Microwave spectroscopy is a gas phase technique typically geared toward measuring the rotational transitions of Molecules. The information contained in this type of spectroscopy pertains to a molecules structure, both geometric and electronic, which give insight into a molecule's chemistry. Typically this type of spectroscopy is high resolution, but narrowband ≤1 MHz in frequency. This is achieved by tuning a cavity, exciting a molecule with electromagnetic radiation in the microwave region, turning the electromagnetic radiation o, and measuring a signal from the molecular relaxation in the form of a free induction decay (FID). The FID is then Fourier transformed to give a frequency of the transition. "Fast passage" is defined as a sweeping of frequencies through a transition at a time much shorter (≤10 s) than the molecular relaxation (≈100 s). Recent advancements in technology have allowed for the creation of these fast frequency sweeps, known as "chirps", which allow for broadband capabilities. This work presents the design, construction, and implementation of one such novel, high-resolution microwave spectrometer with broadband capabilities. The manuscript also provides the theory, technique, and motivations behind building of such an instrument. In this manuscript it is demonstrated that, although a gas phase technique, solids, liquids, and transient species may be studied with the spectrometer with high sensitivity, making it a viable option for many molecules wanting to be rotationally studied. The spectrometer has a relative correct intensity feature that, when coupled with theory, may ease the difficulty in transition assignment and facilitate dynamic chemical studies of the experiment. Molecules studied on this spectrometer have, in turn, been analyzed and assigned using common rotational spectroscopic analysis. Detailed theory on the analysis of these molecules has been provided. Structural parameters such as rotational constants and centrifugal distortion constants have been determined and reported for most molecules in the document. Where possible, comparisons have been made amongst groups of similar molecules to try and get insight into the nature of the bonds those molecules are forming. This has been achieved the the comparisons of nuclear electric quadrupole and nuclear magnetic coupling constants, and the results therein have been determined and reported.

Modification of nanostructures via laser processing is of great interest for a wide range of applications such as aerospace and the storage of nuclear waste. The primary goal of this dissertation is to improve the understanding of nanostructures through two primary routes: the modification of aerogels and pulsed laser ablation in ethanol. A new class of materials, patterned aerogels, was fabricated by photopolymerizing selected regions of homogeneous aerogel monoliths using visible light. The characterization and fabrication of functionally graded, cellular and compositionally anisotropic aerogels and ceramics is discussed. Visible light was utilized due to it’s minimal absorption and scattering by organic molecules and oxide nanoparticles within wet gels. This allowed for the fabrication of deeply penetrating, well resolved patterns. Similarly, nanoporous monoliths with a typical aerogel core and a mechanically robust exterior ceramic layer were synthesized from silica aerogels cross-linked with polyacrylonitrile. Simple variations of the exposure geometry allowed fabrication of a wide variety of anisotropic materials without requiring layering or bonding. Nanoparticle solutions were prepared by laser ablation of metal foils (Fe and Mo) in ethanol. Ablation of Fe generated Fe3O4 and Fe3C nanoparticles which were superparamagnetic with a saturation magnetization Ms = 124 emu/g. Zero field cooled (ZFC) measurements collected at an applied field of 50 Oe displayed a maximum magnetic susceptibility at 120 K with a broad distribution. Field cooled (FC) measurements showed a thermal hysteresis indicative of temperature dependent magnetic viscosity. Pulsed laser ablation of a Mo foil in ethanol generated inhomogeneous nanoparticles where Mo and MoC coexisted within the same aggregate. Formation of these unique nanoparticles is likely due to phase separation that occurs when a high temperature carbide phase cools after the laser pulse terminates. Similarly, magnetic nanoparticle suspensions were generated by pulsed laser ablation of Fe and Mo in ethanol. The formation of several carbide phases with no discernable alloy formation was seen. A decrease in magnetization with a decrease in Fe concentration was seen which was reconciled with the decreased Fe content in the system. However, at Fe concentrations below ~ 40%, an increase in Ms and Hc was observed which was reconciled with the disappearance of the ε–Fe3C. TEM analysis showed the formation of core-shell nanoparticles and Energy Filtered TEM showed the distribution of Fe-based nanoparticles in the suspensions.

Cette thèse visait à développer des techniques d'ablation au laser et de fragmentation dans des liquides pour la synthèse de nouveaux NPs ayant des fonctionnalités utiles. L’approche de la thèse est axée sur l’élaboration de la technique ablative au laser pour la synthèse de matériaux conventionnels avec des paramètres pour des applications biomédicales sélectionnées, ainsi que sur le développement de cette technique pour la synthèse de nouveaux nanomatériaux destinés à des applications biomédicales. En particulier, il comprend:1. Nous avons élaboré un régime de fragmentation laser fs à partir de colloïdes de Si pour la synthèse de NPs de Si ayant une taille, une cristallinité et un état d'oxydation contrôlables.Nous avons testé un certain nombre d’applications biomédiales particulières de Si Si préparés de cette manière.2. Nous avons développé une technique d'ablation et de fragmentation au laser fs pour fabriquer des noyaux Au NPs et des carottes en Au-Si nus pour SERSapplications. Une approche est basée sur l'ablation au laser de la cible Au dans une solution colloïdale de NP Si.3. Pour la première fois, nous avons synthétisé de nouveaux NP plasmoniques à base de nitrure de titane. Nous avons également montré qu’une étape supplémentaire de fragmentation du laser fs entraînait une diminution de la taille des NP à 5 nm. En outre, nous avons constaté que ces NP ont un très large pic d'extinction dans le proche IR.4. Pour la première fois, nous avons démontré la synthèse de NPs organiques fluorescentes d'un luminophore à émission induite par agrégation spécialement conçu (AIE LP). La luminosité de ces NP a été jugée comparable à celle des points quantiques. / This thesis as aimed at the development of techniques of fs laser ablation and fragmentation in liquids for the synthesis of novel NPs having useful functionalities. The approach of the thesis is focused on the elaboration of the laser ablative technique for the synthesis of conventional materials with parameters for selected biomedical applications, as well as the development of this technique for the synthesis of novel nanomaterials for biomedical applications. In particular it includes:1. We elaborated a regime of fs laser fragmentation from Si colloids for the synthesis of Si NPs having controllable size, crystallinity and oxidation state. We tested so-prepared Si NPs a number of particular biomedial applications.2. We elaborated a technique of fs laser ablation and fragmentation to fabricate bare Au NPs and Au-Si core-shells for SERSapplications. One approache is based on laser ablation of Au target in colloidal solution of Si NPs. 3. For the first time we synthesized novel plasmonic NPs based on titanium nitride. We also showed that an additional fs laser fragmentation step leads to the decrease of NPs size to 5 nm. Besides, we found that such NPs have a very broad extinction peak in the near IR.4. For the first time we demonstrated the synthesis of fluorescent organic NPs of specially designed aggregation-induced emission luminophore (AIE LP). The brightness of such NPs was determined to be comparable to that of quantum dots.

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Laser Induced Breakdown Spectroscopy LIBS is a fast non-contact technique for the analysis of the elemental composition using spectral information of the emission from a laser-induced plasma. For the LIBS studies in this thesis the focus has been in using very low energy, microjoule pulses in order to give high spatial resolution and minimize the laser system requirements. This is a regime that we refer to as microLIBS. Under such conditions it is important to maximize the signal detected to give the lowest limit of detection LOD possible. One technique to improve the signal to noise ratios is by coupling LIBS with Laser Induced Fluorescence. This is a technique where the _rst pulse creates a vapor plume and the second pulse tuned to a resonant absorption line of the species of interest re-excites the plume. We term this technique as Laser ablation Laser Induced Fluorescence LA-LIF. We have been investigating the performance of LA-LIF at low pulse energies (_ 1 mJ for both pulses) for the detection of elemental contaminants in water. This technique allows reasonable performance compared to high energy singlepulse LIBS, but at a much reduced total energy expenditure. This allows LODs in the parts per billion range ppb range which typically cannot be obtained with low energy single pulse probing of the systems. This approach or exceeds the sensitivities which can be obtained with many shots using much larger energy systems. In this thesis we investigated the performance of LIBS at low pulse energies for the detection of Pb as a contaminant in water. An LOD of 70 ppb was obtained for an accumulation of 100 shots with the ablation laser pulse energy of 250 _J and an excitation laser pulse energy of 8 _J. A systematic study of the detector conditions was made for the system for the detection of Pb. Scaling laws for the LOD in terms of the pump and probe energies were measured and also the e_ect of detector gain, the gate delay and the gate width were studied. In this thesis LIBS and LA-LIF were also used to analyze ultralow volumes of analyte in liquids in microuidic geometries. LIBS was applied for the detection of Na in liquid droplets in a microuidic system. The detection of Na as low as 360 femtograms was demonstrated for 100 shots integrated in this system. An LOD of 7 ppm for Pb for 100 shot accumulation was demonstrated using the LA-LIF technique on an 18 _m diameter microdroplet. To study the laser interaction with the water targets the MEDUSA one dimensional hydrocode was used. The propagation of the shockwave and plume dynamics were studied using this modeling code. The expansion of the plume was studied and compared to experimentally measured values and to physical models for blast wave expansion and stagnation. Two preconcentration techniques were also studied, one of which used a wood-chip as a substrate to absorb the analyte liquid and wick the salt on to the surface for analysis and the other used an electroplating technique to plate the analyte metal as a thin _lm on a substrate metal used as a cathode. The electroplating method for preconcentration was also studied using a microchip laser and a LOD of 6.4 ppb for Pb in water was obtained for an accumalation of 200,000 shots. / Photonics and Plasmas

This dissertation presents the design, fabrication, and testing of a microfluidic system to be used for whole-cell analysis. The study of cellular function and structure is essential for disease diagnosis and treatment. Microsystems developed to perform these bioanalyses add benefits such as requiring smaller samples and reagents, testing multiple samples in parallel, and supporting point-of-care testing, all of which increases throughput and reduces cost-per-analysis. Traditional methods for designing a microsystem use standard materials and techniques such as silicon, glass, photolithography, and wet and dry etching. This research is focused on utilizing materials and techniques that require less infrastructure, allow for a faster design-to-prototype cycle, and can integrate electrical and fluidic functionality to address a variety of possible applications. The microfluidic system presented in this thesis is comprised of multiple layers of Kapton, a polyimide available from DuPont. Kapton provides a biocompatible substrate that is flexible while maintaining structural stability and can be used in high temperature and other harsh environments. Microchannels with widths of 400 m and thru-hole fluidic vias less than 5 m in diameter are laser ablated through the flexible polyimide sheets using excimer and CO2 lasers. Electrical traces and contact pads are defined on the substrate by vapor deposition through reusable microstencils rather than with photolithography. The patterned layers are bonded using heat staking and then packaged with the addition of wires and a fluidic interface. Validation of the system for whole-cell analysis was first performed with impedance spectroscopy measurements collected on air, DI water, phosphate buffered saline, clusters of human cancer cells, and human cancer tissue samples. This was followed by testing the ability to use the device to control the movement and position of 10 m diameter microbeads and dissociated cells. As a whole, this research demonstrates the realization of a microfluidic system for whole-cell analysis based on non-standard fabrication materials and techniques.

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This thesis is about the phase transformation, shape, size distribution and coalescence of TiO2 (part I) and ZrO2 (part II) nanopartilces produced by Nd-YAG laser ablation on metal targets under oxygen background gas, and characterized by analytical electron microscopy. The optimum laser ablation condition that satisfactory and routinely yield high-pressure phases of TiO2 (i.e. £\-PbO2-type and fluorite-related structures) and ZrO2 with high residual stress were reported. Part I-1 focuses on physical coagulation, by Van der Waals force, of the TiO2 condensates at temperatures up to about 1000 K as a result of post-condensation radiant heating. In part I-2, imperfect oriented attachment of nanoparticles over specific surfaces is rationalized to cause accretion and defects for the rutile condensates. Brownian motion may proceed above a critical temperature for anchorage release at the interface of imperfect attached nanoparticles until an epitaxial relationship is reached. Part I-3 deals with further the Brownian-type rotation of the imperfectly impinged £\-PbO2-type TiO2 and rutile nanocondensates until interfacial-energy cusp was reached. In part I-4 laser ablation condensation synthesis of dense TiO2 polymorphs and their phase transformations were documented. Part II-1 is about dense tetragonal (t)-ZrO2 and cubic (c-) nanocondensates which were synthesized under very rapid heating and cooling by pulsed Nd-YAG laser ablation with oxygen background gas. The t-ZrO2 nanoparticles were found to form deformation twins/faults and followed unique transformation path upon local electron dosage. Electron diffraction indicated that the dense c- and t- phase with specific size and residual stress were allowed to relax and/or kinetically phase change into lower-energy state as constrained by the intersections of the internal energy vs. cell volume plots calculated for the two polymorphs (Part II-2).

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