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You searched for subject:(preboitic chemistry). Showing records 1 – 2 of 2 total matches.

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University of Colorado

1. Perkins, Russell James. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.

Degree: PhD, 2017, University of Colorado

Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous aqueous systems, where interfacial effects are particularly important. Despite the importance of aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of aqueous systems, while examining specific phenomena across several fields. The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU. Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry. Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.

Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Physical Chemistry

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

APA (6th Edition):

Perkins, R. J. (2017). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/219

Chicago Manual of Style (16th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Doctoral Dissertation, University of Colorado. Accessed April 17, 2021. https://scholar.colorado.edu/chem_gradetds/219.

MLA Handbook (7th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Web. 17 Apr 2021.

Vancouver:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2017. [cited 2021 Apr 17]. Available from: https://scholar.colorado.edu/chem_gradetds/219.

Council of Science Editors:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2017. Available from: https://scholar.colorado.edu/chem_gradetds/219


University of Colorado

2. Perkins, Russell James. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.

Degree: PhD, 2018, University of Colorado

Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous aqueous systems, where interfacial effects are particularly important. Despite the importance of aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of aqueous systems, while examining specific phenomena across several fields. The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU. Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry. Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.

Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Organic Chemistry; Physical Chemistry

Record DetailsSimilar RecordsGoogle PlusoneFacebookTwitterCiteULikeMendeleyreddit

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

APA (6th Edition):

Perkins, R. J. (2018). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/273

Chicago Manual of Style (16th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Doctoral Dissertation, University of Colorado. Accessed April 17, 2021. https://scholar.colorado.edu/chem_gradetds/273.

MLA Handbook (7th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Web. 17 Apr 2021.

Vancouver:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2018. [cited 2021 Apr 17]. Available from: https://scholar.colorado.edu/chem_gradetds/273.

Council of Science Editors:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2018. Available from: https://scholar.colorado.edu/chem_gradetds/273

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