Nesta tese estudamos a relação entre as propriedades de absorção de multi-fótons e a estrutura molecular de três classes distintas de compostos orgânicos π-conjugados: derivados de vitamina A, complexos de platina acetilada e compostos quirais. Materiais orgânicos emergiram nas últimas décadas como candidatos para aplicações em dispositivos fotônicos, principalmente aqueles envolvendo processos de absorção multifotônica, uma vez que suas propriedades podem ser facilmente otimizadas através de engenharia molecular. Devido às diferenças inerentes entre as estruturas químicas dos compostos aqui investigados, foi possível verificar individualmente a influência do comprimento de conjugação, da presença de grupos doadores e aceitadores de elétrons (estruturas push-pull), da planaridade molecular e de efeitos de comprimento de ligação sobre a seção de choque de absorção multifotônica. Para tanto, foram utilizadas as técnicas de Varredura-Z convencional e com contínuo de luz branca, espectroscopia de fluorescência por absorção de multi-fótons e fluorescência resolvida no tempo. Para correlacionar as propriedades moleculares com os espectros não-lineares, foram utilizados cálculos de química quântica em conjunto com o modelo de soma de estados essenciais. Através desse modelo foi possível associar aspectos puramente moleculares, como o momento de dipolo de transição, o momento de dipolo estático, a força do oscilador e a largura de linha dos estados eletrônicos com a estrutura molecular dos cromóforos, visando futuras aplicações tecnológicas. Resultados de espectroscopia de absorção de dois fótons revelaram que os derivados da vitamina A, como o trans-β-apo-8-carotenal e all-trans β-caroteno, possuem magnitudes da seção de choque extremamente elevadas (~5000 GM), indicando-os como materiais promissores para armazenamento óptico 3D. Os complexos de platina acetilada apresentaram características impares para aplicações em dispositivos de limitação de potência óptica baseados em processos de absorção de dois e três fótons como, elevadas absortividades não-lineares, boa transparência óptica, baixo limiar de limitação, alto intervalo dinâmico e rápido tempo de resposta. Por fim, os compostos quirais abriram possibilidades de explorar novos efeitos em óptica não-linear como, por exemplo, efeito de dipolo magnético e quadrupolo elétrico, apenas modificando o estado de polarização da luz. / In this thesis we studied the relationship between the multi-photon absorption properties and the molecular structure of three distinct classes of π-conjugated organic compounds: derivatives of vitamin A, platinum acetylide complexes and chiral compounds. Organic materials have emerged as potential candidates for applications involving multiphoton absorption, since their properties can be changed through molecular engineering. Because of the inherent differences between the molecular structures of the compounds investigated here, it was possible to verify the influence of conjugation length, electron donor and acceptors groups (push-pull structures), molecular planarity and effects of bond length alternation on the multi-photon absorption cross-section. To investigate such properties, we have employed the conventional and white-light continuum femtosecond Z-scan technique and multi-photon and time-resolved fluorescence spectroscopy. We have also employed quantum chemical calculation and the essential sum-over-states approach to correlate the impact of molecular properties on the nonlinear spectra. It was possible to link pure molecular features such as transition dipole moment, static dipole moment, oscillator strength and states linewidth with the chromophores structures, aiming at future applications. The two-photon absorption spectroscopy results revealed that the derivatives of vitamin A, such as trans-β-apo-8-carotenal and all-trans β-carotene, present cross-sections values extremely high (~ 5000 GM), indicating them as promising materials for 3D optical storage. The platinum acetylide complexes can be applied in optical power limiting devices based on the two- and three-photon absorption process, since they present unique features, such as high nonlinearity, good optical transparency, low threshold limit, high dynamic range and fast response time. Finally, the chiral compounds opened up new possibilities to be explored in nonlinear optics, such as the effect of magnetic dipole and electric quadrupole, only manipulating the polarization state of the light.

This thesis is an investigation of the fabrication and assembly methodologies employed in the development of a proof-of-principle prototype electric guitar composed of laminated copolyester. The objective of the project was to develop the processes and procedures to create an optimized physical and visual bond between layers to minimize vibratory dissipation, thus maximizing sustain. A high speed CNC router, abrasive waterjet, laser engraver-cutter, as well as various manual fabrication and assembly methods were investigated in the construction of the guitar prototypes. The lamination processes explored include low-temperature, heat-assisted pressure bonding, solvent and chemical welding, and contact adhesives. The project concluded with the completion of a working guitar comprised of a laminated copolyester body and a traditional bolton wooden neck.

This dissertation demonstrates the design of reversibly self-morphing novel liquid crystalline elastomer (LCE) antennas that can dynamically change electromagnetic performance in response to temperature. This change in performance can be achieved by programming the shape change of stimuli-responsive (i.e., temperature-responsive) LCEs, and using these materials as substrates for reconfigurable antennas. Existing reconfigurable antennas rely on external circuitry such as Micro-Electro-Mechanical-Systems (MEMS) switches, pin diodes, and shape memory alloys (SMAs) to reconfigure their performance. Antennas using MEMS or diodes exhibit low efficiency due to the losses from these components. Also, antennas based on SMAs can change their performance only once as SMAs response to the stimuli and is not reversible. Flexible electronics are capable of morphing from one shape to another using various techniques, such as liquid metals, hydrogels, and shape memory polymers. LCE antennas can reconfigure their electromagnetic performance, (e.g., frequency of operation, polarization, and radiation pattern) and enable passive (i.e., battery-less) temperature sensing and monitoring applications, such as passive radio frequency identification device (RFID) sensing tags. Limited previous work has been performed on shape-changing antenna structures based on LCEs. To date, self-morphing flexible electronics, including antennas, which rely on stimuli-responsive LCEs that reversibly change shape in response to temperature changes, have not been previously explored. Here, LCE antennas will be studied and developed. Also, the metallization of LCEs with different metal conductors and their fabrication process, by either electron beam (E-Beam) evaporation or optical gluing of the metal film will be observed. The LCE material can have a significant impact on sensing applications due to its reversible actuation that can enable a sensor to work repeatedly. This interdisciplinary research (material polymer science and electrical engineering) is expected to contribute to the development of morphing electronics, including sensors, passive antennas, arrays, and frequency selective surfaces (FSS).

It has been found that non-magnetic organic semiconductors can show some magnetic responses in low magnetic field (<100 >mT). When applying magnetic field, the electroluminescence, electrical current, photocurrent, and photoluminescence could change with magnetic field, which are called magnetic field effects. Magnetic field effects are generated through spin-dependent process affected by the internal magnetic interaction. In nonmagnetic materials, hyperfine interaction has been supposed to dominantly affect the spin-dependent process recently. But the conclusion was made in weak spin-orbital coupling organic semiconductor. The hyperfine interaction might not be the main reason responsible for magnetic field effects in strong spin-orbital coupling materials. Therefore, the study of magnetic field effects in strong spin-orbital coupling organic semiconductor is important to get a whole view of the origin of the magnetic field effects in nonmagnetic organic semiconductors. This dissertation will clarify the generation mechanism of magnetic field effect in nonmagnetic organic semiconductors and further explore how the strong spin-orbital coupling affecting the magnetic field effect. It has been found the intermolecular excited states are important inter-median for magnetic field effects. The change of intersystem crossing at intermolecular excited states will change the singlet/triplet ratio and further generate magnetic field effects through different recombination and dissociation properties of singlet and triplet intermolecular excited states. Both the energy transfer effect coupled spin orbital coupling and energy transfer effect free spin orbital-coupling are discussed in the dissertation. The tuning of the magnetic field effect by adjusting the spin-orbital coupling is also established through distance effect and interface effect. It has been found that changing inter-molecular spin-orbital coupling is a critical factor to generate magnetic field effects in organic semiconductors. And the sensitivity of different magnetic field effects to strong spin-orbital coupling strength is depending on the final product. The internal magnetic interaction can be hyperfine interaction, spin orbital coupling and spin-spin interaction between electrons. The hyperfine interaction and spin orbital coupling are important in nonmagnetic organic semiconductors. But the electron spin-spin interaction is important in magnetic organic semiconductors. The magnetocurrent for magnetic and nonmagnetic organic semiconductors at different temperature has been compared.

Metal-organic frameworks (MOFs) are a new class of nanoporous materials that have received great interest since they were first synthesized in the late 1990s. Practical applications of MOFs are continuously being discovered as a better understanding of the properties of materials adsorbed within the nanopores of MOFs emerges. One such potential application is as a component of an explosive-sensing system. Another potential application is for hydrogen storage. This work is focused on tailoring MOFs to adsorb/desorb the explosive, RDX. Classical grand canonical Monte Carlo (GCMC) and molecular dynamic (MD) simulations have been performed to calculate adsorption isotherms and self-diffusivities of RDX in several IRMOFs. Because gathering experimental data on explosive compounds is dangerous, data is limited. Simulation can in part fill the gap of missing information. Through these simulations, many of the key issues associated with MOFs preconcentrating RDX have been resolved. The issues include both theoretical issues associated with the computational generation of properties and practical issues associated with the use of MOFs in explosive-sensing system. Theoretically, we evaluate the method for generating partial charges for MOFs and the impact of this choice on the adsorption isotherm and diffusivity. Practically, we show that the tailoring of an MOF with a polar group like an amine can lead to an adsorbent that (i) concentrates RDX from the bulk by as much as a factor of 3000, (ii) is highly selective for RDX, and (iii) retains sufficient RDX mobility allowing for rapid, real time sensing. Many of the impediments to the effective explosive detection can be framed as shortcomings in the understanding of molecule surface interactions. A fundamental, molecular-level understanding of the interaction between explosives and functionalized MOFs would provide the necessary guidance that allows the next generation of sensors to be developed. This is one of the main driving forces behind this dissertation. Another important achievement in this work is the demonstration of a new direction for tailoring MOFs. A new class of tailored MOFs containing porphyrins has been proposed. These tailored MOFs show greater capability for hydrogen storage, which also demonstrated the great functionalization of MOFs and great potential to serve as preconcentrators. The use of a novel multiscale modeling technique to develop equations of state for inhomogeneous fluids is included as a supplement to this dissertation.

Nanoindentation is a method of contacting a material whose mechanical properties are unknown with another material whose properties are known. Nanoindentation has the advantage of being able to probe a material’s microstructure while being sensitive enough to detect variations in mechanical properties. However, nanoindentation has some limitations as a testing technique due to the specific formation and structure of some biomaterials. The main objective of this research is to identify any factors that influence the nanoindentation measurement of wood cell walls (a typical biomaterial). The function of the embedding media in describing the properties of wood cells is poorly understood. This research demonstrated that Spurr’s resin, when diffused into wood cell wall during the embedding process, enhanced both the Young’s modulus and hardness of the cell walls. A substitute sample preparation method was developed to avoid this resin penetration into cell wall and was determined to be both effective and easy to perform. The nanoindentation procedure involves the application of a monitor and an analysis of the load-displacement behavior and the response in the material. It can be anticipated that various ways of loading, including the maximum force, the loading time, and others, will cause a variety of mechanical properties. Thus, our second aim was to study the effect of load function on nanoindentation measurement in wood. It was discovered that a fast loading rate contributed to greater contact depth and lower hardness. Increasing the holding time decreased measured values for both Young’s modulus and hardness. However, no significant difference of Young’s modulus and hardness among three loading functions with different unloading rates. The final part of the research was to study the effect of moisture content on the micromechanical properties of wood material. Several nanoindentations were performed on the wood cell wall while varying the moisture content of wood. Results indicated that both the Young’s modulus and hardness decreased significantly with an increase of moisture content. A rheology model was developed to describe the nanoindentation behaviors of wood cell walls at different moisture contents. Five parameters were extracted from Burger’s model, and the relationships among those five parameters were quantified.

Nanoindentation is a method of contacting a material whose mechanical properties are unknown with another material whose properties are known. Nanoindentation has the advantage of being able to probe a material’s microstructure while being sensitive enough to detect variations in mechanical properties. However, nanoindentation has some limitations as a testing technique due to the specific formation and structure of some biomaterials. The main objective of this research is to identify any factors that influence the nanoindentation measurement of wood cell walls (a typical biomaterial).The function of the embedding media in describing the properties of wood cells is poorly understood. This research demonstrated that Spurr’s resin, when diffused into wood cell wall during the embedding process, enhanced both the Young’s modulus and hardness of the cell walls. A substitute sample preparation method was developed to avoid this resin penetration into cell wall and was determined to be both effective and easy to perform.The nanoindentation procedure involves the application of a monitor and an analysis of the load-displacement behavior and the response in the material. It can be anticipated that various ways of loading, including the maximum force, the loading time, and others, will cause a variety of mechanical properties. Thus, our second aim was to study the effect of load function on nanoindentation measurement in wood. It was discovered that a fast loading rate contributed to greater contact depth and lower hardness. Increasing the holding time decreased measured values for both Young’s modulus and hardness. However, no significant difference of Young’s modulus and hardness among three loading functions with different unloading rates.The final part of the research was to study the effect of moisture content on the micromechanical properties of wood material. Several nanoindentations were performed on the wood cell wall while varying the moisture content of wood. Results indicated that both the Young’s modulus and hardness decreased significantly with an increase of moisture content. A rheology model was developed to describe the nanoindentation behaviors of wood cell walls at different moisture contents. Five parameters were extracted from Burger’s model, and the relationships among those five parameters were quantified.

Solubility enhancement of poorly-soluble active pharmaceutical ingredients (APIs) remains a scientific challenge and poses a practical issue in the pharmaceutical industry. The emergence of pharmaceutical cocrystals has contributed another dimension to the diversity of crystal forms available at the disposal of the pharmaceutical scientist. That pharmaceutical cocrystals are amenable to the design principles of crystal engineering means that the number of crystal forms offered by pharmaceutical cocrystals is potentially greater than the combined numbers of polymorphs, salts, solvates and hydrates for an API. The current spotlight and early-onset dissolution profile ("spring-and-parachute" effect) exhibited by certain pharmaceutical cocrystals draw attention to an immediate question: How big is the impact of cocrystals on aqueous solubility? The scientific literature and in-house data on pharmaceutical cocrystals that are thermodynamically stable in water are reviewed and analyzed for trends in aqueous solubility and melting point between the cocrystal and the cocrystal formers. There is poor correlation between the aqueous solubility of cocrystal and cocrystal former with respect to the API. The log of the aqueous solubility ratio between cocrystal and API has a poor correlation with the melting point difference between cocrystal and API. Structure-property relationships between the cocrystal and the cocrystal formers remain elusive and the actual experiments are still necessary to investigate the desired physicochemical properties. Crystal form (cocrystals, polymorphs, salts, hydrates and solvates) diversity is and will continue to be a contentious issue for the pharmaceutical industry. That the crystal form of an API dramatically impacts its aqueous solubility (a fixed thermodynamic property) is illustrated by the histamine H2-receptor antagonist ranitidine hydrochloride and HIV protease inhibitor ritonavir. For more than a century, the dissolution rate of a solid has been shown to be directly dependent on its solubility, cçterîs paribus. A century later, it remains impossible to predict the properties of a solid, given its molecular structure. If delivery or absorption of an API are limited by its aqueous solubility, aqueous solubility then becomes a critical parameter linking bioavailability and pharmacokinetics of an API. Since the majority of APIs are Biopharmaceutical Classification System (BCS) Class II (low solubility and high permeability) compounds, crystal form screening, optimization and selection have thus received more efforts, attention and investment. Given that the dissolution rate, aqueous solubility and crystal form of an API are intricately linked, it remains a scientific challenge to understand the nature of crystal packing forces and their impact upon physicochemical properties of different crystal forms. Indeed, the selection of an optimal crystal form of an API is an indispensable part of the drug development program. The impact of cocrystals on crystal form diversity is addressed with molecular and ionic targets in ellagic acid and lithium salts. A supramolecular heterosynthon approach was adopted for crystal form screening. Crystal form screening of ellagic acid yields molecular cocrystals, cocrystal solvates/hydrates and solvates. Crystal form screening of lithium salts (chloride, bromide and nitrate salts) afforded ionic cocrystals and cocrystal hydrates.

Complex engineered nanoparticles (CENPs) are being used on various applications. Their properties are different from those of neat nanoparticles. The dissertation explores these differences from four aspects: 1) Modify carbon nanomaterials’ inert surfaces and investigate the effect on thermal and rheological behavior of their dispersions; 2) Generate self-assembly bi-layer structure of oxide nanoparticles via surface modification; 3) Study interaction between lysozyme and different surface-charged ceria nanoparticles; 4) Investigate the biodistribution and transformations of CENPs in biological media. An environment-friendly surface modification was developed to modify surfaces of carbon nanomaterials for increasing their affinity to non-polar fluid. It can offset formation of agglomerates in dispersions. Less agglomerates change thermal conductivity and rheological behavior. One combined model, considering shape factor, was built to fit non-linear enhancement on thermal conductivity with volume fraction of nanoparticles. Constructing bi-layer structure of oxide nanoparticles with different refractive index was crucial for optical thin films. Silanization was used to transform relatively hydrophilic surface of oxide nanoparticles to hydrophobic surface via attaching alkane chains. The self-assembly separation of these nanoparticles can form bi-layer structure in single deposition process since neat nanoparticles keep in hydrophilic monomer while surface-modified nanoparticles settled down. The adsorption behaviors of lysozyme, one protein with net positive charge, on different surface-charged ceria nanoparticles were investigated. The adsorption isotherm curves were fitted with the Toth and Sips equations satisfactorily. The heterogeneity parameters suggest the surface charge predominate adsorption on negatively charged ceria while lateral effect predominate adsorption on positively charged ceria. The local site energy distributions were also estimated. The 26Al-labeled nanoalumina coated by 14C-labeled citrate was synthesized and its dispersion was infused intravenously into rat. The Accelerator Mass Spectrometer (AMS) was used to measure isotopes in dosing material and tissues. The ratio of coating and core in liver was slightly less than dosing material while the ratios in brain and bone are much higher than dosing material. It may suggest that some citrate coating dissociated from nanoalumina’s surface, entered metabolic cycles, and then redistributed to other organs.

Magnesium has been identified as a promising biodegradable implant material because it does not cause systemic toxicity and can reduce stress shielding. However, it corrodes too quickly in the body. Titanium, which is already used ubiquitously for implants, was chosen as the alloying element because of its proven biocompatibility and corrosion resistance in physiological environments. Thus, alloying magnesium with titanium is expected to improve the corrosion resistance of magnesium. Mg-Ti alloys with a titanium content ranging from 5 to 35 at.-% were successfully synthesized by mechanical alloying. Spark plasma sintering was identified as a processing route to consolidate the alloy powders made by ball-milling into bulk material without destroying the alloy structure. This is an important finding as this metastable Mg-Ti alloy can only be heated up to max. 200C° for a limited time without reaching the stable state of separated magnesium and titanium. The superior corrosion behavior of Mg80-Ti20 alloy in a simulated physiological environment was shown through hydrogen evolution tests, where the corrosion rate was drastically reduced compared to pure magnesium and electrochemical measurements revealed an increased potential and resistance compared to pure magnesium. Cytotoxicity tests on murine pre-osteoblastic cells in vitro confirmed that supernatants made from Mg-Ti alloy were no more cytotoxic than supernatants prepared with pure magnesium. Mg and Mg-Ti alloys can also be used to make novel polymer-metal composites, e.g., with poly(lactic-co-glycolic acid) (PLGA) to avoid the polymer’s detrimental pH drop during degradation and alter its degradation pattern. Thus, Mg-Ti alloys can be fabricated and consolidated while achieving improved corrosion resistance and maintaining cytocompatibility. This work opens up the possibility of using Mg-Ti alloys for fracture fixation implants and other biomedical applications.