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Chemical Reaction Dynamics of the Liquid/Vapor Interface Studied by Mass Spectrometry

Citation

Thomas, Daniel Aaron (2016) Chemical Reaction Dynamics of the Liquid/Vapor Interface Studied by Mass Spectrometry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9SN06XG. http://resolver.caltech.edu/CaltechTHESIS:05182016-140524270

Abstract

This thesis presents investigations of chemical reactions occurring at the liquid/vapor interface studied using novel sampling methodologies coupled with detection by mass spectrometry. Chapters 2 and 3 utilize the recently developed technique of field-induced droplet ionization mass spectrometry (FIDI-MS), in which the application of a strong electric field to a pendant microliter droplet results in the ejection of highly charged progeny droplets from the liquid surface. In Chapter 2, this method is employed to study the base-catalyzed dissociation of a surfactant molecule at the liquid/vapor interface upon uptake of ammonia from the gas phase. This process is observed to occur without significant modulation of the bulk solution pH, suggesting a transient increase in surface pH following the uptake of gaseous ammonia. Chapter 3 presents real-time studies of the oxidation of the model tropospheric organic compound glycolaldehyde by photodissociation of iron (III) oxalate complexes. The oxidation products of glycolaldehyde formed in this process are identified, and experiments in a deoxygenated environment identify the role of oxygen in the oxidation pathway and in the regeneration of iron (III) following photo-initiated reduction. Chapter 4 explores alternative methods for the study of heterogeneous reaction processes by mass spectrometric sampling from liquid surfaces. Bursting bubble ionization (BBI) and interfacial sampling with an acoustic transducer (ISAT) generate nanoliter droplets from a liquid surface that can be sampled via the atmospheric pressure interface of a mass spectrometer. Experiments on the oxidation of oleic acid by ozone using ISAT are also presented. Chapters 5 and 6 detail mechanistic studies and applications of free-radical-initiated peptide sequencing (FRIPS), a technique employing gas-phase free radical chemistry to the sequencing of peptides and proteins by mass spectrometry. Chapter 5 presents experimental and theoretical studies on the anomalous mechanism of dissociation observed in the presence of serine and threonine residues in peptides. Chapter 6 demonstrates the combination of FRIPS with ion mobility-mass spectrometry (IM-MS) for the separation of isomeric peptides.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Liquid/Vapor Interface ; Mass Spectrometry ; Fenton ; Interfacial Chemistry ; Ozonolysis ; Ion Mobility
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Mixed availability, specified at file level
Research Advisor(s):
  • Beauchamp, Jesse L.
Thesis Committee:
  • Okumura, Mitchio (chair)
  • Beauchamp, Jesse L.
  • Flagan, Richard C.
  • Ismagilov, Rustem F.
Defense Date:16 May 2016
Funders:
Funding AgencyGrant Number
NSFCHE-1508825
Beckman Institute, CaltechUNSPECIFIED
NASA Astrobiology Institute through NAI TitanUNSPECIFIED
Record Number:CaltechTHESIS:05182016-140524270
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:05182016-140524270
DOI:10.7907/Z9SN06XG
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ac504494tDOIPublication Related to Chapter 4
http://dx.doi.org/10.1021/jp501367wDOIPublication Related to Chapter 5
http://dx.doi.org/10.1021/ac400580uDOIPublication Related to Chapter 6
ORCID:
AuthorORCID
Thomas, Daniel Aaron0000-0001-9415-5991
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9728
Collection:CaltechTHESIS
Deposited By: Daniel Thomas
Deposited On:19 May 2016 21:20
Last Modified:18 May 2017 19:58

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