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Synthesis and structure-property correlations of y-substituted pyrrolidone-based polymers

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Title
Synthesis and structure-property correlations of y-substituted pyrrolidone-based polymers
Name (type = personal)
NamePart (type = family)
Bhat
NamePart (type = given)
Rajani
NamePart (type = date)
1988-
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Rajani Bhat
Role
RoleTerm (authority = RULIB)
author
Name (type = personal)
NamePart (type = family)
Sheridan
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John
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John Sheridan
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Advisory Committee
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chair
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NamePart (type = family)
Huskey
NamePart (type = given)
Philip
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Philip Huskey
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Advisory Committee
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RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Pietrangelo
NamePart (type = given)
Agostino
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Agostino Pietrangelo
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Advisory Committee
Role
RoleTerm (authority = RULIB)
internal member
Name (type = personal)
NamePart (type = family)
Zhou
NamePart (type = given)
Shuiqin
DisplayForm
Shuiqin Zhou
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 - Newark
Role
RoleTerm (authority = RULIB)
school
TypeOfResource
Text
Genre (authority = marcgt)
theses
OriginInfo
DateCreated (encoding = w3cdtf); (qualifier = exact)
2017
DateOther (encoding = w3cdtf); (qualifier = exact); (type = degree)
2017-01
Language
LanguageTerm (authority = ISO 639-3:2007); (type = text)
English
Abstract (type = abstract)
Synthesis and characterization of novel y-substituted pyrrolidone-based polymers and PEG-PPS based polymers have been reported. In this thesis, pyrrolidone-based polymers have been explored with an interest to study the influence of substituents on the y-position. Synthesis of 5-methoxy-2-pyrrolidone was carried out using anodic decarboxylation of pyroglutamic acid. Acid catalyzed alkoxy/thioate exchange of 5-methoxy-2-pyrrolidone, derivatization with acryloyl moiety and subsequent polymerization of the monomers, yielded pyrrolidone-based polymers that varied in their ?-substituents. Polymerization was initially carried out via conventional free radical polymerization but later on was carried out via reversible addition-fragmentation transfer (RAFT) polymerization in order to get molecular weight control and narrower dispersity. The glass transition temperature Tg was found to be significantly influenced by both substituent structure (e.g., saturated linear aliphatic vs cyclic aliphatic vs aromatic) and chemical class.
Inspired by these findings, amphiphilic block copolymers comprising of pyrrolidone-based polymers as the hydrophilic and hydrophobic blocks were synthesized. These block copolymers comprised of poly(MeOEtONP) as the hydrophilic block and poly(N-acryloyl-2-pyrrolidone) (NP), poly (N-acryloyl-5-ethoxy-2-pyrrolidone) (EtONP) or poly(N-acryloyl-5-ethylthiolate-2-pyrrolidone) (EtSNP) as the hydrophobic block. Studies were conducted to assess the influence of the length of hydrophilic block and the chemical class of bridging unit in the hydrophobic block. Critical micelle concentration, turbidimetry and hydrodynamic radii studies indicate an increase in hydrophobicity on addition of a ?-substituent on the pyrrolidone ring. Drug-encapsulation and release studies conducted on the block copolymers suggested that the structure of the hydrophobic block in the copolymer plays an important role in determining the performance of these polymeric nanocarriers.
In a collaborative project with Prof. Robert K. Prud'homme of Princeton University, amphiphilic poly(ethylene glycol)-b- poly(propylene sulfide) (PEG-PPS) block copolymers of variable lengths were synthesized via anionic initiation method for flash nanoprecipitation of drug-loaded polymeric nanoparticle. PEG-PPS based block copolymers of variable lengths were synthesized and thermal properties were analyzed through differential scanning calorimetry and thermal gravimetric analysis. Initial studies conducted in the Prud'homme laboratory indicate a significant change in polymeric nanoparticle size upon subjecting it to oxidizing conditions. This indicates promising applications of the synthesized polymers in the field of drug-delivery.
Subject (authority = RUETD)
Topic
Chemistry
Subject (authority = local)
Topic
Pyrrolidone
Subject (authority = LCSH)
Topic
Polymers -- Synthesis
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_7793
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application/pdf
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text/xml
Extent
1 online resource (xx, 223 pages) : illustrations
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
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Title
Graduate School - Newark Electronic Theses and Dissertations
Identifier (type = local)
rucore10002600001
Location
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NjNbRU
Identifier (type = doi)
doi:10.7282/t3-06rq-ba63
Genre (authority = ExL-Esploro)
ETD doctoral
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Rights

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The author owns the copyright to this work.
RightsHolder (type = personal)
Name
FamilyName
Bhat
GivenName
Rajani
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2016-12-29 14:08:04
AssociatedEntity
Name
Rajani Bhat
Role
Copyright holder
Affiliation
Rutgers University. Graduate School - Newark
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License
Name
Author Agreement License
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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
Type
Embargo
DateTime (encoding = w3cdtf); (qualifier = exact); (point = start)
2017-01-31
DateTime (encoding = w3cdtf); (qualifier = exact); (point = end)
2019-01-31
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after January 31st, 2019.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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2017-01-03T23:56:12
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2017-01-03T23:56:12
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