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Gas phase reactivity studies of organic species using mass spectrometry
Descriptive
TitleInfo
Title
Gas phase reactivity studies of organic species using mass spectrometry
Name
(type = personal)
NamePart
(type = family)
Zhang
NamePart
(type = given)
Sisi
NamePart
(type = date)
1987-
DisplayForm
Sisi Zhang
Role
RoleTerm
(authority = RULIB)
author
Name
(type = personal)
NamePart
(type = family)
Lee
NamePart
(type = given)
Jeehiun K
DisplayForm
Jeehiun K Lee
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
chair
Name
(type = personal)
NamePart
(type = family)
Romsted
NamePart
(type = given)
Larry
DisplayForm
Larry Romsted
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Jimenez
NamePart
(type = given)
Leslie
DisplayForm
Leslie Jimenez
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal 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)
2012
DateOther
(qualifier = exact);
(type = degree)
2012-10
Place
PlaceTerm
(type = code)
xx
Language
LanguageTerm
(authority = ISO639-2b);
(type = code)
eng
Abstract
(type = abstract)
DNA damaged bases are one of the reasons for a variety diseases, such as carcinogenesis, aging and cell death. uracil is a nucleobase that arises from cytosine deamination. N-Deprotonated uracil functions as a leaving group during the deamination process. Theoretically, in the SN2 reaction, leaving group ability tracks with pKa of the conjugate acid in the solution phase, that is, lower pKa is associated with better leaving group ability. In the gas phase, leaving group ability is better with higher acidity of the conjugate acid. The studies we did previously showed that although 3-methyluracil is as acidic as hydrochloric acid in the gas phase, the leaving group ability of chloride is better than deprotonated 3-methyluracil. The reason we propose this is that the electron delocalization in the transition state of SN2 reaction cannot be fully recognized as in acidity. Therefore, we designed substituted aniline and amine with leaving groups with or without the ability of electron delocalization and found that substituted amine with leaving groups that did not have the ability of electron delocalization tracked better with acidity than the one with the ability of electron delocalization. The result is consistent with our proposal. We also tested the Hammond postulate with the calculation results. Another focus of interest is N-heterocyclic singlet carbenes (NHCs), which are ligands of a variety of organometallic catalysts. Presumably the ligands are more effective if they are more basic, that is, with higher proton affinity. The protonated carbenes are also an important class of ionic liquids, known as green solvents with several advantages over traditional organic solvents. Strassner et al designed a new type of ionic liquid imidazolium salt with tunable para-aryl substituent, and we measured the acidity of these tunable aryl-alkyl ionic liquids (TAAILs). The proton-bound dimers of dimethyl imidazole and PCy3 are found to exhibit interesting reactivity. In addition to producing just protonated carbenes and protonated phosphine with collision induced dissociation (CID), the proton-bound dimers generate another ion of interest with m/z 295. We designed and synthesized the di-CD3 imidazole, and proved that the dimethyl system undergoes phosphine methylation during CID process.
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_4184
PhysicalDescription
Form
(authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
x, 57 p. : ill.
Note
(type = degree)
M.S.
Note
(type = bibliography)
Includes bibliographical references
Note
(type = vita)
Includes vita
Note
(type = statement of responsibility)
by Sisi Zhang
Subject
(authority = ETD-LCSH)
Topic
Mass spectrometry
Subject
(authority = ETD-LCSH)
Topic
Protons--Affinity labeling
Subject
(authority = ETD-LCSH)
Topic
Acidity function
Identifier
(type = hdl)
http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000067039
RelatedItem
(type = host)
TitleInfo
Title
Graduate School - New Brunswick Electronic Theses and Dissertations
Identifier
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rucore19991600001
Location
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(displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier
(type = doi)
doi:10.7282/T3DJ5DC4
Genre
(authority = ExL-Esploro)
ETD graduate
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Rights
RightsDeclaration
(ID = rulibRdec0006)
The author owns the copyright to this work.
RightsHolder
(type = personal)
Name
FamilyName
Zhang
GivenName
Sisi
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
(encoding = w3cdtf);
(qualifier = exact);
(point = start)
2012-08-02 15:29:09
AssociatedEntity
Name
Sisi Zhang
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.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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Technical
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