The dissertation is comprised of three manuscripts presenting rare earth element (REE) and neodymium (Nd) isotopic analyses for the groundwaters, surface waters, sediments, and bedrocks of two estuaries along the eastern coast of the United States: Indian River Lagoon, Florida, and Pettaquamscutt Estuary, Rhode Island. This research was performed to understand the behavior of REEs in subterranean estuaries, the REE SGD fluxes, and the Nd isotopic composition of SGD. The selection of these sites offers contrasting geology (carbonate/sand matrix aquifer versus glacial till aquifer sourced from granitoids) and contrasting subterranean estuary structure. In the first site, the flux of REEs to the Indian River Lagoon, FL is comprised of a nearshore source of terrestrial SGD displaying a HREE-enriched fractionation pattern, and LREE- and MREE-enriched sources that originate from the reductive dissolution of Fe (III) oxide/hydroxides in the subterranean estuary and transported by bioirrigation to the overlying lagoon. The εNd(0) value the Indian River Lagoon groundwater is much more radiogenic than those of the surface water and sediments which could be due to the use of fertilizers in adjacent communities. The surface waters Nd isotopic composition appears to be a mixture of weathering of the Anastasia Formation and dissolution of eolian-transported Saharan Dust. In contrast at the second site, phosphate minerals control the surface and groundwaters of the Pettaquamscutt estuary, RI. The weathering of apatite and precipitation of secondary REE phosphate minerals most likely produce the MREE-enriched fractionation patterns of the Pettaquamscutt groundwaters. The further precipitation of the secondary REE phosphates in the surface waters of the Pettaquamscutt yields HREE-enriched fractionation patterns. The radiogenic Nd isotopic ratios of the Pettaquamscutt waters relative to the bedrock further suggest that apatite is the source of REEs. The Nd flux of SGD for both sites is roughly equal to the respective river fluxes; however, the Nd flux of SGD to the Pettaquamscutt is approximately 3 times greater than the SGD flux to the Indian River Lagoon. More research is needed in both environments to evaluate the impact of SGD on the Nd isotopic budget of the oceans. / acase@tulane.edu

HIFU is the upcoming technology for noninvasive or minimally invasive tumor ablation via the localized acoustic energy deposition at the focal region within the tumor target. The presence of cavitation bubbles had been shown to improve the therapeutic effect of HIFU. In this study, we have investigated the effect of HIFU on temperature rise and cavitation bubble activity in ethanol-treated porcine liver and kidney tissues. We have also explored changes in the viability and proliferation rate of HepG2, SW1376, and FB1 cancer cells with their exposure to ethanol and HIFU. Tissues were submerged in 95% ethanol for five hours and then exposed to HIFU generated by a 1.1 MHz transducer or injected into focal spot before HIFU exposure. Cavitation events were measured by a passive cavitation detection technique for a range of acoustic power from 1.17 W to 20.52 W. The temperature around the focal zone was measured by type K or type E thermocouples embedded in the samples. In experiments with cancer cells, 2.7 millions cells were treated with concentration of ethanol at concentration 2%, 4%, 10%, 25%, and 50% and the cell were exposed to HIFU with power of 2.73 W, 8.72 W, and 12.0 W for 30 seconds. Our data show that the treatment of tissues with ethanol reduces the threshold power for inertial cavitation and increases the temperature rise. The exposure of cancer cells to various HIFU power only showed a higher number of viable cells 24 to 72 hours after HIFU exposure. On the other hand, both the viability and proliferation rate were significantly decreased in cells treated with ethanol and then HIFU at 8.7 W and 12.0 W even at ethanol concentration of 2 and 4 percent. In conclusion, the results of our study indicate that percutaneous ethanol injection (PEI) and HIFU have a synergistic effect on cancer cells ablation. / acase@tulane.edu

We develop novel numerical methods for optimization problems subject to constraints given by nonlinear hyperbolic systems of conservation and balance laws in one space dimension. These types of control problems arise in a variety of applications, in which inverse problems for the corresponding initial value problems are to be solved. The optimization method can be seen as a block Gauss-Seidel iteration. The optimization requires one to numerically solve the hyperbolic system forward in time and the corresponding linear adjoint system backward in time. We test the optimization method on a number of control problems constrained by nonlinear hyperbolic systems of PDEs with both smooth and discontinuous prescribed terminal states. The theoretical foundation of the introduced scheme is provided in the case of scalar hyperbolic conservation laws on an unbounded domain with a strictly convex flux. In addition, we empirically demonstrate that using a higher-order temporal discretization helps to substantially improve both the efficiency and accuracy of the overall numerical method. / acase@tulane.edu

This dissertation can be divided into two parts project goals. The first one is the synthesis of rhenium (Re) complexes which are potential reverse saturable absorber (RSA) materials. The second one is the polymerization of ruthenium (Ru) polypyridyl monomers to have an oligomer ensemble for solar light harvesting purposes. THE FIRST part starts with an introduction to optical limiting materials (OLM) (chapter 1). The main discussion in chapter 4 is about the photophysical properties and energy-transfer reactions for three series of facial Re(I) tri-carbonyl complexes. The complexes are of the general type fac-[Re(CO)3(N-N)Cl], where Cl is the chloride and N-N are novel mono functionalized aryl-oligo(p-phenylene-vinylene) bipyridine (bpy) ligands. These series is as a result of changing the aryl group of the ligands to either anthracene or pyrene, and di-alkoxy attachments of phenyl ring in anthracene bipyridine ligands. The synthesis of the bpy ligands involved attaching various aryls by utilizing successive multi-step Wittig-Horner reactions (chapter 2). The ligands were later reacted with Re pentacarbonyl chloride to obtain the complexes. Chromium complexes synthesis is also included (chapter 3). The characterization involved 1H NMR, ESI-MS and elemental analysis. There is also another set of ligands where the aryl group is di-methylaminophenyl where the solvatochromic emission properties of the ligands were studied but were not coordinated to metals. The excited-state properties using both the nanosecond (ns) and picosecond (ps) time resolved transient absorption (TA) of Re(I) complexes shows strong positive excited-state absorption signals in 500-800 nm range. From the TA (ps) and time-resolved infrared of the carbonyl region, the excited state forms instantaneously after excitation. Their observed lifetimes are relatively long (2 μs-40 μs range) and they increase as the phenylene-vinylene linker increases. The excited state triplet energies values for the complexes were obtained experimentally using energy transfer method from the simple Sandros relation. They decreases as the π-conjugated phenylene-vinylene linker decreases, this is because the extended backbone bridge serves to lower the energy of the triplet excited state. Lastly, the Re(I) complexes triplet-triplet molar extinction coefficients(δex) were measured by energy transfer to a standard method and their ratios to the ground state molar absorptivity(δg ) are all (δex/δg ≥40) at 530nm which make them potential candidates for RSA. THE SECOND part involves RAFT polymerization of two new acrylamide functionalized Ru(II) polypyridyl monomers. Photoinduced electron transfer reactions for the obtained Ru oligomers and complexes were done using 10-methylphenothiazine (MPT) quencher (chapter 8). The synthesized acrylamide functionalized bipyridine ligand (chapter 6) was reacted with complex precursors cis-[Ru(L)2Cl2] where the ligand (L) is either 2,2’- bipyridine or biquinoline (chapter 7). The obtained Ru(II) photosensitizers acts as energy donating and accepting respectively. The attachment of these Ru complexes to oligomer backbone as side chains is by a C11 alkyl linker. 1H NMR, UV-Vis spectroscopy, and differential pulse voltammetry (DPV) were used to characterize the ligand, monomers and oligomers. The excited state REDOX potentials were determined using the cyclic voltammetry (CV) values and steady state emission values converted to electron volt (eV). Lastly, the TAs (ns) obtained in the presence of MPT electron donating quencher was in agreement with the ones calculated/ predicted from spectroelectrochemistry. These efforts are toward the goal of making a panchromatic solar light collector in the visible region (chapter 5). / acase@tulane.edu

Contemporary research has been examining potential links existing among sensory, motor and attentional systems. Previous studies using TMS have shown that the abrupt onset of sounds can both capture attention and modulate motor cortex excitability, which may reflect the potential need for a behavioral response to the attended event. TMS, however, only quantifies motor cortex excitability immediately following the deliverance of a TMS pulse. Therefore, the temporal development of how the motor cortex is modulated by sounds can’t be quantified using TMS. Thus, the purpose of the present study is to use time frequency analysis of EEG to identify the time course of cortical mechanisms underlying increased motor cortex excitability after sound onset. Subjects sat in a sound attenuated booth with their hands outstretched at 45-degree angles while frequency modulated sounds were intermittently presented from a speaker either in the left and right hemispace. Our results indicated a transient reduction in EEG power from 18-24 Hz (300-600 ms latency) and then a long lasting increase in EEG power that began at ~800 ms and continued until at least 1.7 sec. The latency of EEG power changes was shorter for sounds presented from the right speaker at both time periods. When sounds were presented from the right speaker the contralateral hemisphere over motor regions also showed greater power increases after 800 ms relative to the ipsilateral hemisphere. In addition, power increases were greater in the left-handed subjects (8-12 Hz). Results showed that sounds increased EEG power at the time of a previously observed increase in motor cortex excitability. Findings also suggest an increased attentional salience to the right hemispace in neurologically normal subjects and asymmetrical hemispheric activations in right and left-handers. / acase@tulane.edu