+publisher:"University of Colorado" +contributor:("Garret Miyake")

University of Colorado

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

Degree: PhD, 2018, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/273

► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key… (more)

▼ 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

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

APA (6^th 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 (16^th 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 (7^th 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

University of Colorado

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

Degree: PhD, 2017, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/219

► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key… (more)

▼ 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

Record Details Similar Records Cite « Share

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

APA (6^th 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 (16^th 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 (7^th 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

3. Hartwig, William T. The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors.

Degree: PhD, Chemistry & Biochemistry, 2015, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/157

► While in the Sammakia Lab, I have focused on developing and applying new approaches to organic synthesis and the creation of novel cell-signaling inhibitors.… (more)

Subjects/Keywords: organic synthesis; cell-signaling inhibitors; Lewis acid; ATNP; unnatural enantiomer morphinans; Biochemistry

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

APA (6^th Edition):

Hartwig, W. T. (2015). The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/157

Chicago Manual of Style (16^th Edition):

Hartwig, William T. “The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors.” 2015. Doctoral Dissertation, University of Colorado. Accessed April 17, 2021. https://scholar.colorado.edu/chem_gradetds/157.

MLA Handbook (7^th Edition):

Hartwig, William T. “The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors.” 2015. Web. 17 Apr 2021.

Vancouver:

Hartwig WT. The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors. [Internet] [Doctoral dissertation]. University of Colorado; 2015. [cited 2021 Apr 17]. Available from: https://scholar.colorado.edu/chem_gradetds/157.

Council of Science Editors:

Hartwig WT. The Vinylogous Aldol Reaction of Furoate Esters and the Synthesis of Unnatural Enantiomer Morphinans as TLR4 Inhibitors. [Doctoral Dissertation]. University of Colorado; 2015. Available from: https://scholar.colorado.edu/chem_gradetds/157

University of Colorado

4. Moran, Mark James Conroy. Structure-Property Relationships in de Vries Smectic A Liquid Crystals.

Degree: PhD, Chemistry & Biochemistry, 2015, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/165

► Liquid crystals (LCs) have become inextricably linked with the display industry in recent years. As screen sizes increase the response time of the LC… (more)

▼ Liquid crystals (LCs) have become inextricably linked with the display industry in recent years. As screen sizes increase the response time of the LC must decrease to maintain picture quality. A rare subset of the chiral smectic A (SmA*) , known as the de Vries SmA* phase, shows fast switching times, large electroclinic tilts, native gray-scale and small layer shrinkage when driven by an electric field, making it an attractive alternative to SmC* materials for next-generation displays. The de Vries SmA* phase is typically formed by molecules with one or more tails that strongly suppress out-of-layer fluctuations. The first part of this thesis describes a set of mesogens with four different liquid crystalline cores built on a scaffold possessing a phenyl and biphenyl moiety linked by an ester with two peripheral alkoxy side-chains (tails). One side-chain is the (S)-1-methylheptyloxy group ortho to a trifluoromethyl group. The second side chain is varied between an n-alkoxy-, n-alkenyloxy- and semifluorinated tails, all of the same length. The latter two tails have been shown to suppress out-of-layer fluctuations. Only the LCs built on the hydroquinone stereopolar unit (W652/W657/W530) show the desired liquid crystalline phases (SmA* and SmC*) over a convenient temperature range. Surprisingly, W652, which possesses no strong out-of-layer suppressing group, shows the de Vries SmA* phase, suggesting the core may be as important as the tails in the design of de Vries smecticss. The second part of this thesis develops structure-property relationships of compounds built on the hydroquinone stereopolar unit, which is particularly good at promoting the de Vries SmA* phase. The set of lateral polar groups (H, Me, Cl, CF₃ or NO₂) and achiral tails were varied. The effect on the width of the SmA* phases, the clearing point, saturated electroclinic tilt, layer shrinkage from SmA* to SmC* and spontaneous polarization in the SmC* phase were examined. Materials with a large electronegative lateral polar group and strongly out-of-layer suppressing tails give the most desirable properties. Advisors/Committee Members: David M. Walba, Joseph E. Maclennan, Noel A. Clark, Richard K. Shoemaker, Garret Miyake.

Subjects/Keywords: de Vries; Electrooptics; Liquid Crystals; Smectic A; Structure-Property Relationships; Organic Chemistry; Semiconductor and Optical Materials

Record Details Similar Records Cite « Share

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

APA (6^th Edition):

Moran, M. J. C. (2015). Structure-Property Relationships in de Vries Smectic A Liquid Crystals. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/165

Chicago Manual of Style (16^th Edition):

Moran, Mark James Conroy. “Structure-Property Relationships in de Vries Smectic A Liquid Crystals.” 2015. Doctoral Dissertation, University of Colorado. Accessed April 17, 2021. https://scholar.colorado.edu/chem_gradetds/165.

MLA Handbook (7^th Edition):

Moran, Mark James Conroy. “Structure-Property Relationships in de Vries Smectic A Liquid Crystals.” 2015. Web. 17 Apr 2021.

Vancouver:

Moran MJC. Structure-Property Relationships in de Vries Smectic A Liquid Crystals. [Internet] [Doctoral dissertation]. University of Colorado; 2015. [cited 2021 Apr 17]. Available from: https://scholar.colorado.edu/chem_gradetds/165.

Council of Science Editors:

Moran MJC. Structure-Property Relationships in de Vries Smectic A Liquid Crystals. [Doctoral Dissertation]. University of Colorado; 2015. Available from: https://scholar.colorado.edu/chem_gradetds/165

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