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Georgia Tech
1.
Woody, Kathy Beckner.
Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications.
Degree: PhD, Chemistry and Biochemistry, 2011, Georgia Tech
URL: http://hdl.handle.net/1853/43627 
► Conjugated polymers comprise some of the most promising materials for new technologies such as organic field effect transistors, solar light harvesting technology and sensing devices.…
(more)
▼ Conjugated polymers comprise some of the most promising materials for new technologies such as organic field effect transistors, solar light harvesting technology and sensing devices. In spite of tremendous research initiatives in materials chemistry, the potential to optimize device performance and develop new technologies is remarkable. Understanding relationships between the structure of conjugated polymers and their electronic properties is critical to improving device performance. The design and synthesis of new materials which self-organize into ordered nanostructures creates opportunities to establish relationships between electronic properties and morphology or molecular packing. This thesis details our progress in the development of synthetic routes which provide access to new classes of conjugated polymers that contain dissimilar side chains that segregate or dissimilar conjugated blocks which phase separate, and summarizes our initial attempts to characterize these materials. Poly(1,4-phenylene ethynylene)s (PPEs) have been used in a variety of organic electronic applications, most notably as fluorescent sensors. Using traditional synthetic methods, asymmetrically disubstituted PPEs have irregular placement of side chains on the conjugated backbone. Herein, we establish the first synthetic route to an asymmetrically substituted regioregular PPEs. The initial PPEs in this study have different lengths of alkoxy side chains, and both regioregular and regiorandom analogs are synthesized and characterized for comparison. The design of amphiphilic structures provides additional opportunities for side chains to influence the molecular packing and electronic properties of conjugated polymers. A new class of regioregular, amphiphilic PPEs has been prepared bearing alkoxy and semifluoroalkoxy side chains, which have a tendency to phase separate. Fully conjugated block copolymers can provide access to interesting new morphologies as a result of phase separation of the conjugated blocks. In particular, donor-acceptor block copolymers that phase separate into electron rich and electron poor domains may be advantageous in organic electronic devices such as bulk heterojunction solar cells, of which the performance relies on precise control of the interface between electron donating and accepting materials. The availability of donor-acceptor block copolymers is limited, largely due to the challenges associated with synthesizing these materials. In this thesis, two new synthetic routes to donor-acceptor block copolymers are established. These methods both utilize the catalyst transfer condensation polymerization, which proceeds by a chain growth mechanism. The first example entails the synthesis of a monofunctionalized, telechelic poly(3-alkylthiophene) which can be coupled to electron accepting polymers in a subsequent reaction. The other method describes the first example of a one-pot synthesis of a donor-acceptor diblock copolymer. The methods of synthesis are described, and characterization of the block copolymers is…
Advisors/Committee Members: David Collard (Committee Chair), Anslem Griffin (Committee Member), Laren Tolbert (Committee Member), Seth Marder (Committee Member), Stefan France (Committee Member).
Subjects/Keywords: Block copolymers; Conjugated polymers; Self-assembly; Poly(phenylene ethynylene); Polymer synthesis; Organic electronics; Organic semiconductors; Organic field-effect transistors; Polymerization
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APA (6th Edition):
Woody, K. B. (2011). Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/43627
Chicago Manual of Style (16th Edition):
Woody, Kathy Beckner. “Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications.” 2011. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/43627.
MLA Handbook (7th Edition):
Woody, Kathy Beckner. “Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications.” 2011. Web. 20 Jan 2021.
Vancouver:
Woody KB. Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications. [Internet] [Doctoral dissertation]. Georgia Tech; 2011. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/43627.
Council of Science Editors:
Woody KB. Design, synthesis and characterization of self-assembling conjugated polymers for use in organic electronic applications. [Doctoral Dissertation]. Georgia Tech; 2011. Available from: http://hdl.handle.net/1853/43627
Georgia Tech
2.
Hibbs, Michael R.
Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate).
Degree: PhD, Chemistry, 2003, Georgia Tech
URL: http://hdl.handle.net/1853/30554
Subjects/Keywords: Polyethylene teraphthalate Fatigue; Copolymers Testing; Vapor barriers
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APA (6th Edition):
Hibbs, M. R. (2003). Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate). (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/30554
Chicago Manual of Style (16th Edition):
Hibbs, Michael R. “Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate).” 2003. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/30554.
MLA Handbook (7th Edition):
Hibbs, Michael R. “Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate).” 2003. Web. 20 Jan 2021.
Vancouver:
Hibbs MR. Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate). [Internet] [Doctoral dissertation]. Georgia Tech; 2003. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/30554.
Council of Science Editors:
Hibbs MR. Design and synthesis of comonomers to enhance the physical properties of poly(ethylene terephthalate). [Doctoral Dissertation]. Georgia Tech; 2003. Available from: http://hdl.handle.net/1853/30554
3.
Phun, Lien Hoang.
Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles.
Degree: PhD, Chemistry and Biochemistry, 2013, Georgia Tech
URL: http://hdl.handle.net/1853/47542
► Natural products and small molecules play a major role in drug development. However, using natural products as a source of medicine comes with many challenges,…
(more)
▼ Natural products and small molecules play a major role in drug development. However, using natural products as a source of medicine comes with many challenges, such as lack of natural abundance and difficulty in isolation. Consequently, synthetic organic chemistry is a solution in order to access these compounds in usable quantities. However, synthetic chemisty comes with its own challenges such as efficiency, chemoselectivity, stereoselectivity and enantioselectivity. Therefore, synthetic tools that addresses these challenges are required solve these limitations. This thesis discusses new methodologies using strained carbocycles (cyclopropanes and cyclopropenes) as the reactive subunit for the construction of different carbocyclic and heterocyclic compounds. The homo-Nazarov cyclization of alkenyl and heteroaryl cyclopropyl ketones was used in order to construct cyclohexenones, cyclohexenols, heteroaryl ring-fused cyclohexenones, dihydrofurans, furans and furanones in a mild and efficient manner. Benzofused heteroaromatic compounds were achieved via the Lewis acid-catalyzed cycloisomerization of cyclopropene-3,3-dicarbonyls and furan-3-carboxylates. These heteroaromatic compounds can be applied to medicinal chemistry and material science.
Advisors/Committee Members: [email protected] (Committee Chair), charles liotta (Committee Member), christoph fahrni (Committee Member), david collard (Committee Member), julia kubanek (Committee Member).
Subjects/Keywords: Furans; Carbocycles; Heterocycles; Cyclopropane; Cyclopropene; Diazo; Drug development; Pharmacognosy
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APA (6th Edition):
Phun, L. H. (2013). Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/47542
Chicago Manual of Style (16th Edition):
Phun, Lien Hoang. “Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles.” 2013. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/47542.
MLA Handbook (7th Edition):
Phun, Lien Hoang. “Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles.” 2013. Web. 20 Jan 2021.
Vancouver:
Phun LH. Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles. [Internet] [Doctoral dissertation]. Georgia Tech; 2013. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/47542.
Council of Science Editors:
Phun LH. Innovative approaches to carbocyclic and heterocyclic compounds using strained carbocycles. [Doctoral Dissertation]. Georgia Tech; 2013. Available from: http://hdl.handle.net/1853/47542
4.
Aiyar, Avishek R.
Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene).
Degree: PhD, Chemical Engineering, 2012, Georgia Tech
URL: http://hdl.handle.net/1853/43574
► Conjugated polymers represent the next generation of conducting materials that will enable technological devices incorporating thin film transistors, photovoltaic cells etc., in a cost-effective roll-to-roll…
(more)
▼ Conjugated polymers represent the next generation of conducting materials that will enable technological devices incorporating thin film transistors, photovoltaic cells etc., in a cost-effective roll-to-roll manner. Given the importance of microstructure on charge transport, ordered self-assembly in polymeric semiconductors assumes paramount relevance. This thesis thus focuses on a fundamental investigation of the correlations between the morphology and microstructure of the first high mobility solution processable semiconducting polymer, poly(3-hexylthiophene)(P3HT), and its corresponding charge transport properties. The evolution of polymer chain conformations is first studied, leading up to the formation of the conducting channel. An intermediate lyotropic liquid crystalline phase is identified, characterized by anisotropic ordering of the polymer chains. Methods for tuning the microstructure of P3HT thin films are also discussed, with an emphasis on understanding the role of molecular parameters, such as regioregularity and process parameters such as the film formation method. An ultrasound based technique for inducing the formation of ordered π-stacked molecular aggregates is also introduced. The results presented here not only provide understanding of microstructure-charge transport correlations, but also the very process of film formation in solution processable organic semiconductors, which could in turn hold the key to approaching the mobility benchmark represented by single crystals.
Advisors/Committee Members: Elsa Reichmanis (Committee Chair), Bernard Kippelen (Committee Member), Carson Meredith (Committee Member), David Collard (Committee Member), Dennis Hess (Committee Member).
Subjects/Keywords: Mobility; Ultrasound; Aggregation; Molecular order; Regioregularity; Microstructure; P3HT; Organic electronics; Field effect transistors
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APA (6th Edition):
Aiyar, A. R. (2012). Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene). (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/43574
Chicago Manual of Style (16th Edition):
Aiyar, Avishek R. “Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene).” 2012. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/43574.
MLA Handbook (7th Edition):
Aiyar, Avishek R. “Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene).” 2012. Web. 20 Jan 2021.
Vancouver:
Aiyar AR. Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene). [Internet] [Doctoral dissertation]. Georgia Tech; 2012. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/43574.
Council of Science Editors:
Aiyar AR. Understanding the impact of polymer self-organization on the microstructure and charge transport in poly(3-hexylthiophene). [Doctoral Dissertation]. Georgia Tech; 2012. Available from: http://hdl.handle.net/1853/43574
5.
Kasson, Tina Michelle Dreaden.
High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair.
Degree: PhD, Chemistry and Biochemistry, 2012, Georgia Tech
URL: http://hdl.handle.net/1853/45759
► Oxidative stress is a natural consequence of photosynthetic oxygen evolution and redox enzyme processes. Trp oxidation to N-formylkynurenine (NFK) is a specific, reactive oxygen species…
(more)
▼ Oxidative stress is a natural consequence of photosynthetic oxygen evolution and redox enzyme processes. Trp oxidation to N-formylkynurenine (NFK) is a specific, reactive oxygen species (ROS)-mediated reaction. This thesis work describes the identification and functional characterization of NFK in oxygen evolving Photosystem II (PSII). Although proteomics studies have confirmed NFK modifications in many types of proteins, limited knowledge on the biochemical significance exists. In vitro studies in thylakoids and PSII membranes were used to establish a correlation between oxidative stress, NFK formation, and photoinhibition. The in vivo effect of preventing Trp oxidation to NFK was assessed by site-directed mutation in the cyanobacteria Synechocystis sp. PCC 6803. This work provides insight into the role of NFK in photosynthetic oxygen evolution and photoinhibition. Based on the current knowledge of NFK, ROS, and repair, a new model is described. In this modified model for photoinhibition and repair, NFK plays a role in signaling for turnover of damaged proteins. NFK may play a similar role in replacement of damaged proteins in other systems.
Advisors/Committee Members: Bridgette A. Barry (Committee Chair), David Collard (Committee Member), Ingeborg Schmidt-Krey (Committee Member), Wendy Kelly (Committee Member), Yomi Oyelere (Committee Member).
Subjects/Keywords: Tryptophan; Reactive oxygen species; Photosynthesis; Photosystem II; N-formylkynurenine; Synechocystis 6803; Amino acids; Plants Effect of light on
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APA (6th Edition):
Kasson, T. M. D. (2012). High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/45759
Chicago Manual of Style (16th Edition):
Kasson, Tina Michelle Dreaden. “High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair.” 2012. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/45759.
MLA Handbook (7th Edition):
Kasson, Tina Michelle Dreaden. “High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair.” 2012. Web. 20 Jan 2021.
Vancouver:
Kasson TMD. High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair. [Internet] [Doctoral dissertation]. Georgia Tech; 2012. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/45759.
Council of Science Editors:
Kasson TMD. High light stress in photosynthesis:
the role of oxidative post-translational modifications in signaling and repair. [Doctoral Dissertation]. Georgia Tech; 2012. Available from: http://hdl.handle.net/1853/45759
6.
Charney, Reagan R.
Coupling reactions and separations for improved synthetic processes.
Degree: PhD, Chemistry and Biochemistry, 2008, Georgia Tech
URL: http://hdl.handle.net/1853/26675
► This thesis showcases a work that focused on developing processes with improved economic and environmental signatures. It illustrates the strengths of chemists and chemical engineers…
(more)
▼ This thesis showcases a work that focused on developing processes with improved economic and environmental signatures. It illustrates the strengths of chemists and chemical engineers working together towards sustainable solutions. The joint collaboration between Drs. Liotta and Eckert allows the combination of disciplines to overcome economic and environment obstacles. This thesis depicts the application of chemical engineering and chemistry for industrial processes towards reducing cost and environmental impact.
In chapter 2, a synthetic sequence yielding a pharmaceutical precursor was optimized for continuous processing. The precursor was for the pharmaceutical drug Ro 31-8959, which acts as a human immunodeficiency virus (HIV) protease inhibitor. A continuous flow reactor was designed, built and utilized successfully for the two-step reaction of the diazoketone pharmaceutical precursor, (1-benzyl-3-chloro-2-hydroxy-propyl)-carbamic acid tert-butyl ester. The best configuration for the continuous flow reactor involved a single and double coiled stainless steel reactor packed with glass beads. The yield obtained for the diazoketone was quantitative.
In chapter 3, the cleavable surfactant (cleavable surfactants decompose in non-surface active ingredients upon stimulus), n-octyl thiirane oxide was synthesized, characterized and its surface activity and loss of surface activity upon heating was demonstrated. The n-octyl thiirane oxide surfactant activity was measured using a dye, Suddan III, and compared to a commercially available surfactant sodium dodecyl sulfate.
In chapter 4, 5-amino-1H-tetrazole was synthesized using two novel synthetic routes starting from benign chemicals. Both routes involved Sharpless click chemistry in the first step to form the tetrazole ring. Both routes also used hydrogen transfer as the last step for the formation of the 5-amino-1H-tetrazole. These syntheses eliminated the use of highly toxic and/or explosive chemicals such as cyanamide, hydrazoic acid, and hydrazine.
Finally in chapter 5, phase transfer catalysis was used as a means to improve reaction rates and yields between a siloxylated reagent (in the liquid phase) and insoluble ionic reagents (in the solid phase). The activity of commercial phase transfer catalysts like tetra-n-butylammonium bromide was compared to the activity of two novel custom-made siloxylated phase transfer catalysts. Surprisingly, the tetra-n-butylammonium resulted in superior rate constants to the custom made siloxylated phase transfer catalysts.
Advisors/Committee Members: Dr. Charles Liotta (Committee Chair), Dr. Charles Eckert (Committee Co-Chair), Dr. David Collard (Committee Member), Dr. Facundo Fernandez (Committee Member), Dr. Rigoberto Hernandez (Committee Member).
Subjects/Keywords: 5-aminotetrazole; Cleavable surfactants; Siloxylated aminoacids; Continuous flow reactor; PTC; Metabolomics; Reactivity (Chemistry); Sustainable engineering; Technology transfer
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APA (6th Edition):
Charney, R. R. (2008). Coupling reactions and separations for improved synthetic processes. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/26675
Chicago Manual of Style (16th Edition):
Charney, Reagan R. “Coupling reactions and separations for improved synthetic processes.” 2008. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/26675.
MLA Handbook (7th Edition):
Charney, Reagan R. “Coupling reactions and separations for improved synthetic processes.” 2008. Web. 20 Jan 2021.
Vancouver:
Charney RR. Coupling reactions and separations for improved synthetic processes. [Internet] [Doctoral dissertation]. Georgia Tech; 2008. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/26675.
Council of Science Editors:
Charney RR. Coupling reactions and separations for improved synthetic processes. [Doctoral Dissertation]. Georgia Tech; 2008. Available from: http://hdl.handle.net/1853/26675
Georgia Tech
7.
Bryant, Jonathan James.
Oligo(ethylene glycol) chains: applications and advancements in biosensing.
Degree: MS, Chemistry and Biochemistry, 2010, Georgia Tech
URL: http://hdl.handle.net/1853/37147
► Oligo(ethylene glycol) groups have been used as substituents in poly(p-phenyleneethynylene)s (PPEs) to provide solubility, and to boost quantum yield. Properties such as water-solubility and increased…
(more)
▼ Oligo(ethylene glycol) groups have been used as substituents in poly(p-phenyleneethynylene)s (PPEs) to provide solubility, and to boost quantum yield. Properties such as water-solubility and increased quantum yield in aqueous solution make these conjugated systems promising for biosensory applications.
In this thesis, a PPE containing a branched ethylene glycol side chain is synthesized as part of a polymer array for glycan biosensing. I also report that the same side chain can be put to use in a red-emissive polymer to lend water solubility. Another monomeric unit, containing ethylene glycol chains, is incorporated into a PPE to create an ampiphilic polymer. The versatility of these polymers allows them to be used for a variety of purposes, some of which will be described herein.
Advisors/Committee Members: Uwe Bunz (Committee Chair), David Collard (Committee Member), Stefan France (Committee Member).
Subjects/Keywords: Ethylene glycol; Biosensing; Biosensors; Conjugated polymers; Electronics Materials; Fluorescent polymers
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APA (6th Edition):
Bryant, J. J. (2010). Oligo(ethylene glycol) chains: applications and advancements in biosensing. (Masters Thesis). Georgia Tech. Retrieved from http://hdl.handle.net/1853/37147
Chicago Manual of Style (16th Edition):
Bryant, Jonathan James. “Oligo(ethylene glycol) chains: applications and advancements in biosensing.” 2010. Masters Thesis, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/37147.
MLA Handbook (7th Edition):
Bryant, Jonathan James. “Oligo(ethylene glycol) chains: applications and advancements in biosensing.” 2010. Web. 20 Jan 2021.
Vancouver:
Bryant JJ. Oligo(ethylene glycol) chains: applications and advancements in biosensing. [Internet] [Masters thesis]. Georgia Tech; 2010. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/37147.
Council of Science Editors:
Bryant JJ. Oligo(ethylene glycol) chains: applications and advancements in biosensing. [Masters Thesis]. Georgia Tech; 2010. Available from: http://hdl.handle.net/1853/37147
Georgia Tech
8.
White, Bryan M.
Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)].
Degree: PhD, Chemistry and Biochemistry, 2004, Georgia Tech
URL: http://hdl.handle.net/1853/5136
► Polyrotaxanes possess a molecular architecture resembling that of a wheel and axle: linear polymer chains are threaded by cyclic molecules with no covalent bonds linking…
(more)
▼ Polyrotaxanes possess a molecular architecture resembling that of a wheel and axle: linear polymer chains are threaded by cyclic molecules with no covalent bonds linking the two species. One of two methods can be employed for the preparation of polyrotaxanes: a template method to guide threading or an in situ polymerization of monomers in the presence of cyclic molecules. The research described in this dissertation was divided into two distinct sections, which were devoted to each method of polyrotaxane preparation.
The first step of synthesizing polyrotaxanes via the in situ polymerization method was to prepare a cyclic molecule. α,Ï -Dihydroxy-PDMS was cyclized and then efficiently purified by an anion-exchange resin to remove uncyclized, yet anionically charged, linear PDMS.
The second part of this dissertation included examining polyrotaxanes created by the template-directed threading of α-CD onto polyoctene (PO). End-capped PO, which was unthreadable by α-CD, was synthesized from 1,9-decadiene and a monovinyl bulky compound by acyclic diene metathesis. PO and ecPO each were sonicated in aqueous solutions of α -CD; PO formed a white precipitate indicative of a rotaxanated polymer, but no precipitate formed by the addition of ecPO. These results provided evidence that PO had been included within the cavity of α-CD.
Advisors/Committee Members: Haskell Beckham (Committee Chair), Andrew Lyon (Committee Member), David Collard (Committee Member), Laren Tolbert (Committee Member), Pete Ludovice (Committee Member).
Subjects/Keywords: Rotaxanes; Polyrotaxanes; Polymers; Siloxanes; Cyclic
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APA (6th Edition):
White, B. M. (2004). Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)]. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/5136
Chicago Manual of Style (16th Edition):
White, Bryan M. “Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)].” 2004. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/5136.
MLA Handbook (7th Edition):
White, Bryan M. “Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)].” 2004. Web. 20 Jan 2021.
Vancouver:
White BM. Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)]. [Internet] [Doctoral dissertation]. Georgia Tech; 2004. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/5136.
Council of Science Editors:
White BM. Rotaxanated Polymers: I. Synthesis and Purification of Cyclic Polydimethylsiloxane II. Synthesis of Poly[octene-pseudorotaxa-(a-cyclodextrin)]. [Doctoral Dissertation]. Georgia Tech; 2004. Available from: http://hdl.handle.net/1853/5136
Georgia Tech
9.
Keselowsky, Benjamin George.
Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation.
Degree: PhD, Biomedical Engineering, 2004, Georgia Tech
URL: http://hdl.handle.net/1853/8092
► Cell adhesion to proteins adsorbed onto implanted surfaces is particularly important to host responses in biomedical and tissue engineering applications. Biomaterial surface properties influence the…
(more)
▼ Cell adhesion to proteins adsorbed onto implanted surfaces is particularly important to host responses in biomedical and tissue engineering applications. Biomaterial surface properties influence the type, quantity and functional presentation (activity) of proteins adsorbed upon contact with physiological fluids, and modulate subsequent cell response. Cell adhesion to extracellular matrix proteins (e.g. fibronectin) is primarily mediated by the integrin family of cell-surface receptors. Integrins not only anchor cells, supporting cell spreading and migration, but also trigger signals that regulate survival, proliferation and differentiation. A fundamental understanding of the adhesive interactions at the biomaterial interface is critical to the rational design of biomaterial surfaces. Using model surfaces of self-assembled monolayers of alkanethiols on gold presenting well-defined surface chemistries (CH3, OH, COOH, NH2), we investigated the effects of surface chemistry on osteoblastic differentiation. We report that surface chemistry effectively modulates fibronectin adsorption, integrin binding, focal adhesion assembly and signaling to direct the osteoblast cellular functions of adhesion strength, gene expression and matrix mineralization. Specifically, surfaces presenting OH and NH2 functionalities provide enhanced functional presentation of adsorbed fibronectin, promoting specificity of integrin binding as well as elevating focal adhesion assembly and signaling. Furthermore, the OH and NH2 surfaces supported elevated levels of osteoblast differentiation as evidenced by osteoblast-specific gene expression and matrix mineralization. These results contribute to the development of design principles for the engineering of surfaces that direct cell adhesion for biomedical and tissue engineering applications. In particular, the understanding provided by this analysis may be useful in the engineering of surface properties for bone tissue repair and regeneration.
Advisors/Committee Members: Andres J. Garcia (Committee Chair), Cheng Zhu, David Collard, Elliot Chaikoff, Harish Radhakrishna, and Robert Guldberg (Committee Members).
Subjects/Keywords: Protein adsorption; Osteoblast; Cell adhesion; Surface chemistry; Integrin; Fibronectin
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APA (6th Edition):
Keselowsky, B. G. (2004). Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/8092
Chicago Manual of Style (16th Edition):
Keselowsky, Benjamin George. “Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation.” 2004. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/8092.
MLA Handbook (7th Edition):
Keselowsky, Benjamin George. “Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation.” 2004. Web. 20 Jan 2021.
Vancouver:
Keselowsky BG. Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation. [Internet] [Doctoral dissertation]. Georgia Tech; 2004. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/8092.
Council of Science Editors:
Keselowsky BG. Engineering surfaces to direct integrin binding and signaling to promote osteoblast differentiation. [Doctoral Dissertation]. Georgia Tech; 2004. Available from: http://hdl.handle.net/1853/8092
Georgia Tech
10.
Englert, Brian Carl.
Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry.
Degree: PhD, Chemistry and Biochemistry, 2005, Georgia Tech
URL: http://hdl.handle.net/1853/7102
► The synthesis and investigation of new types of poly(paraphenyleneethynylene)s, PPEs, is presented. PPEs which are Jacketed are there by shielded from electronic and plararization effects…
(more)
▼ The synthesis and investigation of new types of poly(paraphenyleneethynylene)s, PPEs, is presented. PPEs which are Jacketed are there by shielded from electronic and plararization effects in the solid state. Other PPEs contain pendent groups which may functionalized before or after polymerization to afford two versitle routes to newly functionalized polymeric materials. Based on the PPE structure, metals may be introduced and these polymers may be used as precursors for other types of materials such as ceramics.
Advisors/Committee Members: Uwe Bunz (Committee Chair), Anselm Griffin (Committee Member), David Collard (Committee Member), Joseph Perry (Committee Member), Laren Tolbert (Committee Member).
Subjects/Keywords: Poly(paraphenyleneethynylene)s
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APA (6th Edition):
Englert, B. C. (2005). Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/7102
Chicago Manual of Style (16th Edition):
Englert, Brian Carl. “Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry.” 2005. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/7102.
MLA Handbook (7th Edition):
Englert, Brian Carl. “Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry.” 2005. Web. 20 Jan 2021.
Vancouver:
Englert BC. Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry. [Internet] [Doctoral dissertation]. Georgia Tech; 2005. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/7102.
Council of Science Editors:
Englert BC. Jacketed and Functionalized Poly(paraphenyleneethynylene)s: Nonaggregating Conjugated Polymers and Materials Functionalized Through Click-Chemistry. [Doctoral Dissertation]. Georgia Tech; 2005. Available from: http://hdl.handle.net/1853/7102
Georgia Tech
11.
Wei, Shuting.
Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers.
Degree: PhD, Chemistry and Biochemistry, 2007, Georgia Tech
URL: http://hdl.handle.net/1853/24817
► Advantages such as chemical, mechanical and thermal stability together with high selectivity for the templated analyte render molecularly imprinted polymers MIPs interesting alternatives to routinely…
(more)
▼ Advantages such as chemical, mechanical and thermal stability together with high selectivity for the templated analyte render molecularly imprinted polymers MIPs interesting alternatives to routinely applied separation materials or antibodies. Nevertheless, many factors such as the choice of functional monomer, cross-linker, and porogenic solvent, as well as the ratio between template, functional monomer, and cross-linker will affect the resulting imprinting efficiency and polymer particle size and morphology. The research described in this thesis contributes to the development of new synthetic strategies for the generation of imprinted micro- and nanospheres for 17beta-estradiol (E2) focusing on accurate control and optimization of the governing parameters for precipitation polymerization, including the polymerization temperature and the cross-linker, yielding a one-step synthetic approach with superior control on the bead diameter, shape, monodispersity and imprinting efficiency. Thus synthesized imprinting materials for E2 were successfully applied in HPLC separation, solid phase extraction and radioligand binding assays. As the optimization of imprinted materials is based on fundamental understanding of the binding site properties, the investigations is aimed at establishing a more rational basis for further tailoring imprinted materials to the desired analytical application. The relationships between the particle porosity and rebinding properties were detailed, providing useful guidelines for controlling the particle properties for the desired application including, SPE pre-concentration, HPLC separations, and biomimetic binding assays. Furthermore, analytical techniques (1H-NMR and IR, etc.) and molecular modeling were combined in this thesis to facilitate advanced understanding of the fundamental principles governing selective recognition of molecularly imprinted polymers at a molecular level. The molecular interactions involved in the templating process of molecularly imprinted polymers based on the self-assembly approach were simulated in molecular dynamic simulation model by building a modeling system include all the imprinting components with correct ratio, which has never been reported before. Molecular level interactions such as hydrogen bonding, π-π stacking interactions as well as the free energy governing complex formation of E2 with the functional monomers 4-vinylpyridine (4VP) and methacrylic acid (MAA), and the cross-linker divinylbenzene (DVB) were discussed.
Advisors/Committee Members: Boris Mizaikoff (Committee Chair), Andrew Lyon (Committee Member), Ching-Hua Huang (Committee Member), David Collard (Committee Member), Facundo M. Fernandez (Committee Member).
Subjects/Keywords: Molecular modeling; Spectroscopic Analysis; Molecular imprinted polymers; Solid phase extraction; Liquid chromatographic separation; Chemical templates; Imprinted polymers Synthesis; Molecular imprinting
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APA (6th Edition):
Wei, S. (2007). Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/24817
Chicago Manual of Style (16th Edition):
Wei, Shuting. “Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers.” 2007. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/24817.
MLA Handbook (7th Edition):
Wei, Shuting. “Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers.” 2007. Web. 20 Jan 2021.
Vancouver:
Wei S. Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers. [Internet] [Doctoral dissertation]. Georgia Tech; 2007. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/24817.
Council of Science Editors:
Wei S. Capturing molecules with templated materials: analysis and rational design of molecularly imprinted polymers. [Doctoral Dissertation]. Georgia Tech; 2007. Available from: http://hdl.handle.net/1853/24817
Georgia Tech
12.
Aronson, Joshua Boyer.
The Synthesis and Characterization of Energetic Materials From Sodium Azide.
Degree: PhD, Chemistry and Biochemistry, 2004, Georgia Tech
URL: http://hdl.handle.net/1853/7597
► A tetrazole is a 5-membered ring containing 4 nitrogens and 1 carbon. Due to its energetic potential and structural similarity to carboxylic acids, this ring…
(more)
▼ A tetrazole is a 5-membered ring containing 4 nitrogens and 1 carbon. Due to its energetic potential and structural similarity to carboxylic acids, this ring system has a wide number of applications. In this thesis, a new and safe sustainable process to produce tetrazoles was designed that acheived high yields under mild conditions. Also, a technique was developed to form a trityl-protected tetrazole in situ. The rest of this work involved the exploitation of the energetic potential of tetrazoles. This moiety was successfully applied in polymers, ionic liquids, foams, and gels. The overall results from these experiments illustrate the fact that tetrazoles have the potential to serve as a stable alternative to the troublesome azido group common in many energetic materials. Due to these applications, the tetrazole moiety is a very important entity.
Advisors/Committee Members: Liotta, Charles (Committee Chair), Charles Eckert (Committee Co-Chair), David Collard (Committee Member), Julia Kubanek (Committee Member), Kent Richman (Committee Member).
Subjects/Keywords: Energetic materials; Tetrazoles; Sodium azide; Tetrazoles; Sodium compounds; Propellants Thermomechanical properties; Propellants Analysis; Explosives Thermomechanical properties; Explosives Analysis; Azides
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APA (6th Edition):
Aronson, J. B. (2004). The Synthesis and Characterization of Energetic Materials From Sodium Azide. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/7597
Chicago Manual of Style (16th Edition):
Aronson, Joshua Boyer. “The Synthesis and Characterization of Energetic Materials From Sodium Azide.” 2004. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/7597.
MLA Handbook (7th Edition):
Aronson, Joshua Boyer. “The Synthesis and Characterization of Energetic Materials From Sodium Azide.” 2004. Web. 20 Jan 2021.
Vancouver:
Aronson JB. The Synthesis and Characterization of Energetic Materials From Sodium Azide. [Internet] [Doctoral dissertation]. Georgia Tech; 2004. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/7597.
Council of Science Editors:
Aronson JB. The Synthesis and Characterization of Energetic Materials From Sodium Azide. [Doctoral Dissertation]. Georgia Tech; 2004. Available from: http://hdl.handle.net/1853/7597
Georgia Tech
13.
Zhang, Xiefei.
Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers.
Degree: PhD, Textile and fiber engineering, 2004, Georgia Tech
URL: http://hdl.handle.net/1853/7610
► Single wall carbon nanotubes (SWNT) have been extensively studied over the last decade due to their excellent comprehensive properties for a variety of applications. This…
(more)
▼ Single wall carbon nanotubes (SWNT) have been extensively studied over the last decade due to their excellent comprehensive properties for a variety of applications. This study is focused on the applications of SWNTs as reinforcement for polymer matrices. Due to van der Waal interactions, SWNTs form bundles of about 30 nm diameters. In order to take full advantage of the SWNT mechanical properties, SWNT must exfoliate or at least disperse in small diameter bundle size. Optical microscopy and SEM only give qualitative information of dispersion. Quantitative characterization through TEM or AFM can be time consuming in order to get statistical result. In this study, simple method is developed to quantitatively estimate the size of SWNT bundle in dispersion based on the geometry controlled electrical percolation behavior. The SWNTs can be dispersed /exfoliated via PVP wrapped SWNT aqueous dispersion assisted by surfactants such as sodium dodycel sulfate. PVA / SWNT composite films prepared through PVP wrapped SWNTs exhibit improved mechanical properties as well as the evidence of load transfer from the polymer matrix to the SWNT as monitored by the Raman spectroscopy. SWNT can also be well dispersed into PVA/DMSO/H2O solution. Gel spinning of PVA/SWNT composite fiber has been successfully carried out with improved mechanical properties. Functionalized tubes can be used to enhance SWNT dispersion and exfoliation. Oxidation in strong acids is one method used for functionalizing nanotubes. SWNTs have been functionalized in nitric acid. The structure and properties of films (buckypaper) processed from nitric acid functionalized tubes have been studied exhibiting high tensile strength and high electrical conductivity. Nitric acid treatment results in selective degradation of the small diameter tubes.
Advisors/Committee Members: Satish Kumar (Committee Chair), Anselm Griffin (Committee Member), David Collard (Committee Member), Hamid Garmestani (Committee Member), Pete Ludovice (Committee Member), Samuel Graham (Committee Member).
Subjects/Keywords: SWNT; Polymers; Composite; Film; Fiber; Nanostructured materials; Polymeric composites
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APA (6th Edition):
Zhang, X. (2004). Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/7610
Chicago Manual of Style (16th Edition):
Zhang, Xiefei. “Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers.” 2004. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/7610.
MLA Handbook (7th Edition):
Zhang, Xiefei. “Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers.” 2004. Web. 20 Jan 2021.
Vancouver:
Zhang X. Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers. [Internet] [Doctoral dissertation]. Georgia Tech; 2004. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/7610.
Council of Science Editors:
Zhang X. Studies on Single Wall Carbon Nanotube and Polymer Composite Films and Fibers. [Doctoral Dissertation]. Georgia Tech; 2004. Available from: http://hdl.handle.net/1853/7610
Georgia Tech
14.
Roberson, Luke Bennett.
Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells.
Degree: PhD, Chemistry and Biochemistry, 2005, Georgia Tech
URL: http://hdl.handle.net/1853/7629
► The objective of this work is to understand how the thin film characteristics of p-type organic and polymer semiconductors affect their electronic properties in microelectronic…
(more)
▼ The objective of this work is to understand how the thin film characteristics of p-type organic and polymer semiconductors affect their electronic properties in microelectronic applications. To achieve this goal, three main objectives were drawn out: (1) to create single-crystal organic field-effect transistors and measure the intrinsic charge carrier mobility, (2) to develop a platform for measuring and depositing polymer thin films for organic field-effect transistors, and (3) to deposit polythiophene thin films for inorganic-organic hybrid solar cells and determine how thin film properties effect device performance.
Pentacene single-crystal field-effect transistors (OFETs) were successfully manufactured on crystals grown via horizontal vapor-phase reactors designed for simultaneous ultrapurification and crystal growth. These OFETs led to calculated pentacene field-effect mobility of 2.2 cm2/Vs. During the sublimation of pentacene at atmospheric pressure, a pentacene disporportionation reaction was observed whereby pentacene reacted with itself to form a peripentacene, a 2:1 cocrystal of pentacene:6,13-dihydropentacene and 6,13-dihydropentacene. This has led to the proposal of a possible mechanism for the observed disproportionation reaction similar to other polyaromatic hydrocarbons, which may be a precursor for explaining the formation of graphite.
Several silicon-based and PET-based field-effect transistor platforms were developed for the measurement of mobility of materials in the thin film state. These platforms were critically examined against one another and the single-crystal devices in order to determine the optimal device design for highest possible mobility data, both theoretically based on silicon technology and commercially based on individual devices on flexible substrates. Novel FET device designs were constructed with a single gate per device on silicon and PET as well as the commonly used common-gate device. It was found that the deplanarization effects and poor gate insulator quality of the individual gate devices led to lower overall performance when compared to the common gate approach; however, good transistor behavior was observed with field modulation.
Additionally, these thin films were implemented into inorganic-organic hybrid and purely organic solid-state photovoltaic cells. A correlation was drawn between the thin film properties of the device materials and the overall performance of the device. It was determined that each subsequent layer deposited on the device led to a planarization effect, and that the more pristine the individual layer, the better device performance. The hybrid cells performed at VOC = 0.8V and JSC = 55A/cm2.
Advisors/Committee Members: Laren Tolbert (Committee Chair), Art Janata (Committee Member), David Collard (Committee Member), Marcus Weck (Committee Member), Mohan Srinivasarao (Committee Member), Uwe Bunz (Committee Member).
Subjects/Keywords: Transistors; Thin films; Solar cells; OFET; Organic semiconductors; Field-effect transistors; Thin film transistors; Solar cells
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APA (6th Edition):
Roberson, L. B. (2005). Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/7629
Chicago Manual of Style (16th Edition):
Roberson, Luke Bennett. “Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells.” 2005. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/7629.
MLA Handbook (7th Edition):
Roberson, Luke Bennett. “Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells.” 2005. Web. 20 Jan 2021.
Vancouver:
Roberson LB. Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells. [Internet] [Doctoral dissertation]. Georgia Tech; 2005. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/7629.
Council of Science Editors:
Roberson LB. Understanding organic thin film properties for microelectronic organic field-effect transistors and solar cells. [Doctoral Dissertation]. Georgia Tech; 2005. Available from: http://hdl.handle.net/1853/7629
Georgia Tech
15.
Shotwell, Sandra Leigh.
Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers.
Degree: PhD, Chemistry and Biochemistry, 2006, Georgia Tech
URL: http://hdl.handle.net/1853/10449
► In the first part of this thesis, the synthesis, characterization and investigation of ortho-phenyleneethynylenes containing heterocycles, are presented. These compounds display changes in absorption and…
(more)
▼ In the first part of this thesis, the synthesis, characterization and investigation of ortho-phenyleneethynylenes containing heterocycles, are presented. These compounds display changes in absorption and emission spectra varying with their functionalization and size. These compounds also have the ability to coordinate with metals. The synthesis of coordination compounds and their crystallographic data are reported. The synthesis and characterization of tetraethynyl thiophene compounds containing pyridines are also presented. These compounds exhibit differences in absorption and emission spectra upon exposure to various metal salts. The final topic to be discussed is the synthesis and characterization of diphenyl amine polymers. These polymers could in principle be used in NLO applications or light emitting devices.
Advisors/Committee Members: Dr. Uwe Bunz (Committee Chair), Dr. Anselm Griffin (Committee Member), Dr. David Collard (Committee Member), Dr. Joseph Perry (Committee Member), Dr. Laren Tolbert (Committee Member).
Subjects/Keywords: Polymers; Thiophenes Synthesis; Pyridinium compounds Synthesis; Ligands; Diphenylamine Synthesis; Oligomers
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APA (6th Edition):
Shotwell, S. L. (2006). Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/10449
Chicago Manual of Style (16th Edition):
Shotwell, Sandra Leigh. “Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers.” 2006. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/10449.
MLA Handbook (7th Edition):
Shotwell, Sandra Leigh. “Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers.” 2006. Web. 20 Jan 2021.
Vancouver:
Shotwell SL. Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers. [Internet] [Doctoral dissertation]. Georgia Tech; 2006. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/10449.
Council of Science Editors:
Shotwell SL. Synthesis and Characterization of ortho-Phenyleneethynylenes and Diphenylamine Polymers. [Doctoral Dissertation]. Georgia Tech; 2006. Available from: http://hdl.handle.net/1853/10449
Georgia Tech
16.
Carlise, Joseph Raymond.
Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers.
Degree: PhD, Chemistry and Biochemistry, 2006, Georgia Tech
URL: http://hdl.handle.net/1853/10571
► This thesis begins with a brief overview of current strategies used in the synthesis of side-chain functionalizad polymers and materials. The discussion then focuses more…
(more)
▼ This thesis begins with a brief overview of current strategies used in the synthesis of side-chain functionalizad polymers and materials. The discussion then focuses more explicitly on transition metal-based motifs and methodologies that are employed in polymer functionalization and continues with a more detailed overview of this field.
The primary hypothesis that is addressed herein is that combining the versatility and strength of metal-ligand interactions with the efficiency and functional group tolerance of ROMP comprises a useful method of generating a variety of functionalized polymers and materials via side-chain metal coordination. Thus, the goal is to test this hypothesis by synthesizing functionalized polymers with a range of useful properties to demonstrate the relevance and importance of this methodology, by employing several different strategies to show the synthetic ease by which the materials can be realized.
The strategies and methods discussed in the synthesis of side-chain functionalized polymers are divided into three subgroups: (1) pre-polymerization functionalization, in which all of the modifications take place on the monomer with polymerization as the last step, (2) post-polymerization functionalization, in which the polymer itself is subsequently modified, and (3) combinations of the first two strategies.
It is shown that useful functional polymers and materials can be synthesized by any of the above strategies, and representative examples of each are given in both the introduction and in the body of work presented.
Modes of functionalization are all based on transition metal coordination, and polymerizations are primarily carried out via ROMP. Metal coordination is shown to be a useful technique for functionalizing polymers, to creating supported emissive complexes, to modulating solution viscosity.
Finally, conclusions are drawn regarding the various strategies presented herein, and potential future directions are discussed.
Advisors/Committee Members: Prof. Marcus Weck (Committee Chair), Prof. Charles Liotta (Committee Member), Prof. David Collard (Committee Member), Prof. Kent Barefield (Committee Member), Prof. Will Rees (Committee Member).
Subjects/Keywords: ATRP; Bipyridine; Chelation; Copolymers; Functional materials; Graft; Guar; Hydrolysis; Iridium; Ligands; Luminescent polymers; OLED; Photoluminescence; Photoluminescent; Polymerization; Polymers synthesis; ROMP; Ruthenium; Transition metal; Transition metal complexes; Viscosity
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APA (6th Edition):
Carlise, J. R. (2006). Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/10571
Chicago Manual of Style (16th Edition):
Carlise, Joseph Raymond. “Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers.” 2006. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/10571.
MLA Handbook (7th Edition):
Carlise, Joseph Raymond. “Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers.” 2006. Web. 20 Jan 2021.
Vancouver:
Carlise JR. Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers. [Internet] [Doctoral dissertation]. Georgia Tech; 2006. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/10571.
Council of Science Editors:
Carlise JR. Poly(norbornene) supported side-chain coordination complexes: an efficient route to functionalized polymers. [Doctoral Dissertation]. Georgia Tech; 2006. Available from: http://hdl.handle.net/1853/10571
Georgia Tech
17.
Sibert, Robin S.
Redox active tyrosine residues in biomimetic beta hairpins.
Degree: PhD, Chemistry and Biochemistry, 2009, Georgia Tech
URL: http://hdl.handle.net/1853/29753
► Biomimetic peptides are autonomously folding secondary structural units designed to serve as models for examining processes that occur in proteins. Although de novo biomimetic peptides…
(more)
▼ Biomimetic peptides are autonomously folding secondary structural units designed to serve as models for examining processes that occur in proteins. Although de novo biomimetic peptides are not simply abbreviated versions of proteins already found in nature, designing biomimetic peptides does require an understanding of how native proteins are formed and stabilized. The discovery of autonomously folding fragments of ribonuclease A and tendamistat pioneered the use of biomimetic peptides for determining how the polypeptide sequence stabilizes formation of alpha helices and beta hairpins in aqueous and organic solutions. A set of rules for constructing stable alpha helices have now been established. There is no exact set of rules for designing beta hairpins; however, some factors that must be considered are the identity of the residues in the turn and non-covalent interactions between amino acid side chains. For example, glycine, proline, aspargine, and aspartic acid are favored in turns. Non-covalent interactions that stabilize hairpin formation include salt bridges, pi-stacked aromatic interactions, cation-pi interactions, and hydrophobic interactions. The optimal strand length for beta hairpins depends on the numbers of stabilizing non-covalent interactions and high hairpin propensity amino acids in the specific peptide being designed. Until now, de novo hairpins have not previously been used to examine biological processes aside from protein folding. This thesis uses de novo designed biomimetic peptides as tractable models to examine how non-covalent interactions control the redox properties of tyrosine in enzymes.
The data in this study demonstrate that proton transfer to histidine, a hydrogen bond to arginine, and a pi-cation interaction create a peptide environment that lowers the midpoint potential of tyrosine in beta hairpins. Moreover, these interactions contribute equally to control the midpoint potential. The data also show that hydrogen bonding is not the sole determinant of the midpoint potential of tyrosine. Finally, the data suggest that the Tyr 160D2-Arg 272CP47 pi-cation interaction contributes to the differences in redox properties between Tyr 160 and Tyr 161 of photosystem II.
Advisors/Committee Members: Bridgette Barry (Committee Chair), David Collard (Committee Member), Ingeborg Schmidt-Krey (Committee Member), Jake Soper (Committee Member), Mira Josowicz (Committee Member).
Subjects/Keywords: Midpoint potential; Tyrosine; Proton coupled electron transfer; Photosystem II; Tyrosine; Biomimetics; Peptides Synthesis
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APA (6th Edition):
Sibert, R. S. (2009). Redox active tyrosine residues in biomimetic beta hairpins. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/29753
Chicago Manual of Style (16th Edition):
Sibert, Robin S. “Redox active tyrosine residues in biomimetic beta hairpins.” 2009. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/29753.
MLA Handbook (7th Edition):
Sibert, Robin S. “Redox active tyrosine residues in biomimetic beta hairpins.” 2009. Web. 20 Jan 2021.
Vancouver:
Sibert RS. Redox active tyrosine residues in biomimetic beta hairpins. [Internet] [Doctoral dissertation]. Georgia Tech; 2009. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/29753.
Council of Science Editors:
Sibert RS. Redox active tyrosine residues in biomimetic beta hairpins. [Doctoral Dissertation]. Georgia Tech; 2009. Available from: http://hdl.handle.net/1853/29753
Georgia Tech
18.
Meyers, Amy.
The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes.
Degree: PhD, Chemistry and Biochemistry, 2004, Georgia Tech
URL: http://hdl.handle.net/1853/6985
► The use of polymers in electro-optical devices, especially light-emitting diodes (OLEDs), has become very popular in recent years, due to their ease of processability. The…
(more)
▼ The use of polymers in electro-optical devices, especially light-emitting diodes (OLEDs), has become very popular in recent years, due to their ease of processability. The major drawback of using polymers in these systems is their time-consuming synthesis when trying to improve upon their physical properties. For example, each time a new color or better conducting properties are desired, a new monomer must be synthesized. To circumvent these problems, the system described in this work is designed to connect the well-known chromophore aluminum tris(8-hydroxyquinoline) (Alq3) to a norbornene monomer unit, followed by polymerization using ring-opening metathesis polymerization (ROMP), thus allowing for the processability of a polymer while maintaining the fluorescent properties of the metalloquinolate.
The benefit of this system is that the monomers can be easily altered in order to tune color emission or to enhance the polymer properties. Some of the alterations include changing the metal center from aluminum to zinc in order to improve electron injection, adding substituents to the 8-hydroxyquinoline ligand in order to tune the emission color, and copolymerizing the Alq3-monomer with other norbornene monomers containing either a hole- or an electron-transport material side-chain to improve conductivity. These alterations lead to improved device performance and, more importantly, to a new method of designing polymeric systems for use in electronic devices.
Advisors/Committee Members: Marcus Weck (Committee Chair), Charles Liotta (Committee Member), Christopher Jones (Committee Member), David Collard (Committee Member), E. Kent Barefield (Committee Member).
Subjects/Keywords: Metaloquinolates; Fluorescent polymers; Poly(norbornenes); Light emitting diodes; Organic thin films; Fluorescent polymers
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APA (6th Edition):
Meyers, A. (2004). The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/6985
Chicago Manual of Style (16th Edition):
Meyers, Amy. “The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes.” 2004. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021.
http://hdl.handle.net/1853/6985.
MLA Handbook (7th Edition):
Meyers, Amy. “The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes.” 2004. Web. 20 Jan 2021.
Vancouver:
Meyers A. The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes. [Internet] [Doctoral dissertation]. Georgia Tech; 2004. [cited 2021 Jan 20].
Available from: http://hdl.handle.net/1853/6985.
Council of Science Editors:
Meyers A. The Design and Synthesis of Metal-Functionalized Poly(norbornenes) for Potential Use in Light-Emitting Diodes. [Doctoral Dissertation]. Georgia Tech; 2004. Available from: http://hdl.handle.net/1853/6985
. 
Open Access Theses and Dissertations
