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Exploring the impacts of nanoconfinement using nuclear magnetic resonance (NMR) spectroscopy

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dc.contributor.authorMiller, Samantha L., author
dc.contributor.authorLevinger, Nancy, advisor
dc.contributor.authorKrummel, Amber, committee member
dc.contributor.authorCrans, Debbie, committee member
dc.contributor.authorGraham, James, committee member
dc.date.accessioned2022-08-29T10:17:12Z
dc.date.available2023-08-22T10:17:12Z
dc.date.issued2022
dc.description.abstractThe chemical reactivity of molecules is typically studied under bulk aqueous conditions in the research laboratory. Although this standard may be appropriate for processes destined to be scaled up for industrial purposes, it ignores the fact that a great deal of the chemistry underlying physiological reactions occur in confined environments, like cellular organelles, protein pockets, or porous interfaces. The dissertation begins by describing the methodology for synthesizing size tunable reverse micelles, or surfactant enveloped nanodroplets. After physical perturbation, the ternary mixture of polar (usually aqueous), nonpolar, and amphiphilic surfactant self-assemble. Two small molecules, glucose and urea, were studied in these nano environments using a combination of analytical techniques including dynamic light scattering, differential scanning calorimetry, and molecular dynamics simulations that complemented the myriad nuclear magnetic resonance (NMR) spectroscopy studies. Quantification of single hydrogen exchange between glucose and water using exchange spectroscopy NMR in conjunction with custom MatLab code revealed that confinement of glucose and water within 8-10 nanometer reverse micelles slows the process of exchange by introducing a quantifiable energy barrier of ~75 kJ/mol. Deuterium NMR spectroscopy provided evidence for hydrogen tunneling below 283 K, a surprisingly high temperature for this phenomenon. The same robust methods of kinetic and structural analysis were used to characterize urea in water reverse micelles. Results showed that in addition to its well-known ability to denature proteins, urea can disrupt amphiphilic membranes and cause a ten-fold increase in the membrane surface area at low temperatures ~273 K as a result of this destabilization. Finally, the use of fluorine NMR spectroscopy demonstrated that the reverse micelle nanodroplet environments could achieve higher ionic strengths (~9.0 M) with simple divalent salts than possible in standard bulk solutions (~5.0 M). Together, these results presented compelling evidence that utilization of reverse micelle nanodroplets could provide alternative environments to facilitate previously inaccessible, novel conditions.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierMiller_colostate_0053A_17308.pdf
dc.identifier.urihttps://hdl.handle.net/10217/235702
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2020-
dc.rightsCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.
dc.subjectnanoconfinement
dc.subjectreverse micelles
dc.subjectNMR
dc.subjectkinetic modeling
dc.titleExploring the impacts of nanoconfinement using nuclear magnetic resonance (NMR) spectroscopy
dc.typeText
dcterms.embargo.expires2023-08-22
dcterms.embargo.terms2023-08-22
dcterms.rights.dplaThis Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
thesis.degree.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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