FT-ICR MS and provides examples of applications as a proof of concept of the potential of this platform for solving complex analytical challenges.
Identifier
FIDC004019
ORCID
0000-0002-5298-289X
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial 4.0 License
Recommended Citation
Benigni, Paolo, "Trapped Ion Mobility Spectrometry coupled to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry for the analysis of Complex Mixtures." (2017). FIU Electronic Theses and Dissertations. 3547.
https://digitalcommons.fiu.edu/etd/3547
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