Lanterna Rally

Author: Jennifer Lien

Publisher:

Published: 2017

Total Pages:

ISBN-13: 9780355462173

The first chapter of this thesis deals with the introduction of X-ray nanochemistry, a topic or area of study which has been formally created during my Ph. D. tenure. The principles and systems discussed are illustrated by example in Chapters 2 through 4. The second chapter describes early stage work on X-ray driven photocatalysis which is being developed to learn whether and how energy flow controls X-ray catalysis of CO2 reduction. X-ray irradiation results with 2 wt% Cu-TiO2 (the catalyst giving highest methanol yields in photocatalysis) yielded the formate intermediate CHO at a conversion efficiency of less than 0.01%. Photocatalysis efficiencies are very low due to a lack of mechanistic understanding and subsequent optimization, although this result shows that it is possible to use X-rays in combination with nanomaterials to control the flow of energy. A nanosystem comprised of a fluorophore, 6-FAM-DNA, covalently conjugated to 15 nm silica coated onto 90 nm gold nanoparticles was successfully made. Under 21 Gy of 100 keV X-ray irradiation at a dose rate of 1.05 Gy/min, 0.75 wt% gold in water produced a local physical enhancement of hydroxyl radicals of 2.60 ± 0.12 DEU. This is roughly in agreement with the simulated enhancement of 4.33 DEU. Employing the local enhancement result from X-ray nanochemistry in X-ray catalysis can improve the yield of CO2 reduction. The third chapter details a mechanistic study of complex multiple step reactions. Often one or more steps in complex reactions can be catalyzed when gold nanoparticles or other catalysts are present, and the goal of the chapter is to identify which step is catalyzed. A general triple-jump (TJ) reaction model for complex reactions is developed through the study of radical trapping reactions such as hydroxylation reactions and catalysts are dialyzed sub-five nm gold nanoparticles. Three main steps are recognized, each of which can be catalyzed: first is production hydroxyl radicals, second is trapping, and third is conversion to the final product. Through electron paramagnetic resonance (EPR) detection, the first step was found to be mildly reduced due to scavenging of hydroxyl radicals by gold nanoparticles. The second step of spin trapping is nearly unchanged. The third step is a radical conversion reaction, which is highly catalyzed. All three steps combined create an overall catalytic reaction, even though the first and second steps are nearly non-catalytic. The TJ model for radical reactions can be used to explain results observed in a commonly used dosimetric reaction to detect hydroxyl radicals. The forth chapter presents a unique material called Agu (thin silver layers coated onto gold) with a sensitive surface plasmon resonance response between 0.5 and 2 nm silver thickness that can detect down to a 0.3 angstrom, or a sub-monolayer change in silver thickness. Agu is used as a sensor for X-ray irradiation etching. The fifth chapter discusses a nanotechnology as it relates to plant genetics and points to the potential use of X-rays for targeted delivery of genetic material via nanomaterials such as quantum dots which connects plant nanotechnology to X-ray nanochemistry. Two generations of microneedle arrays with nanoscale features are fabricated using a state-of-the-art focused ion beam technology. Nanoscale features are created to house higher payloads of editing material or nanomaterials. Quantum dots delivered by the microneedle arrays have been successfully employed as a location reporter in lettuce cells. Particle bombardment is also explored as a comparison, but this traditional method along with single microneedle injectors do not have the precision or spatial resolution and delivery capacity of these novel microneedle delivery arrays. Finally, the sixth chapter offers concluding remarks connecting the materials, technologies, and principles discussed in this thesis to point towards potential overlap in various subfields of catalysis, sensors, plant biology and X-ray nanochemistry.