Matching Items (3)
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- All Subjects: Nanoparticles
- Genre: Academic theses
- Genre: Doctoral Dissertation
- Creators: Green, Matthew
- Status: Published
Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
Description
Rapid development of new technology has significantly disrupted the way radiotherapy is planned and delivered. These processes involve delivering high radiation doses to the target tumor while minimizing dose to the surrounding healthy tissue. However, with rapid implementation of these new technologies, there is a need for the detection of prescribed ionizing radiation for radioprotection of the patient and quality assurance of the technique employed. Most available clinical sensors are subjected to various limitations including requirement of extensive training, loss of readout with sequential measurements, sensitivity to light and post-irradiation wait time prior to analysis. Considering these disadvantages, there is still a need for a sensor that can be fabricated with ease and still operate effectively in predicting the delivered radiation dose.
The dissertation discusses the development of a sensor that changes color upon exposure to therapeutic levels of ionizing radiation used during routine radiotherapy. The underlying principle behind the sensor is based on the formation of gold nanoparticles from its colorless precursor salt solution upon exposure to ionizing radiation. Exposure to ionizing radiation generates free radicals which reduce ionic gold to its zerovalent gold form which further nucleate and mature into nanoparticles. The generation of these nanoparticles render a change in color from colorless to a maroon/pink depending on the intensity of incident ionizing radiation. The shade and the intensity of the color developed is used to quantitatively and qualitatively predict the prescribed radiation dose.
The dissertation further describes the applicability of sensor to detect a wide range of ionizing radiation including high energy photons, protons, electrons and emissions from radioactive isotopes while remaining insensitive to non-ionizing radiation. The sensor was further augmented with a capability to differentiate regions that are irradiated and non-irradiated in two dimensions. The dissertation further describes the ability of the sensor to predict dose deposition in all three dimensions. The efficacy of the sensor to predict the prescribed dose delivered to canine patients undergoing radiotherapy was also demonstrated. All these taken together demonstrate the potential of this technology to be translatable to the clinic to ensure patient safety during routine radiotherapy.
The dissertation discusses the development of a sensor that changes color upon exposure to therapeutic levels of ionizing radiation used during routine radiotherapy. The underlying principle behind the sensor is based on the formation of gold nanoparticles from its colorless precursor salt solution upon exposure to ionizing radiation. Exposure to ionizing radiation generates free radicals which reduce ionic gold to its zerovalent gold form which further nucleate and mature into nanoparticles. The generation of these nanoparticles render a change in color from colorless to a maroon/pink depending on the intensity of incident ionizing radiation. The shade and the intensity of the color developed is used to quantitatively and qualitatively predict the prescribed radiation dose.
The dissertation further describes the applicability of sensor to detect a wide range of ionizing radiation including high energy photons, protons, electrons and emissions from radioactive isotopes while remaining insensitive to non-ionizing radiation. The sensor was further augmented with a capability to differentiate regions that are irradiated and non-irradiated in two dimensions. The dissertation further describes the ability of the sensor to predict dose deposition in all three dimensions. The efficacy of the sensor to predict the prescribed dose delivered to canine patients undergoing radiotherapy was also demonstrated. All these taken together demonstrate the potential of this technology to be translatable to the clinic to ensure patient safety during routine radiotherapy.
ContributorsSubramaniam Pushpavanam, Karthik (Author) / Rege, Kaushal (Thesis advisor) / Sapareto, Stephen (Committee member) / Nannenga, Brent (Committee member) / Green, Matthew (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2019
Description
A comprehensive and systematic investigation on the diffusion and phase behaviors of nanoparticles and macromolecules in two component liquid-liquid systems via Molecule Dynamic (MD) simulations is presented in this dissertation.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
The interface of biphasic liquid systems has attracted great attention because it offers a simple, flexible, and highly reproducible template for the assembly of a variety of nanoscale objects. However, certain important fundamental issues at the interface have not been fully explored, especially when the size of the object is comparable with the liquid molecules. In the first MD simulation system, the diffusion and self-assembly of nanoparticles with different size, shape and surface composition were studied in an oil/water system. It has been found that a highly symmetrical nanoparticle with uniform surface (e.g. buckyball) can lead to a better-defined solvation shell which makes the “effective radius” of the nanoparticle larger than its own radius, and thus, lead to slower transport (diffusion) of the nanoparticles across the oil-water interface. Poly(N-isopropylacrylamide) (PNIPAM) is a thermoresponsive polymer with a Lower Critical Solution Temperature (LCST) of 32°C in pure water. It is one of the most widely studied stimulus-responsive polymers which can be fabricated into various forms of smart materials. However, current understanding about the diffusive and phase behaviors of PNIPAM in ionic liquids/water system is very limited. Therefore, two biphasic water-ionic liquids (ILs) systems were created to investigate the interfacial behavior of PNIPAM in such unique liquid-liquid interface. It was found the phase preference of PNIPAM below/above its LCST is dependent on the nature of ionic liquids. This potentially allows us to manipulate the interfacial behavior of macromolecules by tuning the properties of ionic liquids and minimizing the need for expensive polymer functionalization. In addition, to seek a more comprehensive understanding of the effects of ionic liquids on the phase behavior of PNIPAM, PNIPAM was studied in two miscible ionic liquids/water systems. The thermodynamic origin causes the reduction of LCST of PNIPAM in imidazolium based ionic liquids/water system was found. Energy analysis, hydrogen boding calculation and detailed structural quantification were presented in this study to support the conclusions.
ContributorsGao, Wei (Author) / Dai, Lenore (Thesis advisor) / Jiao, Yang (Committee member) / Liu, Yongming (Committee member) / Green, Matthew (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2017