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Gas phase studies of N-heterocyclic organic species using mass spectrometry

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TitleInfo
Title
Gas phase studies of N-heterocyclic organic species using mass spectrometry
Name (type = personal)
NamePart (type = family)
Wang
NamePart (type = given)
Kai
NamePart (type = date)
1985-
DisplayForm
Kai Wang
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Lee
NamePart (type = given)
Jeehiun Katherine
DisplayForm
Jeehiun Katherine Lee
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
chair
Name (type = personal)
NamePart (type = family)
Warmuth
NamePart (type = given)
Ralf
DisplayForm
Ralf Warmuth
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Krogh-Jespersen
NamePart (type = given)
Karsten
DisplayForm
Karsten Krogh-Jespersen
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Buckley
NamePart (type = given)
Brian
DisplayForm
Brian Buckley
Affiliation
Advisory Committee
Role
RoleTerm (authority = RULIB)
outside member
Name (type = corporate)
NamePart
Rutgers University
Role
RoleTerm (authority = RULIB)
degree grantor
Name (type = corporate)
NamePart
Graduate School - New Brunswick
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (qualifier = exact)
2014
DateOther (qualifier = exact); (type = degree)
2014-05
Place
PlaceTerm (type = code)
xx
Language
LanguageTerm (authority = ISO639-2b); (type = code)
eng
Abstract (type = abstract)
This dissertation focuses on the examination of thermochemical properties, including gas phase acidities, proton affinities and tautomerism of two types of N-heterocyclic organic species: damaged nucleobases and 1,2,3-triazoles via mass spectrometry methods (bracketing method on FTMS and Cooks kinetics method on LCQ) and theoretical studies (quantum mechanical calculations). Reactivities of N-heterocyclic carbenes as organocatalysts were also studied in the gas phase. 3-Methyladenine DNA glycosylase II (AlkA), which is found in Escherichia coli, is an enzyme that cleaves a wide range of damaged nucleobases from DNA. Herein we study the 3-methylated AlkA purine substrates, 3-methyladenine, non-substituted purine and and a potential AlkA substrate, 6-chloropurine. We found that the damaged nucleobases are more acidic than normal nucleobases. Resulting from this increasing of acidity, it is expected that damaged nucleobases are easier to be cleaved from the DNA chain since their conjugate bases should be better leaving groups. We also find that the gas phase acidities correlate with AlkA excision rate. Thus, the results lend support to the theory that AlkA differentiates among substrates by cleaving those nucleobases which are the most facile to remove. We also focus on studying the gas phase properties of 1,2,3-triazoles, which, compared with their applications, are largely unknown. The gas phase acidities and proton affinities of benzotriazole, 4-phenyl-1,2,3-triazole, substituted 4-phenyl-1,2,3-triazoles are discussed herein. Moreover, the tautomerism prevalence of 4-phenyl-1,2,3-triazole is acertained by ion-molecule reaction coordinate analysis and H/D exchange studies. In order to study the reaction mechanism of N-heterocyclic carbenes catalyzed reactions such as benzoin condensation, we synthesized a thiazolium catalyst with ethyl sulfonyl group on C4 position of five-membered thiazolium ring. Upon deprotonation, the thiazolium-based carbene is given a negative charge, which renders the visibility for both the carbene and reaction intermediates via mass spectrometry. We herein isolate and study the fragmentation pattern of both free carbene and reaction intermediates using ESI-MS/MS technique. As comparison, we also employ an imidazolium-based NHC to study the benzoin condensation via mass spectrometry and characterize the catalyst as well as the intermediates.
Subject (authority = RUETD)
Topic
Chemistry and Chemical Biology
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_5510
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
xvi, 96 p. : ill.
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Kai Wang
Subject (authority = ETD-LCSH)
Topic
Thermochemistry
Subject (authority = ETD-LCSH)
Topic
Heterocyclic chemistry
Subject (authority = ETD-LCSH)
Topic
Mass spectrometry
RelatedItem (type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier (type = local)
rucore19991600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T3H993H7
Genre (authority = ExL-Esploro)
ETD doctoral
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Rights

RightsDeclaration (ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Wang
GivenName
Kai
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2014-04-15 04:38:21
AssociatedEntity
Name
Kai Wang
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - New Brunswick
AssociatedObject
Type
License
Name
Author Agreement License
Detail
I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
RightsEvent
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2014-05-31
DateTime (encoding = w3cdtf); (qualifier = exact); (point = end)
2016-05-30
Type
Embargo
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after May 30th, 2016.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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ETD
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