Thesis (M.S.)--University of North Texas, May, 2007. / Title from title page display. Includes bibliographical references.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on October 18, 2007) Vita. Includes bibliographical references.

No description available.

Low concentrations of the group IIA metals Mg²⁺, Ca²⁺, and Ba²⁺ stimulated energy-independent transhydrogenase activity. High concentrations of Mg²⁺ inhibited this activity. Transhydrogenase requires Mg²⁺-complexed NADP(H) rather than free NADP(H) as its substrate. High concentrations of Mg2+, however, may change the conformation of the enzyme to inhibit its enzymatic reaction by binding directly to the NADP(H) site. Upon transhydrogenation between NADPH and 3-acetylpyridine dinucleotide, E. coli pyridine nucleotide transhydrogenase can establish a proton gradient across the cell membrane. The primary component of the proton gradient for energization of transhydrogenase was found to be the pH gradient and not the membrane potential. A similar conclusion was drawn for the ATP-driven transhydrogenase reactions. In strains of E. coli that harbored plasmids to give the cells elevated levels of transhydrogenase, it was found that uncouplers stimulated the aerobic-driven transhydrogenase reaction. This is a chemiosmotic anomaly and is in contrast to the non-plasmid containing parent strains where uncouplers inhibited the activity. Further investigation revealed that the plasmid strains contained a much lower NADH oxidase activity than the non-plasmid strains and that neither KCN nor QNO can inhibit the aerobic-dependent activity in both types of strains even though they were effective in blocking the respiratory chain. These effects prompted us to inquire whether the anomaly was due to differences in the respiratory chain, but no differences were found between the NADH dehydrogenase activities, quinone and cytochrome contents of the plasmid and non-plasmid strains. The bacterial cells with amplified transhydrogenases induce extra intracellular tubular membrane structures to accomodate the extra proteins (Clark, D.M., Pyridine Nucleotide Transhydrogenase, PhD thesis, University of British Columbia, 1986). Separation of the E. coli membrane vesicles on a shallow sucrose gradient, however, did not reveal any differences between the vesicles of the plasmid and non-plasmid strains. Therefore, it seems unlikely that the anomaly is due to the plasmid strains performing a unique form of energization on these induced structures. Finally, it was established by SDS-PAGE and Western blot using anti-transhydrogenase antisera that the plasmid strains express a much higher level of transhydrogenase enzymes in their cell membranes than do the non-plasmid strains. / Medicine, Faculty of / Biochemistry and Molecular Biology, Department of / Graduate

There are lots of important applications for lanthanides (Ln) because of their unique properties. The properties are closely linked to the environment of the crystal field. Thus, two kind of crystals Cs2NaLn(NO2)6 with high Th point-group symmetry and LnPO4 with monoclinic symmetry were chosen to study quantum cutting and Stokes shift. Quantum cutting is a kind of down-conversion energy transfer in which one excitation ultraviolet photon is transformed into multiple near infrared photons. This phenomenon has been studied in Cs2NaY0.96Yb0.04(NO2)6. The emission from Yb3+ can be excited via the NO2- antenna. The electronic transition of NO2- is situated at more than twice the energy of the Yb3+. At room temperature, one photon absorbed at 470 nm in the triplet state produced no more than one photon emitted. Some degree of quantum cutting was observed at 298 K under 420 nm excitation into the singlet state and at 25 K using excitation into singlet and triplet state. The quantum efficiency was about 10% at 25 K. In Chapter 3, Stokes shift which is the energy shift between the peak maxima in absorption and emission was studied. Stokes shift is related to the flexibility of the lattice and the coordination environment. Cs2NaCe(NO2)6 with 12-coordinated Ce3+ situated at a site of Th symmetry demonstrated the largest Ce-O Stokes shift of 8715 cm−1. The 4f1 ground state and 5d1 potential surfaces have displaced so much along the configuration coordinate that overlap takes place above the 5d1 minimum, leading to thermal quenching of emission at 53 K. A comparison of Stokes shifts with other Ce-O systems with different coordination number demonstrated larger Stokes shifts for Ce3+ ions with higher coordination number. Systematic research about the energy transfer (ET) and energy migration phenomenon is still scarce, although they exist extensively among lanthanide ions. The energy migration in highly doped materials has been stated as very fast or slow, but no experimental proof was reported. In Chapter 4, the ET between Tb3+ and Eu3+ was investigated experimentally and compared with available theoretical models in the regime of high Tb3+ concentrations in 30 nm LaPO4 nanoparticles at room temperature. The ET efficiency approached 100% even for lightly Eu3+-doped materials. The use of pulsed laser excitation and switched-off continuous wave laser diode excitation demonstrated that the energy migration between Tb3+ ions, situated on La3+ sites with a 4 Å separation was not fast. The quenching of Tb3+ emission in singly doped LaPO4 only reduced the luminescence lifetime by about 50% in heavily doped samples. Various theoretical models have been applied to simulate the luminescence decays of Tb3+ and Eu3+-doped LaPO4 samples of various concentrations. The transfer mechanism has been identified as forced electric dipole at each ion. The control of energy transfer rate and efficiency is also an important issue. There are many chemical and geometrical factors that affect energy transfer, including the spectra overlap, the dipole orientation and the distance between the donor and acceptor. The local field of the emission center is another factor that affect the energy transfer by changing the photonic environment. In Chapter 5, the local field effect on the energy transfer between Tb3+ and Eu3+ doped in LaPO4 dispersed in different solvents and solids with a wide range of refractive indexes was studied. The effects of local field (reflected by refractive index) on the ET efficiency and ET rates were clarified that the ET efficiency would decrease with increasing refractive index, while ET rates were independent of the refractive index

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Indiana University-Purdue University of Indianapolis (IUPUI) / A Near-field Scanning Optical Microscope (NSOM) is used to study the resonant energy transfer between different size CdSe/ZnS quantum dots (QDs). The NSOM system is used to bring the small QDs which are 6 nm in diameter close to 8 nm diameter QDs which are embed with PMMA on a cover glass. The PMMA is used to prevent the 8 nm QDs from aggregation, which allows us to locate one dot on the cover slide and have the potential to get the interaction of two individual dots. A systematic methodology is used to localize a single QD on the cover glass and align the small and large QDs. Since the ground energy state of the small QDs match the excitation energy level of the large QDs. When the small dots get excited, part of the energy transfers to the large QDs. As the separation between small and large QDs is changed in near-field range (20-50nm), the transition probability is observed, indicating that the FRET level changes as a function of separation between small and large QDs. Possible future improvements are also discussed.

Electronic Excitation Energy Transfer is an important intermolecular photophysical process that can affect the excited state lifetime of a chromophore. A molecule in an electronically excited state can return to the ground state by radiative as well as non-radiative processes. During the excited state lifetime, if the chromophore (energy donor) finds a suitable species (energy acceptor) nearby with resonant energy levels, it can transfer the excitation energy to that species and return to the ground state. This process is called Electronic Excitation Energy Transfer. When the energy donor is fluorescent, the process is called Fluorescence Resonance Energy Transfer (FRET) [1]. FRET is a non-radiative process that affects the fluorescence intensity as well as the excited state lifetime of the donor. It occurs due to the electrostatic coulombic interaction between the transition charge densities of the donor and the acceptor. The rate of energy transfer can be evaluated using the Fermi golden rule of quantum mechanics [2]. When the donor and the acceptor are separated by distances that are much larger in comparison with the sizes of the donor and the acceptor, the interaction between them can be thought of as that between their transition dipoles. In such a case, the interaction between the donor and the acceptor is dipolar and the rate of energy transfer has an R−6 dependence, where R is the distance between the donor and the acceptor [3]. This dependence has first been suggested theoretically by Forster in 1947 [4] followed by the experimental verification by Stryer and Haugland [5]. Since then the process has been used as a spectroscopic ruler to study the conformational dynamics of biopolymers like DNA, RNA, proteins etc [6]. A variety of dye molecules have been explored for donors and acceptors in FRET and the range of distances that can be measured using FRET involving dyes is in the range 1 − 10 nm. When the distances between the donor and the acceptor are not much larger in comparison with their sizes, the dipolar approximation to the interaction is not a very good approximation, thereby leading to deviations from the traditional R-6 dependence. Such non-R-6dependencies are found for polymers, quantum wells, quantum wires etc [7–9]. The interest in such dependencies is due to the need for developing nanoscopic rulers that can measure distances well beyond 10 nm. The objective of our work has been to study energy transfer from fluorophores to various kinds of acceptors that have extended charge densities and understand the distance dependence of the rate of energy transfer [10]. We use the Fermi golden rule as the starting point and develop analytical models for evaluating the rate as a function of the distance between the donor and the acceptor. We study the process of energy transfer from fluorescent dye molecules that serve as energy donors to a variety of energy acceptors namely, graphene, doped graphene, single-walled carbon nanotubes and metal nanoparticles. We also study transfer from fluorophores to a semiconducting sheet and a semiconducting tube of electronic charge density. There have been experimental studies in the literature of the fluorescence quenching of dyes near single-walled carbon nanotubes [11–13]. But, there are no studies of the distance dependence of rate. Single-walled carbon nanotubes can be thought of as rolled up sheets of graphene. However, interestingly, there were no reports of fluorescence quenching by graphene at the time when we thought of this possibility. Therefore, we first study the process of energy transfer from a fluorophore, which is kept at a distance z above a layer of graphene to the electronic energy levels of graphene. We find that the long range behavior of the rate has an z -4 dependence on the distance [14, 15]. From our study of transfer from pyrene to graphene, we find that fluorescence quenching can be experimentally observed up to a distance of ~ 30 nm, which is quite large in comparison with the traditional FRET limit (10 nm). Recent experiments that have been performed after our theory was reported have in fact observed the fluorescence quenching of dyes near graphene. Further, the process has been found to be very useful in fabricating devices based on graphene [16], in eliminating fluorescence signals in resonance Raman spectroscopy [17] and in visualizing graphene based sheets using fluorescence quenching microscopy [18]. The process has also been found to be useful in quantitative DNA analysis [19, 20]. We study the transfer of an amount of energy hΩ from a dye molecule to doped graphene [21]. We consider the shift of the Fermi level from the K-point into the conduction band of graphene as a result of doping and evaluate the rate of transfer. We find a crossover of the distance dependence of the rate from z -4 to exponential as the Fermi level is increasingly shifted into the conduction band, with the crossover occurring at a shift of the Fermi level by an amount hΩ/2. We study the process of transfer of excitation energy from a fluorophore kept at a distance d away from the surface of a carbon nanotube to the electronic energy levels of the nanotube. We find both exponential and d−5 behavior of the rate [22]. For the case of metallic nanotubes, when the emission energy of the fluorophore is less than a threshold, the dependence is exponential. Otherwise, it is d−5 . For the case of semiconducting nanotubes, we find that the rate follows an exponential dependence if the amount of energy that is transferred can cause only the excitonic transition of the tube. However, if any other band gap transition is allowed, the rate follows a d−5 dependence. For the case of transfer from pyrene to a (6, 4) nanotube, we find that energy transfer is appreciable up to a distance of ~ 17 nm. We then study the process of energy transfer from a fluorophore to a semiconducting sheet of electronic charge density [10]. We find that the rate has an z-4 dependence. For the case of transfer to a semiconducting tube, we find that the rate has a d -5dependence. The dependencies are in agreement with those obtained for graphene and carbon nanotubes respectively. This shows that the asymptotic distance dependencies are a consequence of the dimensionality of the transition charge densities and are robust. Strouse et al. [23, 24] have studied the process of energy transfer from the dye fluorescein to a 1.4 nm diameter gold nanoparticle. Double-stranded DNA molecules of various lengths were used to fix the distances between the donor and the acceptor. The rate was found to have a d-4distance dependence. They refer to this process as Nanoparticle Surface Energy Transfer (NSET) and the range of distances that can be measured using NSET is more than double that of the traditional FRET experiments. However, theoretical studies that consider the transfer to the plasmonic modes of the nanoparticle find a predominant R-6 dependence [25]. We study the process of energy transfer from the dye fluorescein to a 1.4 nm diameter gold nanoparticle considering the excitation of plasmons as well as electron-hole pairs of the nanoparticle [26]. We find that the rate follows the usual Forster type R−6 distance dependence at large distances. But, at short distances, there are contributions of the form R−-n with n > 6. This is due to the quadrupolar and octupolar modes of excitation of the nanoparticle, the rates corresponding to which have R-8 and R−-10 dependencies respectively. Recent calculations using DFT also find similar deviations at short distances [27].

This work is centered on low-frequency and high-frequency multiphysics problems of piezoelectric structures submerged in a quiescent fluid domain for the applications of vibration energy harvesting, biomimetic actuation, and contactless acoustic energy transfer. In the first part of this research, Macro-Fiber Composite (MFC)-based piezoelectric structures are employed for underwater mechanical base excitation and electrical biomimetic actuation in bending mode at low frequencies (the fundamental underwater bending resonance being in the infrasonic frequency range). The MFC technology (fiber-based piezoelectric composites with interdigitated electrodes) exploits the effective 33-mode of piezoelectricity, and strikes a balance between structural deformation and force levels for actuation to use in underwater locomotion, in addition to offering high power density for energy harvesting to enable battery-less aquatic sensors. Following in-air electroelastic composite model development, the fundamental research problem is to establish semi-analytical models that can predict the underwater dynamics of thin MFC cantilevers for different length-to-width aspect ratios. In-air analytical electroelastic dynamics of MFCs is therefore coupled with added mass and nonlinear hydrodynamic damping effects of fluid to describe the underwater electrohydroelastic dynamics in harvesting and actuation. To this end, passive plates of different aspect ratios are tested to extract and explore the repeatability of the inertia and drag coefficients in Morison’s equation. The focus is placed on the first two bending modes in this semi-empirical approach. In particular, electrode segmentation is studied for performance enhancement in the second bending mode. Additionally, nonlinear dependence of the output power density to aspect ratio is characterized theoretically and experimentally in the underwater base excitation problem. In the second part of this work, Ultrasonic Acoustic Energy Transfer via piezoelectric transduction is investigated theoretically and experimentally. Contactless energy transfer using acoustic excitation offers larger distances of power transmission as compared to well-studied inductive method. Various transmitter configurations (e.g. spherical, cylindrical, and focused) are explored for energy transfer to a piezoelectric receiver bar (operating in the longitudinal/thickness mode) that is shunted to a generalized resistive-reactive circuit. Fixed-free and free-free mechanical boundary conditions of the receiver are explored in detail. The resulting multiphysics analytical model framework is compared with finite-element simulations and experiments conducted in fluid (water and oil). Optimal piezoelectric receiver material and electrical loading conditions are sought for performance and bandwidth enhancement.

No description available.