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Investigation of Structure-Property Relationships in Metal-Organic Frameworks for Applications in Industry and Medical Imaging.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Investigation of Structure-Property Relationships in Metal-Organic Frameworks for Applications in Industry and Medical Imaging./
作者:	Robison, Lee.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2021,
面頁冊數:	209 p.
附註:	Source: Dissertations Abstracts International, Volume: 82-12, Section: B.
Contained By:	Dissertations Abstracts International82-12B.
標題:	Chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28316894
ISBN:	9798516063268

Investigation of Structure-Property Relationships in Metal-Organic Frameworks for Applications in Industry and Medical Imaging.
Robison, Lee.

Investigation of Structure-Property Relationships in Metal-Organic Frameworks for Applications in Industry and Medical Imaging. - Ann Arbor : ProQuest Dissertations & Theses, 2021 - 209 p.

Source: Dissertations Abstracts International, Volume: 82-12, Section: B.

Thesis (Ph.D.)--Northwestern University, 2021.

This item must not be sold to any third party vendors.

The idea that structure determines the properties of a material is a powerful concept in chemistry and in all fields in which chemistry is important, including engineering, medicine, and materials science. My research aims to better understand the structure-property relationships of a class of materials known as metal-organic frameworks (MOFs). MOFs are hybrid, porous materials, comprising metal nodes and organic linkers that self-assemble to form multi-dimensional, crystalline lattices. I have investigated MOFs in my graduate research for use as potential imaging contrast agents in biomedicine and studied the ability of postsynthetic modifications of MOF structures to alter their mechanical properties. To investigate the relationship between these postsynthetic modifications and the resultant bulk mechanical properties of these MOFs, I used in-situ high-pressure powder X-ray diffraction (PXRD) diffraction, nanoindentation, and density functional theory simulations. Overall, my research aims to guide the field in delineating new design rules to improve the functionality and bulk mechanical stability of these materials using molecular-level chemical strategies.To implement MOF-based technologies in the commercial sector, we must process powdered MOF samples into shaped forms. During pelletization processes, samples experience large hydrostatic pressures capable of inducing framework collapse, which reduces their porosity. I sought to reinforce these porous materials by post-synthetically installing structural linkers into the parent MOF framework. I envisioned this strategy would allow us to precisely control the physical stability of the MOF by fine-tuning the mechanical properties of the framework at the molecular level.To this end, I synthesized a Zr6-based MOF and post-synthetically installed size-matching linkers using solvent assisted linker incorporation (SALI). I investigated the pressure dependent behavior of the materials using in-situ powder X-ray diffraction (PXRD) within a diamond anvil cell (DAC). The mechanical properties of the post-synthetically modified frameworks indicate that installation of these additional structural linkers improved the structural integrity by up to a factor of 1.75 and reduced the compressibility of the framework, preserving the porosity and pore size distribution of the modified framework. In another study, I investigated the interpenetration of a zirconium cluster-based MOF from its evolution from a noninterpenetrated material to an interpenetrated isomer of the same structure. This transition can be thought of as a postsynthetic rearrangement reaction, whereby the lattice of the parent framework, upon the introduction of some chemical stimulus, undergoes a rearrangement of its structure. I observed this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy (HR-TEM). I also investigated the mechanical stability of both lattices experimentally by in situ PXRD within a DAC, nanoindentation, as well as computationally studying the structures using density functional theory (DFT) calculations. We found that the doubly interpenetrated structure is considerably more mechanically stable than the noninterpenetrated material and we document a coding script that can automatically process (HR-TEM) images of the crystallites to distinguish between the two phases. I concluded this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent, sulfur mustard gas.In addition to exploring the fundamental structure and physical properties of MOFs, I also investigated the potential use of several MOFs as biomedical contrast agents. In my first project in this area, we postsynthetically incorporated Gd(III) complexes into Zr-MOFs using solvent-assisted ligand incorporation (SALI). By inserting Gd(III) complexes in the pores of a metal-organic framework (MOF) we found a unique strategy to explore the parameters of nanomaterial structure and composition that influence its contrast performance. By studying the Zr-based MOFs, NU-1000 (nano and micron size particles) and NU-901, we investigated the impact of particle size and pore shape on proton relaxivity. The SALI-functionalized Gd nano NU-1000 hybrid material displayed the highest loading of the Gd(III) complex (1.9 ± 0.1 complexes per node) and exhibited the most enhanced proton relaxivity (r1 of 26 ± 1 mM-1s-1 at 1.4 T). We determined the performance of Gd nano NU-1000 to the nanoscale size of the MOF particles and larger pore size that allows for rapid water exchange. We found that SALI is a promising postsynthetic method for incorporating Gd(III) complexes into MOF materials and identified crucial design parameters for the preparation of next generation Gd(III)-functionalized MOF MRI contrast agents.Lastly, I investigated the performance of a novel bismuth-based MOF for use as an X-ray computed tomography (CT) contrast agent. I synthesized this new bismuth MOF, which is stable under physiological conditions and nontoxic. In vitro studies revealed the bismuth MOF displayed 7x better contrast compared to a zirconium MOF featuring the same topology and 14x better contrast than a commercially available CT contrast agent.

ISBN: 9798516063268Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Contrast media

Investigation of Structure-Property Relationships in Metal-Organic Frameworks for Applications in Industry and Medical Imaging.
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520 $a The idea that structure determines the properties of a material is a powerful concept in chemistry and in all fields in which chemistry is important, including engineering, medicine, and materials science. My research aims to better understand the structure-property relationships of a class of materials known as metal-organic frameworks (MOFs). MOFs are hybrid, porous materials, comprising metal nodes and organic linkers that self-assemble to form multi-dimensional, crystalline lattices. I have investigated MOFs in my graduate research for use as potential imaging contrast agents in biomedicine and studied the ability of postsynthetic modifications of MOF structures to alter their mechanical properties. To investigate the relationship between these postsynthetic modifications and the resultant bulk mechanical properties of these MOFs, I used in-situ high-pressure powder X-ray diffraction (PXRD) diffraction, nanoindentation, and density functional theory simulations. Overall, my research aims to guide the field in delineating new design rules to improve the functionality and bulk mechanical stability of these materials using molecular-level chemical strategies.To implement MOF-based technologies in the commercial sector, we must process powdered MOF samples into shaped forms. During pelletization processes, samples experience large hydrostatic pressures capable of inducing framework collapse, which reduces their porosity. I sought to reinforce these porous materials by post-synthetically installing structural linkers into the parent MOF framework. I envisioned this strategy would allow us to precisely control the physical stability of the MOF by fine-tuning the mechanical properties of the framework at the molecular level.To this end, I synthesized a Zr6-based MOF and post-synthetically installed size-matching linkers using solvent assisted linker incorporation (SALI). I investigated the pressure dependent behavior of the materials using in-situ powder X-ray diffraction (PXRD) within a diamond anvil cell (DAC). The mechanical properties of the post-synthetically modified frameworks indicate that installation of these additional structural linkers improved the structural integrity by up to a factor of 1.75 and reduced the compressibility of the framework, preserving the porosity and pore size distribution of the modified framework. In another study, I investigated the interpenetration of a zirconium cluster-based MOF from its evolution from a noninterpenetrated material to an interpenetrated isomer of the same structure. This transition can be thought of as a postsynthetic rearrangement reaction, whereby the lattice of the parent framework, upon the introduction of some chemical stimulus, undergoes a rearrangement of its structure. I observed this transient catenation process indirectly using ensemble methods, such as nitrogen porosimetry and X-ray diffraction, and directly, using high-resolution transmission electron microscopy (HR-TEM). I also investigated the mechanical stability of both lattices experimentally by in situ PXRD within a DAC, nanoindentation, as well as computationally studying the structures using density functional theory (DFT) calculations. We found that the doubly interpenetrated structure is considerably more mechanically stable than the noninterpenetrated material and we document a coding script that can automatically process (HR-TEM) images of the crystallites to distinguish between the two phases. I concluded this study by demonstrating the potential of these MOFs and their mixed phases for the capture of gaseous n-hexane, used as a structural mimic for the chemical warfare agent, sulfur mustard gas.In addition to exploring the fundamental structure and physical properties of MOFs, I also investigated the potential use of several MOFs as biomedical contrast agents. In my first project in this area, we postsynthetically incorporated Gd(III) complexes into Zr-MOFs using solvent-assisted ligand incorporation (SALI). By inserting Gd(III) complexes in the pores of a metal-organic framework (MOF) we found a unique strategy to explore the parameters of nanomaterial structure and composition that influence its contrast performance. By studying the Zr-based MOFs, NU-1000 (nano and micron size particles) and NU-901, we investigated the impact of particle size and pore shape on proton relaxivity. The SALI-functionalized Gd nano NU-1000 hybrid material displayed the highest loading of the Gd(III) complex (1.9 ± 0.1 complexes per node) and exhibited the most enhanced proton relaxivity (r1 of 26 ± 1 mM-1s-1 at 1.4 T). We determined the performance of Gd nano NU-1000 to the nanoscale size of the MOF particles and larger pore size that allows for rapid water exchange. We found that SALI is a promising postsynthetic method for incorporating Gd(III) complexes into MOF materials and identified crucial design parameters for the preparation of next generation Gd(III)-functionalized MOF MRI contrast agents.Lastly, I investigated the performance of a novel bismuth-based MOF for use as an X-ray computed tomography (CT) contrast agent. I synthesized this new bismuth MOF, which is stable under physiological conditions and nontoxic. In vitro studies revealed the bismuth MOF displayed 7x better contrast compared to a zirconium MOF featuring the same topology and 14x better contrast than a commercially available CT contrast agent.
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