Dissertation
QUANTIFICATION OF SUPRAMOLECULAR ASSEMBLY IN COMPLEX LIQUIDS WITH NMR SPECTROSCOPY
Doctor of Philosophy (PhD), Washington State University
01/2018
Handle:
https://hdl.handle.net/2376/111321
Abstract
Many molecules self-assemble through subtle interactions into supramolecular complexes that significantly influence overall liquid structure and transport properties. Such liquids are inhomogeneous at the nanoscale, and are often found in industrial processes including the synthesis of nanoparticles involving the use of phase transfer catalysts, heavy metal extractions in supercritical carbon dioxide, and ion pairing in concentrated electrolytes. These complexes are in rapid, dynamic equilibrium at timescales prohibiting spectral resolution of discrete species with techniques such as Nuclear Magnetic Resonance Spectroscopy (NMR). Herein, we demonstrate a theory-guided analysis of supramolecular assembly in which diffusion ordered, pulsed field gradient (PFG) and magic angle spinning (MAS) NMR experiments are utilized to quantify the morphology and distribution of supramolecular species in industrially relevant systems. A refinement on the calculation of cluster distributions from ensemble diffusometry is presented and limitations on the use of ensemble measurements to generate cluster distributions are noted. In-situ MAS-NMR experiments are used to monitor the dissolution of colloidal phases and to detect subtle changes in the local structure of aluminate ions in supersaturated solutions with respect to the aluminate ion. The described experimental methodologies and integration with theory-based computational simulations provide significant improvements in the analysis of complex systems and are widely applicable in industrially relevant processes.
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Details
- Title
- QUANTIFICATION OF SUPRAMOLECULAR ASSEMBLY IN COMPLEX LIQUIDS WITH NMR SPECTROSCOPY
- Creators
- Trenton Robert Graham
- Contributors
- Steven R. Saunders (Advisor)Nehal Abu-Lail (Committee Member)Cornelius Ivory (Committee Member)William Hiscox (Committee Member)David Heldebrant (Committee Member)
- Awarding Institution
- Washington State University
- Academic Unit
- Chemical Engineering and Bioengineering, School of
- Theses and Dissertations
- Doctor of Philosophy (PhD), Washington State University
- Number of pages
- 221
- Identifiers
- 99900581511401842
- Language
- English
- Resource Type
- Dissertation