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Rewritable photochrome-based 3D optical data storage requires photochromic molecules with high two-photon absorption (2PA) cross sections. Currently, the low value of two-photon absorption cross sections of existing photochromes makes them unsuitable for practical application in 3D data storage. Worldwide attempts to increase the cross section of photochromic molecules by altering the chemical structure have yielded poor results. In this work, two ways to increase the two-photon absorption cross sections of photochromes were investigated. In the first method, partial success demonstrated by extending the conjugation of a photochromic molecule, a high two-photon absorption cross section of the closed form isomer and high photoconversion to the closed form were realized. At the same time, a decrease in photoswitching quantum yield and low photoconversion to open form was observed. A discussion is provided to explain the results, suggesting that the proposed method of extending the conjugation may not solve the problem. For this reason a new method for effective two-photon absorption cross section enhancement of photochromes was proposed. As a proof of principle, a new two-photon absorbing dye with a hydrogen bonding moiety was synthesized and used for the formation of supramolecular structures with a photochromic compound. Theoretical reasoning and experimental demonstration of energy transfer from the dye to the photochrome under one and two-photon excitation confirmed the practical value of the method. The effects of a 2PA dye on the photochromic properties of a diarylethene were investigated using a model compound to simplify data analysis. Formation of supramolecular structures was revealed using ¹H NMR spectroscopic methods. The model compound, having the same hydrogen bonding moiety as 2PA dye, has been demonstrated to bind with photochrome molecules at very low concentrations. Photochromic properties of 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, including conversions at the photostationary state, extinction coefficients, photoisomerization reaction rates and quantum yields, were shown to be affected by hydrogen bonding with the model compound - 2,6-bis-(acetamido)pyridine. The extent of this change was determined and discussed, demonstrating a balanced supramolecular strategy to modulate photochemical and photophysical properties of this important class of photochromic material.

Energy harvesting can be used to consume the potential power of the surrounding environment. This harvesting can be done in different ways, some common energy harvesting modalities are vibrations, heat differences, solar power, and RF energy. In this Master Thesis, these different methods for harvesting energy are studied and the one that is the most suitable for an environment inside an embankment dam is further explored. If some energy harvesting modalities can operate well in that environment then it might be possible to monitor the embankment dam from the inside. The hope is to create an energy harvesting platform equipped with some suitable sensors which can be placed inside an embankment dam and collect data for a longer duration of time. Considering how an embankment dam is structured, it was concluded that the best possible energy harvesting method is wireless ultra-high frequency radio signals. An RF energy harvesting platform was created and tested, both in a laboratory and buried underground, mimicking the environment inside an embankment dam. These tests were measured and the results showed some promise that it is possible to use this energy harvesting method to power a sensor platform underground.

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A full understanding of chemical reaction dynamics at the gas/organic-surface interface requires knowledge of energy-transfer processes that happen during the initial gas/surface collision. We have examined the influence of mass and rovibrational motion on the energy-transfer dynamics of gas-phase species scattering from model organic surfaces using theory and experiment. Molecular-beam scattering techniques were used to investigate the rare gases, Ne, Ar, Kr, and Xe, and the diatomics, N₂ and CO, in collisions with CH₃- and CF₃-terminated self-assembled monolayer (SAM) surfaces. Complementary molecular-dynamics simulations were employed to gain an atomistic view of the collisions and elucidate mechanistic details not observable with our current experimental apparatus. We developed a systematic approach for obtaining highly accurate analytic intermolecular potential-energy surfaces, derived from high-quality ab initio data, for use in our classical-trajectory simulations. Results of rare gas scattering experiments and simulations indicate mass to be the determining factor in the energy-transfer dynamics, while other aspects of the potential-energy surface play only a minor role. Additionally, electronic-structure calculations were used to correlate features of the potential-energy surface with the energy-transfer behavior of atoms and small molecules scattering from polar and non-polar SAM surfaces. Collisions of diatomic molecules with SAMs are seen to be vibrationally adiabatic, however translational energy transfer to and from rotational modes of the gas species, while relatively weak, is readily apparent. Examination of the alignment and orientation of the final rotational angular momentum of the gas species reveals that the collisions induce a stereodynamic preference for the expected "cartwheel" motion, as well as a surprising propensity for "corkscrew" or "propeller" motion. The calculated stereodynamic trends suggest that the CH₃-SAM is effectively more corrugated than the CF₃-SAM. Finally, the feasibility for collisional-energy promoted, direct gas/organic-surface reactions was interrogated using the 1,3-dipolar azide-alkyne cycloaddition reaction. We found that geometrical constraints prevented the reaction from proceeding at the probed conditions. / Ph. D.

Technological advances require novel solutions for contactless energy transfer. Many engineering applications require unique approaches to power electrical components without using physical wires. In the past decade, awareness of the need to wirelessly power electrical components spawned many forays into the field of wireless power transfer (WPT). WPT techniques include capacitive energy transfer, electromagnetic inductive power transfer, electromagnetic radiative power transfer, electrostatic induction, and acoustic energy transfer. Acoustic energy transfer (AET) has many advantages over other methods. These advantages include lower operating frequency, shorter wavelengths enabling the use of smaller sized receiver and transmitter, extended transmitter-to-receiver distance therefore more manageable design constraints, achieving lower attenuation, higher penetration depth, and no electromagnetic losses. Most AET systems operate in the ultrasonic frequency range and are more commonly referred to as ultrasonic acoustic energy transfer (UAET) systems. Through-wall UAET systems are constructed of a transmitter bonded to a transmission elastic layer, which in turn is bonded to a receiver. The transmitter and receiver layers are constructed of a piezoelectric material. Piezoelectric materials behave according to the piezoelectric effect, which is when a material generates an electric charge in response to mechanical strain. The transmitter utilizes the reverse of the piezoelectric effect. A sinusoidal input voltage is applied to the transmitter, inducing vibrations in the transmitter. The vibration-induced acoustic waves emanating from the transmitter travel through the initial bonding layer, the transmission layer, and the final bonding layer to the receiver. In turn, the acoustic waves cause the receiver to deform and undergo strain. This induces a flow of charge in the receiver, which is an electric current. The receiver feeds current to a resistive load. In this manner, energy is acoustically transferred between two transducers without wires. The performance of UAET systems can be evaluated based on power transfer efficiency, voltage magnification, and input admittance. UAET systems require extensive modeling before experimental assembly can be attempted. The analytical models of UAET are either based on the mechanics of the constitutive relations of piezoelectricity and solid mechanics or using equivalent circuit methods. The equivalent circuit method approximates the physics of the UAET system with electrical assumptions. The mechanics-based method is the most comprehensive description of the physics of all the intermediate layers in a UAET system. The mechanics-based method has been based on the assumption that the UAET system is operated in the thickness mode of vibration, i.e., piston-like vibration mode where the transmitter and receiver disks vibrate only in the thickness direction. This poses an issue for disks with aspect ratios between 0.1 and 20 because the piezoelectric transducers vibrate in both the radial and thickness modes. In addition to this assumption, most of the works on UAET models only have accounted for the piezoelectric and transmission layers. The effects of the bonding layers were not considered. Bonding the piezoelectric layers to the transmission layer introduces epoxy material with mechanical properties that are not accounted for. The epoxy layers are extra barriers to the transmission that introduce attenuation and alter the vibrational and acoustical behaviors of the UAET system. Investigations into UAET commonly focus on metal through-wall applications. Alternate transmission layer materials are not investigated and the impact of varying mechanical properties on the performance of a through-wall UAET system has not been comprehensively studied. Even with the metal transmission layers, the impact of the metal thickness has not been extensively investigated thoroughly. This work addresses the issues of the thickness-mode assumption in UAET modeling, the effects of epoxy layers, the impacts of the metal layer geometry, and the performance of UAET systems with alternate transmission layer materials. Particularly, (1) we showed that the thickness-mode assumption, that has been used in the UAET modeling leads to inaccurate results. (2) We modified the available acoustic electro- elastic theoretical modeling to include the effects of radial modes as well as the epoxy bonding layers. (3) We showed that the geometry of the elastic/metal layer requires optimization for peak system efficiency. (4) The results show that using alternate transmission layer materials impacts the performance of UAET systems. The results of this work were investigated using an improved 5-layer analytical model and finite element modeling in COMSOL Multiphysics. / Master of Science / Wireless power transfer (WPT) is an innovative solution to the problem of powering sophisticated technological applications. Such instances include the powering of implanted medical devices, recharging inaccessible sensor networks, and wireless powering of components in sealed containers. Acoustic energy transfer (AET) is a feasible WPT method that addresses these needs. AET is based on the propagation of acoustic waves to a piezoelectric receiver which converts the vibrations caused by incident acoustic waves into electrical energy. Most AET systems operate in the ultrasonic frequency range, and so AET can also be referred to as ultrasonic acoustic energy transfer (UAET). Through-wall UAET systems are constructed from a transmitter that is bonded to a transmission elastic layer. The transmission layer is bonded to a receiver. The transmitter and receiver are made of a piezoelectric material. This thesis addresses the modeling process of through-wall UAET systems. In previous works, the fundamental assumption has been that such systems vibrate purely in the thickness mode. Additionally, other investigations did not comprehensively analyze the effects of the bonding layers, ascertain the performance of non-metal transmission layers, or provide practical insight on the effect of the resistive loading on such systems. This work addresses all these issues with a mathematical framework and finite element modeling results.

[EN] Bile acids are a family of amphiphilic steroids that play a pivotal role in physiological functions such as elimination of cholesterol or solubilization of lipids. Chemically, they share a steroidal skeleton with an unusual cis fusion between rings A and B, a short lateral chain ending in a carboxylic acid moiety and different number of hydroxyl groups on the alpha-face. Hence, bile acids offer a versatile architecture that can be used to investigate photophysical processes of interest such as hydrogen atom transfer, through-bond energy trasfer, through-bond exciplex formation and DNA photodamage-related reactions. First, unmodified bile acids have been used to evaluate hydrogen atom trasfer to benzophenone-like triplet carbonyls. Dehydrogenation of bile acids at positions C-3 and/or C-7 by a radical-mediated mechanism from the excited state of benzophenone has been demonstrated. Moreover, synthesized lithocholic acid derivatives including benzophenone or carbazole as donors and a naphthalene, biphenyl or thymine as acceptors have been employed to investigate through-bond energy transfer and exciplex formation processes. Thus, energy transfer from benzophenone to naphthalene or biphenyl and extended through-bond exciplex formation in benzophenone/naphthalene and benzophenone/biphenyl linked systems has been demostrated by laser flash photolysis. Finally, bile acid derivatives incorporating one benzophenone and two thymine units with different degrees of freedom have been prepared to investigate the photochemical formation of oxetanes or thymine dimers. Photosensitized formation of cyclobutane pyrimidine dimers through the generation of a delocalized triplet excited state has been demonstrated in intermolecular systems, while oxetane formation is observed when the degrees of freedom are reduced. / [ES] Los ácidos biliares son una familia de esteroides anfifílicos que juegan un papel clave en diferentes funciones fisiológicas tales como la eliminación del colesterol o la solubilización de lípidos. Su estructura química está constituida por un esqueleto esteroideo con una fusión cis poco común entre los anillos A y B, una cadena lateral corta que termina con una función ácida y un número variable de grupos hidroxilo en la cara alfa. Por tanto, los ácidos biliares ofrecen una estructura versátil que puede ser utilizada para investigar procesos fotofísicos de interés como abstracción de hidrógeno, transferencia de energía y formación de exciplejos a larga distancia o reacciones relacionadas con el daño fotoinducido al ADN. En esta Tesis, en primer lugar, los ácidos biliares naturales se han utilizado para evaluar la abstracción de hidrógeno a carbonilos triplete en compuestos derivados de la benzofenona, demostrándose la deshidrogenación de los ácidos biliares en las posiciones C-3 y/o C-7 por un mecanismo radicalario desde el mencionado triplete de la benzofenona. En segundo lugar, se han preparado derivados de ácido litocólico que incluyen los dadores benzofenona o carbazol y los aceptores naftaleno, bifenilo o timina, que a continuación se han utilizado para investigar los procesos de transferencia de energía y formación de exciplejo intramolecular a larga distancia. De hecho, en los sistemas benzofenona/naftaleno y benzofenona/bifenilo, se demostró por fotólisis de destello láser la transferencia de energía desde benzofenona a naftaleno o bifenilo y la formación de exciplejo a larga distancia. Por último, se han preparado derivados de ácidos bliares que incorporan una unidad de benzofenona y dos de timina en diferentes posiciones del esqueleto para investigar la influencia de los diferentes grados de libertad en la formación fotosensibilizada de oxetanos o dímeros de timina. Gracias a ellos, se ha demostrado la formación fotosensibilizada de dímeros ciclobutánicos pirimidínicos a través de la generación de estados excitados triplete deslocalizados en sistemas en los que la benzofenona es intermolecular, mientras que se observa formación de oxetanos cuando los grados de libertad se ven reducidos. / [CA] Els àcids biliars són una família d'esteroides anfifílics que juguen un paper clau en funcions fisiològiques com l'eliminació del colesterol o la solubilització de lípids. La seua estructura química està constituïda per un esquelet esteroïdal amb una fusió cis entre els anells A i B poc comuna, una cadena lateral curta que acaba amb una funció àcida i un nombre diferent de grups hidroxil en la cara alfa. D'aquesta manera, els àcids biliars ofereixen una estructura versàtil que pot ser utilitzada per investigar processos fotofísics d'interès com abstracció d'hidrogen, transferència d'energia i formació de exciplexes a llarga distància o reaccions relacionades amb el dany a l'ADN induït per llum. En primer lloc, els àcids biliars naturals s'han utilitzat per avaluar la abstracció d'hidrogen a carbonils triplets derivats de la benzofenona, demostrant-se la deshidrogenació dels àcids biliars en les posicions C-3 i/o C-7 per un mecanisme radicalari des de l'estat excitat de la benzofenona. A més, derivats d'àcid litocòlic que inclouen els donadors benzofenona o carbazol i els acceptors naftalé, bifenil o timina s'han utilitzat per investigar els processos de transferència d'energia i formació de exciplexe a llarga distància. En els sistemes benzofenona /naftalé i benzofenona/bifenil la fotòlisis làser va demostrar la transferència d'energia des de benzofenona a naftalé o bifenil i la formació d'exciplexe a llarga distància. Finalment, per tal d'investigar la formació fotosensibilitzada d'oxetans o dímers de timina, s'han preparat derivats d'àcids bliars que incorporen una unitat de benzofenona i dues de timina amb diferents graus de llibertat. La formació fotosensibilitzada de dímers ciclobutànics pirimidínics mitjançant la generació d'estats excitats triplet deslocalitzats ha estat demostrada en sistemes intermoleculars, mentre que la formació d'oxetans s'observa quan els graus de llibertat es veuen reduïts. / Miró Richart, P. (2016). Hydrogen-Abstraction, Energy Transfer and Exciplex Formation in Photoactive Systems Based on Bile Acids [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/64084