The laminar flow in the small bronchial tubes is quite complex due to the presence of vortex-dominated, secondary flows. Contributing to this complexity are the geometrical characteristics of the bronchial tubes that include asymmetric and nonplanar branching. These secondary flow fields play a crucial role in particle deposition; however, the actual mechanisms that determine the particle distributions are not fully understood. The research reported here increases understanding of this phenomenon by studying flow structure/ particle interaction in the small bronchial tubes for steady and unsteady respiratory conditions. Specifically, the effects of simultaneous nonplanar and asymmetric branching were investigated. The nonplanar model was generated by applying a 90◦ out-of-plane rotation to the third-generation branches. Steady-state inspiratory flows for a Reynolds number of 1,000 and unsteady periodic flows with a 30-respiration-per-minute breathing frequency were simulated in three-generation, asymmetric, planar and nonplanar models. The asymmetry and nonplanarity produced asymmetric secondary flow patterns and unequal mass flow partitioning in the third-generation branches. Ten micron water droplet deposition in the nonplanar model was found to be significantly different from the planar model, demonstrating the impact of simultaneous nonplanar and asymmetric branching. The unsteady nature of the flow also affected particle deposition. Particles released at the same instantaneous inflow conditions during off-peak inhalation conditions, generated significantly different particle deposition patterns. The differences were attributed to the high temporal variations of the fluid velocities at these off-peak times and history effects in the flows. It was also observed that the initial particle velocities had a significant impact on particle deposition. The study of flow structure and particle interaction was facilitated by the development of a novel visualization technique that employs finite-time Lyapunov exponents (FTLE). This research provides a better understanding of the fluid dynamics driving the particle deposition in the bronchial tubes.

The aim of the thesis is to utilize Raman optical activity (ROA) to get unique information on peptide/protein conformation, which is otherwise difficult or even impossible to obtain. We have focused on investigation of amide and disulfide groups. Utilizing tailor-made model structures (rigid tricyclic spirodilactams with two interacting nonplanar amide groups), special model peptides and even biologically active molecules (neurohypophyseal hormones and their agonistic and antagonistic analogs, antimicrobial peptide lasiocepsin and its analogs having different disulfide pattern) we have traced specific spectral manifestation of nonplanar amides and disulfides. ROA results were supplemented by data obtained by complementary chiroptical methods - electronic (including vacuum UV - SRCD) and vibrational circular dichroism. When used in a concerted fashion, these techniques provide complex information on peptide/protein secondary structure. Where possible, experimental chiroptical data were compared to ab initio calculations. In chiroptical spectra we have found and interpreted signals reflecting nonplanarity of the amide group. Moreover, in ROA spectra we have identified signals due to S-S stretching vibrations which seem to reflect sense of the disulfide group torsion.

3D printing technology, which has its origins in rapid prototyping, is increasingly used to build functional devices. Although 3D printing technology has been well developed for thermoplastic polymers and metals, it is still in the research phase for soft polymeric materials such as silicones. Silicones are an industrially vital polymer characterized by a broad spectrum of chemical and physical properties for several smart applications, including on skin printing, smart sensors, multigradient material, and soft actuators. Extrusion-based multimaterial printing is one of the 3D printing techniques that have been adapted due to its compatibility to process silicone-based materials for constructing various functional devices. However, there are several challenges such as achieving on the fly mixing at low Reynolds numbers regime, achieving fast switching while using Newtonian/non-Newtonian inks, and achieving multimaterial printing on nonplanar surfaces. The development of suitable and robust printheads that are able to tackle those challenges can expand the application of this technology to a wide range of fields. In this thesis, several deposition-controlled printhead designs have been created for 3D printing multifunctional devices using an understanding of microfluidics. The established printhead can be controlled to formulate different multigradient structures through on the fly mixing during the material printing. Moreover, the developed printhead can be adapted to print multi viscous inks with high switching rates up to 50 Hz. Through the developed system, the printhead was able to track topologies in real-time, allowing objects to be printed over complex substrates. These new capabilities were applied to fabricate functional structures in order to demonstrate the potential of the developed printhead approaches that can be used in various applications, including smart sensors, soft robotics and multigradient objects. / Thesis / Doctor of Philosophy (PhD) / 3D printing techniques, such as extrusion-based multimaterial printing, have recently been utilized to process silicones due to their versatility in different smart applications, including multigradient material and soft actuators. Although it represents significant progress, there are still several challenges, including the proper mixing during printing with a laminar flow regime, the fast switching between different inks, and the printing over complex topographies. Therefore, various printhead designs have been developed in this thesis to tackle these challenges. In particular, a mixer printhead has been designed to allow mixing during printing for building multigradient objects. Also, a scalable printhead has been developed to allow fast switching for creating pixelated structures. Finally, a simple mechanical system has achieved multimaterial printing over various nonplanar surfaces. To the best of the author's knowledge, the developed printheads can be used in many fields, such as soft robotics and smart devices.

Various models featuring horizontal wells with multiple induced fractures have been proposed to characterize flow behavior over time in tight gas and shale gas systems. Currently, there is little consensus regarding the effects of non-ideal fracture geometries and coupled primary-secondary fracture interactions on reservoir performance in these unconventional gas reservoirs. This thesis provides a grid construction tool to generate high-resolution unstructured meshes using Voronoi grids, which provides the flexibility required to accurately represent complex geologic domains and fractures in three dimensions. Using these Voronoi grids, the interaction between propped hydraulic fractures and secondary "stress-release" fractures were evaluated. Additionally, various primary fracture configurations were examined, where the fractures may be non-planar or non-orthogonal. For this study, a numerical model was developed to assess the potential performance of tight gas and shale gas reservoirs. These simulations utilized up to a half-million grid-blocks and consider a period of up to 3,000 years in some cases. The aim is to provide very high-definition reference numerical solutions that will exhibit virtually all flow regimes we can expect in these unconventional gas reservoirs. The simulation results are analyzed to identify production signatures and flow regimes using diagnostic plots, and these interpretations are confirmed using pressure maps where useful. The coupled primary-secondary fracture systems with the largest fracture surface areas are shown to give the highest production in the traditional "linear flow" regime (which occurs for very high conductivity vertical fracture cases). The non-ideal hydraulic fracture geometries are shown to yield progressively lower production as the angularity of these fractures increases. Hence, to design optimum fracture completions, we should endeavor to keep the fractures as orthogonal to the horizontal well as possible. This work expands the current understanding of flow behavior in fractured tight-gas and shale-gas systems and may be used to optimize fracture and completion design, to validate analytical models and to facilitate more accurate reserves estimation.

The thesis inquires the specific and advantageous applications of Raman optical activity (ROA) in wide range of diverse structural and conformational studies of biomolecules and other biologically important molecules. Our investigation was focused on several interconnected topics covering the fields of methodology, basic and applied research. The combination of experimental and theoretical approaches facilitated deeper understanding of studied phenomena, and allowed for the effects of solute-solvent interactions. High-quality spectra of model molecules in the C-H stretching region, acquired as a result of successful extension of ROA measurements to the whole region of fundamental molecular vibrations, enabled verification and further development of methods for ROA spectra simulations encompassing anharmonic corrections. Utilizing spirodilactams with highly nonplanar amide groups, we have traced the specific ROA spectral manifestations of amide nonplanarity. In case of antimicrobial peptide lasiocepsine, we have successfully simulated ROA signals of S-S stretching vibrations which contrary to current belief do not seem to reflect sense of the S-S group torsion. In larger molecular systems, we have better understood the process of the formation of stable polyproline II conformation and proved that ROA may...