subject:(Reversible ionic liquids)

Georgia Tech

1. Ethier, Amy Lynn. Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis.

Degree: PhD, Chemical and Biomolecular Engineering, 2013, Georgia Tech

URL: http://hdl.handle.net/1853/52913

► A multidisciplinary approach has been applied to the development of sustainable technologies for three industrially relevant projects. Reversible ionic liquids are novel carbon dioxide capture… (more)

Subjects/Keywords: Carbon dioxide capture; Amine protection; Nanoparticle synthesis; Reversible ionic Liquids

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APA (6^th Edition):

Ethier, A. L. (2013). Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/52913

Chicago Manual of Style (16^th Edition):

Ethier, Amy Lynn. “Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis.” 2013. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/52913.

MLA Handbook (7^th Edition):

Ethier, Amy Lynn. “Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis.” 2013. Web. 20 Jan 2021.

Vancouver:

Ethier AL. Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis. [Internet] [Doctoral dissertation]. Georgia Tech; 2013. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/52913.

Council of Science Editors:

Ethier AL. Applications of reversible and sustainable amine-based chemistries: carbon dioxide capture, in situ amine protection and nanoparticle synthesis. [Doctoral Dissertation]. Georgia Tech; 2013. Available from: http://hdl.handle.net/1853/52913

Princeton University

2. Vallon, Matthew. The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces .

Degree: PhD, 2017, Princeton University

URL: http://arks.princeton.edu/ark:/88435/dsp019019s4982

► Reversible electrochemical mirrors are a relatively recent field of research wherein an electrochemical reaction, in this case the electrodeposition of silver, is used to control… (more)

▼ Reversible electrochemical mirrors are a relatively recent field of research wherein an electrochemical reaction, in this case the electrodeposition of silver, is used to control the reflectivity of a transparent conductive window. This can be applied to the infrared spectrum of light as well, however doing so presents unique challenges as most transparent conductive materials are not transparent to infrared light. To address this challenge, graphene can be utilized given its atomic thickness and relatively high conductivity may allow for a window to be transparent while also serving as an electrode for silver electrodeposition. Further challenges can be raised when these applications are brought into low-pressure or vacuum environments. While most electrolytes used for these applications will evaporate under low-pressure or vacuum conditions, ionic liquids are a unique class of electrolytes capable of tolerating vacuum conditions without undergoing evaporation or mass loss. In this work, we have addressed both of these challenges to further the goal of a vacuum-compatible reversible electrochemical mirror device that is effective with infrared light. Thus we have investigated the use of various chemical forms of graphene particles and carbon nanotubes, to produce thin conductive films on infrared-transparent sapphire windows. We have also studied the electrodeposition process and long-term reversibility of silver in the ionic liquid 3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM TFSI) on model electrode systems. Transparent indium-tin oxide and opaque graphene films were used to observe changes in transparency and reflectivity, and to model the deposition onto graphene-like materials, respectively. Additionally, the use of germanium as an infrared-transparent conductive was investigated. Also presented are results on the oxidation of bismuth chalcogenide topological insulators from ambient conditions. Topological insulators are a recently discovered semiconductor material possessing interesting electronic states allowing them to conduct electricity like a metal along the surfaces. Furthermore, the electrons in this surface conduction possess a spin that is directly influenced by the electron’s momentum. However, these states are very sensitive to chemical effects, such as those brought on by atmospheric exposure. Thus we have studied the systematic exposure of atmospheric reactants on these material surfaces, and monitored the change via photoelectron spectroscopic methods. Advisors/Committee Members: Bernasek, Steven L (advisor).

Subjects/Keywords: Electrochemistry; Ionic Liquids; Reversible Electrochemical Mirror; Surface Science; Topological Insulators; Transparent Carbon Films

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APA (6^th Edition):

Vallon, M. (2017). The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces . (Doctoral Dissertation). Princeton University. Retrieved from http://arks.princeton.edu/ark:/88435/dsp019019s4982

Chicago Manual of Style (16^th Edition):

Vallon, Matthew. “The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces .” 2017. Doctoral Dissertation, Princeton University. Accessed January 20, 2021. http://arks.princeton.edu/ark:/88435/dsp019019s4982.

MLA Handbook (7^th Edition):

Vallon, Matthew. “The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces .” 2017. Web. 20 Jan 2021.

Vancouver:

Vallon M. The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces . [Internet] [Doctoral dissertation]. Princeton University; 2017. [cited 2021 Jan 20]. Available from: http://arks.princeton.edu/ark:/88435/dsp019019s4982.

Council of Science Editors:

Vallon M. The Reversible Electrochemical Deposition of Silver onto Transparent Conductive Films and The Effects of Ambient Oxidation on Bismuth Chalcogenide Topological Insulator Surfaces . [Doctoral Dissertation]. Princeton University; 2017. Available from: http://arks.princeton.edu/ark:/88435/dsp019019s4982

Virginia Tech

3. Cheng, Shijing. Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers.

Degree: PhD, Chemistry, 2011, Virginia Tech

URL: http://hdl.handle.net/10919/77185

► Non-covalent interactions including nucleobase hydrogen bonding and phosphonium/ammonium ionic aggregation were studied in block and random polymers synthesized using controlled radical polymerization techniques such as… (more)

▼ Non-covalent interactions including nucleobase hydrogen bonding and phosphonium/ammonium ionic aggregation were studied in block and random polymers synthesized using controlled radical polymerization techniques such as nitroxide mediated polymerization (NMP) and reversible addition-fragmentation chain transfer polymerization (RAFT). Non-covalent interactions were expected to increase the effective molecular weight of the polymeric precursors through intermolecular associations and to induce microphase separation. The influence of non-covalent association on the structure/property relationships of these materials were studied in terms of physical properties (tensile, DMA, rheology) as well as morphological studies (AFM, SAXS). Ionic interactions, which possess stronger interaction energies than hydrogen bonds (~150 kJ/mol) were studied in the context of phosphonium-containing acrylate triblock (ABA) copolymers and random copolymers. Phosphonium-containing ionic liquid monomers with different alkyl substituent lengths and counterions enabled an investigation of the effects of ionic aggregation of phosphonium cations on the polymer physical properties. The polymerization of styrenic phosphonium-containing ionic liquid monomers using a difunctional alkoxyamine initiator, DEPN2, afforded an ABA triblock copolymer with an n-butyl acrylate soft center block and symmetric phosphonium-containing external reinforcing blocks. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) of triblock copolymers revealed pronounced microphase separation at the nanoscale. Phosphonium aggregation governed block copolymer flow activation energies. In random copolymers, the phosphonium cations only weakly aggregated, which strongly depended on the length of alkyl substituents and the type of counterions. Acrylate random copolymers consisting of quaternary ammonium functionalities were synthesized using reversible addition-fragmentation chain transfer polymerization (RAFT). The obtained copolymers possessed controlled compositions and narrow molecular weight distributions with molecular weights ranging from Mn =50,000 to 170,000 g/mol. DMA evidenced the weak aggregation of ammonium cations in the solid state. Additionally, this ionomer was salt-responsive in NaCl aqueous solutions. Hydrogen bonding, a dynamic interaction with intermediate enthalpies (10-40 kJ/mol) was introduced through complementary heterocyclic DNA nucleobases such as adenine, thymine and uracil. Our investigations in this field have focused on the use of DNA nucleobase pair interactions to control polymer self-assembly and rheological behavior. Novel acrylic adenine- and thymine-containing monomers were synthesized from aza-Michael addition reaction. The long alkyl spacers between nucleobase and polymer backbone afforded structural flexibility in self-assembly process. Adenine-containing polyacrylates exhibited unique morphologies due to adenine-adenine π-π interactions. The complementary hydrogen bonding of adenine and thymine resulted in… Advisors/Committee Members: Long, Timothy E. (committeechair), Davis, Richey M. (committee member), Moore, Robert Bowen III (committee member), Riffle, Judy S. (committee member), Turner, S. Richard (committee member).

Subjects/Keywords: non-covalent interactions; molecular recognition; hydrogen bonding; ionomers; nitroxide mediated polymerization; reversible addition-fragmentation chain transfer p; nucleobase; ammonium; phosphonium; polyacrylates; Michael addition; ionic liquids

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APA (6^th Edition):

Cheng, S. (2011). Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers. (Doctoral Dissertation). Virginia Tech. Retrieved from http://hdl.handle.net/10919/77185

Chicago Manual of Style (16^th Edition):

Cheng, Shijing. “Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers.” 2011. Doctoral Dissertation, Virginia Tech. Accessed January 20, 2021. http://hdl.handle.net/10919/77185.

MLA Handbook (7^th Edition):

Cheng, Shijing. “Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers.” 2011. Web. 20 Jan 2021.

Vancouver:

Cheng S. Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers. [Internet] [Doctoral dissertation]. Virginia Tech; 2011. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/10919/77185.

Council of Science Editors:

Cheng S. Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers. [Doctoral Dissertation]. Virginia Tech; 2011. Available from: http://hdl.handle.net/10919/77185

4. Hart, Ryan J. Designing switchable solvents for sustainable process development.

Degree: PhD, Chemical Engineering, 2010, Georgia Tech

URL: http://hdl.handle.net/1853/39631

► Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on… (more)

Subjects/Keywords: Reversible ionic liquids; CO₂ capture; Reactions; Separations; Solvents; Ionic solutions; Sustainable engineering

…6 CHAPTER 2 SYNTHESIS AND CHARACTERIZATION OF REVERSIBLE IONIC LIQUIDS… …8 INTRODUCTION AND BACKGROUND ON REVERSIBLE IONIC LIQUIDS ...................... 8 ONE… …COMPONENT REVERSIBLE IONIC LIQUIDS ...................................................11 Materials… …14 Structures of One-Component Reversible Ionic Liquids .............................15 1… …36 TWO-COMPONENT REVERSIBLE IONIC LIQUIDS…

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Hart, R. J. (2010). Designing switchable solvents for sustainable process development. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/39631

Chicago Manual of Style (16^th Edition):

Hart, Ryan J. “Designing switchable solvents for sustainable process development.” 2010. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/39631.

MLA Handbook (7^th Edition):

Hart, Ryan J. “Designing switchable solvents for sustainable process development.” 2010. Web. 20 Jan 2021.

Vancouver:

Hart RJ. Designing switchable solvents for sustainable process development. [Internet] [Doctoral dissertation]. Georgia Tech; 2010. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/39631.

Council of Science Editors:

Hart RJ. Designing switchable solvents for sustainable process development. [Doctoral Dissertation]. Georgia Tech; 2010. Available from: http://hdl.handle.net/1853/39631

5. Bouchardy, Lucie. Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction.

Degree: Docteur es, Chimie, 2016, Université Paris-Saclay (ComUE)

URL: http://www.theses.fr/2016SACLS400

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Ce travail de thèse porte, dans un premier temps, sur le développement d'une nouvelle synthèse de liquides ioniques chiraux réversibles, en système mono-composant, à partir… (more)

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Ce travail de thèse porte, dans un premier temps, sur le développement d'une nouvelle synthèse de liquides ioniques chiraux réversibles, en système mono-composant, à partir d'aminoacides naturels. La réversibilité a été démontrée par RMN, par analyse thermogravimétrique et par calorimétrie différentielle à balayage. Ces composés ont été testés comme catalyseurs organiques dans la réaction d’addition de Michael asymétrique. Des rendements modérés ont été obtenus. Les silylamines chirales, précurseurs des liquides ioniques chiraux réversibles, ont été évaluées dans la synthèse de Warfarine via une addition de Michael asymétrique. De bons rendements ont été obtenus. Toutefois, ces catalyseurs n'ont permis de conduire qu'à de faibles énantiosélectivités. L'utilisation de liquides ioniques réversibles comme groupements protecteurs temporaires en glycochimie, pour la synthèse de disaccharides, a été mise en œuvre. Dans un second temps, de nouveaux sels d'imidazolinium chiraux précurseurs de NHCs ont été synthétisés, à partir de l'acide (S)-pyroglutamique en vue de leur application dans la réaction d'addition conjuguée de cétones α, β-insaturées catalysée au cuivre avec des réactifs de Grignard. Les excès énantiomériques sont modestes mais de bons résultats en termes d’activité catalytique et de régiosélectivité ont été obtenus.

At first, this work deals with the synthesis of a novel class of single-component reversible chiral ionic liquids derived from natural aminoacids. Reversibility was demonstrated by NMR, thermogravimetric analysis and differential scanning calorimetry. These compounds were tested as organocatalysts in an asymmetric Michael addition leading to the formation of expected product in moderate yields. Chiral silylamines, precursors to reversible ionic liquids were also evaluated in the synthesis of Warfarin through an asymmetric Michael addition. Good yields were obtained. However, these catalysts have resulted in only low enantioselectivity. Moreover, the use of reversible ionic liquid as a temporary protecting group in glycochemistry, for the synthesis of disaccharides was also implemented. Secondly, some new chiral imidazolinium salts, precursors to NHCs, were synthesized from (S)-pyroglutamic acid, for copper-catalyzed conjugate addition of Grignard reagents to α,β-unsaturated ketones applications. The results have shown moderate enantioselectivity with very good catalytic activity and excellent regioselectivity.

Advisors/Committee Members: Vo-Thanh, Giang (thesis director), Boyer, François-Didier (thesis director).

Subjects/Keywords: NHC; Carbènes N-hétérocycliques; LICRev; Glycochimie; Liquides ioniques réversibles; Catalyse asymétrique; Aminoacides naturels; Acide (S)-pyroglutamique; NHC; N-heterocyclic carbenes; RevCILs; Glycochemistry; Reversible ionic liquids; Asymmetric catalysis; Natural aminoacids; (S)-pyroglutamic acid

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Bouchardy, L. (2016). Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction. (Doctoral Dissertation). Université Paris-Saclay (ComUE). Retrieved from http://www.theses.fr/2016SACLS400

Chicago Manual of Style (16^th Edition):

Bouchardy, Lucie. “Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction.” 2016. Doctoral Dissertation, Université Paris-Saclay (ComUE). Accessed January 20, 2021. http://www.theses.fr/2016SACLS400.

MLA Handbook (7^th Edition):

Bouchardy, Lucie. “Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction.” 2016. Web. 20 Jan 2021.

Vancouver:

Bouchardy L. Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction. [Internet] [Doctoral dissertation]. Université Paris-Saclay (ComUE); 2016. [cited 2021 Jan 20]. Available from: http://www.theses.fr/2016SACLS400.

Council of Science Editors:

Bouchardy L. Elaboration de liquides ioniques (chiraux) réversibles et applications en catalyse organique et en glycochimie. Carbènes N-hétérocycliques chiraux : synthèse et application dans la réaction d'addition conjuguée : Elaboration of reversible (chiral) ionic liquids and applications in organic catalysis and in glycochemistry. Chiral N-heterocyclic carbenes : synthesis and application in the conjugate addition reaction. [Doctoral Dissertation]. Université Paris-Saclay (ComUE); 2016. Available from: http://www.theses.fr/2016SACLS400

6. Rumple, Amber C. Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates.

Degree: PhD, Chemistry and Biochemistry, 2014, Georgia Tech

URL: http://hdl.handle.net/1853/53474

► The thermal degradation of polyvinyl chloride (PVC) is a significant processing challenge which can lead to deleterious mechanical and optical properties in a wide range… (more)

▼ The thermal degradation of polyvinyl chloride (PVC) is a significant processing challenge which can lead to deleterious mechanical and optical properties in a wide range of products. Synergetic studies on PVC model compounds and blends of bulk PVC provide unique insights into the thermal degradation and stabilization pathways in the presence of common additives. Model PVC compounds were selected to replicate specific defects (e.g., allylic, vicinal and tertiary) and tacticity (i.e., utilizing stereochemistry to investigate tacticity) commonly found in PVC. Model studies were conducted neat (solvent-free) with metal carboxylates. Experimental results highlight that the allylic and tertiary defects are more reactive than pristine PVC and isotactic sites are more reactive than their syndiotactic counterparts. Zinc stearate was found to act not in the role of substituent, but as a Lewis acid by facilitating dehydrochlorination of labile chlorides. This prevents the accumulation of hydrogen chloride and autocatalytic chain unzipping. In contrast, calcium stearate delayed the formation of zinc chloride, a much stronger Lewis acid than zinc stearate, through an ion exchange process to form calcium chloride. Thermal weight loss studies using blends of bulk PVC proved critical in transferring mechanistic insights into the context of a polymeric matrix. Post-combustion carbon capture has traditionally involved the use of aqueous alkanol amine solutions. The regeneration of such systems, however, can be costly and energy intensive. We have developed an alternative system utilizing silylated alkylamines to reversibly capture CO2 under near ambient conditions. The silyl amines developed capture CO2 through chemical reaction to form reversible ionic liquids (RevIL). RevILs utilize no added water and are tunable by molecular design allowing us to influence industrially relevant carbon capture properties such as viscosity, temperature of reversal, and enthalpy of regeneration, while maximizing overall CO2 capture capacity. We demonstrate a strong structure-property relationship among the silyl amines where minor structural modifications lead to significant changes in the bulk properties of the RevIL. Amine containing substrates are important building blocks for a variety of biological and pharmaceutical compounds. However, application of the otherwise versatile Suzuki reaction to these substrates has proved challenging due to either ligation of the amine to the palladium or to electronic effects slowing the oxidative addition step. Conventional methods to overcome these challenges involve protection-deprotection strategies or the use of designer ligands to facilitate reaction. We have shown that application of CO2 pressure and adjusting the water content of the reaction system facilitate the Suzuki coupling of 4-amino-2-halopyridines in high yield with the simple Pd(TPP)2Cl2 catalyst. The protocol was expanded to 2-halopyridines. The results of these investigations will be discussed. Advisors/Committee Members: Liotta, Charles L. (advisor), Eckert, Charles A. (advisor), France, Stefan (committee member), Oyelere, Adeboyega (committee member), Jones, Christopher (committee member).

Subjects/Keywords: Sustainable; PVC; Suzuki; pH; Sustainable chemistry; CO₂ capture; Reversible ionic liquids; CO₂; PVC stabilization; PVC degradation

…97 Figure 72 - Reaction of silylamine to form Reversible Ionic Liquid… …reversible ionic liquid… …polyvinyl chloride RevIL reversible ionic liquid RT SDMESA room temperature N-methyl-3-(… …The second project investigated silylamines and their application as reversible ionic… …TPSA 2-methyl-4-(tripropylsilyl)-butyl-2-amine TSIL task-specific ionic liquid…

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APA (6^th Edition):

Rumple, A. C. (2014). Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/53474

Chicago Manual of Style (16^th Edition):

Rumple, Amber C. “Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates.” 2014. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/53474.

MLA Handbook (7^th Edition):

Rumple, Amber C. “Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates.” 2014. Web. 20 Jan 2021.

Vancouver:

Rumple AC. Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates. [Internet] [Doctoral dissertation]. Georgia Tech; 2014. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/53474.

Council of Science Editors:

Rumple AC. Sustainable chemistry solutions for industrial challenges: mechanisms of PVC degradation and stabilization; reversible ionic liquids for CO₂ capture; efficient Suzuki coupling of basic, nitrogen containing substrates. [Doctoral Dissertation]. Georgia Tech; 2014. Available from: http://hdl.handle.net/1853/53474

Georgia Tech

7. Blasucci, Vittoria Madonna. Organic solvents for catalysis and organic reactions.

Degree: PhD, Chemical Engineering, 2009, Georgia Tech

URL: http://hdl.handle.net/1853/31723

► We develop, characterize, and apply novel solvent systems for enhanced separations. The field of separations has long been explored by chemical engineers. One way to… (more)

Subjects/Keywords: Smart solvents; Reversible ionic liquids; Alternative solvents; Tunable solvents; Polymer grafting; Amines; Solvents; Organic compounds

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APA (6^th Edition):

Blasucci, V. M. (2009). Organic solvents for catalysis and organic reactions. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/31723

Chicago Manual of Style (16^th Edition):

Blasucci, Vittoria Madonna. “Organic solvents for catalysis and organic reactions.” 2009. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/31723.

MLA Handbook (7^th Edition):

Blasucci, Vittoria Madonna. “Organic solvents for catalysis and organic reactions.” 2009. Web. 20 Jan 2021.

Vancouver:

Blasucci VM. Organic solvents for catalysis and organic reactions. [Internet] [Doctoral dissertation]. Georgia Tech; 2009. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/31723.

Council of Science Editors:

Blasucci VM. Organic solvents for catalysis and organic reactions. [Doctoral Dissertation]. Georgia Tech; 2009. Available from: http://hdl.handle.net/1853/31723

8. Flack, Kyle M. Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents.

Degree: PhD, Chemistry and Biochemistry, 2012, Georgia Tech

URL: http://hdl.handle.net/1853/44802

► Green chemistry principles have been applied to the enhancement of two industrial chemistry problems. An industrially used reaction to form alcohols from aldehydes and ketones,… (more)

▼ Green chemistry principles have been applied to the enhancement of two industrial chemistry problems. An industrially used reaction to form alcohols from aldehydes and ketones, the Meerwein-Ponndorf-Verley reduction, was improved by introducing a new catalyst Al(OtBu)₃. Due to the lower state of aggregation of this catalyst versus the conventional Al(OiPr)₃ catalyst, reduction rates were found to be faster in both pure iPrOH and mixed solvent systems for three model compounds: benzaldehyde, acetophenone, and a complex, chiral ketone, (S)-CMK. This allowed for the successful implementation of two important milestones; lowering the amount of catalyst needed necessary to complete the reactions (an economic benefit and lower waste) and the conversion from traditional batch reactions to continuous flow (a processing benefit) whereby reactions can be scaled-out rather than scaled-up. Another industrially important field of research that was focused on was CO₂ capture. High energy demands from current CO₂ capture methods such as aqueous amine solvents, specifically from coal-fired power plant flue gas, led to the development of non-aqueous reversible ionic liquids based on silylated amines. Structural modifications of the substitution around the silicon atom, the length of the alkyl chain bonding the silicon and amine, branching along the alkyl backbone, and investigating secondary and primary amines within this class of silylated amines were completed. These amines were reacted with CO₂ and the CO₂ capacity, the ionic liquid viscosity, reversal temperature and reaction enthalpy were all considered as a function of structure. In all cases the capacity was found to be not only greater than that of monethanolamine, an industrial standard, but higher than theoretical predictions through the formation of carbamic acid. Viscosity, reversal temperature, and reaction enthalpy were all found to be tunable through structure. These modifications gave significant insight into the necessary direction for optimization of these solvents as energy-efficient replacements of current CO₂ capture technology. Advisors/Committee Members: Dr. Charles L. Liotta (Committee Chair), Dr. Charles A. Eckert (Committee Co-Chair), Dr. Angelo Bongiorno (Committee Member), Dr. Christopher Jones (Committee Member), Dr. Stefan France (Committee Member).

Subjects/Keywords: Silylated amines; Continuous flow; MPV reduction; Reversible ionic liquids; Carbon capture; Environmental chemistry Industrial applications; Carbon sequestration; Chemistry, Organic

…124 4.3.2 Conversion of reversible ionic liquids systems… …108 Figure 4.10. Alkoxysilylamines as one-component reversible ionic liquids… …CO2 to form ionic liquids that are thermally reversible. It was found that small structural… …100 4.1.2 Ionic liquids (ILs) for CO2 capture… …105 Figure 4.7. Proline anion functionalized task-specific ionic liquids…

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APA (6^th Edition):

Flack, K. M. (2012). Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/44802

Chicago Manual of Style (16^th Edition):

Flack, Kyle M. “Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents.” 2012. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/44802.

MLA Handbook (7^th Edition):

Flack, Kyle M. “Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents.” 2012. Web. 20 Jan 2021.

Vancouver:

Flack KM. Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents. [Internet] [Doctoral dissertation]. Georgia Tech; 2012. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/44802.

Council of Science Editors:

Flack KM. Two approaches to green chemistry in industrially driven processes: aluminum tert-butoxide as a rate enhancing Meerwein-Ponndorf-Verley reduction catalyst applied to the technological transfer from batch to continuous flow and structural modifications of functionalized trialkylsilylamines as energy efficient carbon dioxide capture solvents. [Doctoral Dissertation]. Georgia Tech; 2012. Available from: http://hdl.handle.net/1853/44802

9. Nixon, Emily Cummings. Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis.

Degree: PhD, Chemistry and Biochemistry, 2012, Georgia Tech

URL: http://hdl.handle.net/1853/45847

► Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation… (more)

▼ Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs. Advisors/Committee Members: Eckert, Charles (Committee Co-Chair), Liotta, Charles (Committee Co-Chair), France, Stefan (Committee Member), Gelbaum, Leslie (Committee Member), Meredith, Carson (Committee Member).

Subjects/Keywords: Green chemistry; Carbon dioxide capture; Crosslinked polyethylene; Gold nanoparticles; Reversible ionic liquids; Green solvents; Silanes; Environmental chemistry Industrial applications; Carbon dioxide mitigation; Polymerization; Silane compounds; Silane

…132 CHAPTER 4. REVERSIBLE IONIC LIQUIDS AS SWITCHABLE SURFACTANTS FOR THE SYNTHESIS OF GOLD… …195 5.3 Chapter 4: Reversible Ionic Liquids as Switchable Surfactants for the Synthesis of… …agents known as reversible ionic liquids (RevILs)4 has been synthesized and evaluated… …reversible ionic liquids for energy applications. Fuel 2010, 89 (6), 1315-1319. 6… …3 Figure 1.4. Reaction of CO2 with molecular liquid, left, to form reversible ionic liquid…

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APA (6^th Edition):

Nixon, E. C. (2012). Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis. (Doctoral Dissertation). Georgia Tech. Retrieved from http://hdl.handle.net/1853/45847

Chicago Manual of Style (16^th Edition):

Nixon, Emily Cummings. “Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis.” 2012. Doctoral Dissertation, Georgia Tech. Accessed January 20, 2021. http://hdl.handle.net/1853/45847.

MLA Handbook (7^th Edition):

Nixon, Emily Cummings. “Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis.” 2012. Web. 20 Jan 2021.

Vancouver:

Nixon EC. Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis. [Internet] [Doctoral dissertation]. Georgia Tech; 2012. [cited 2021 Jan 20]. Available from: http://hdl.handle.net/1853/45847.

Council of Science Editors:

Nixon EC. Silanes in sustainable synthesis: applications in polymer grafting, carbon dioxide capture, and gold nanoparticle synthesis. [Doctoral Dissertation]. Georgia Tech; 2012. Available from: http://hdl.handle.net/1853/45847

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