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An investigation into the parameters that define a good anchor block for a copolymer steric stabilizer was performed. The study focused on the effects of different functional groups on the adsorption properties of polymers. In addition, the effect of chain architecture as well as the impact of a hydrophobic end-group on polymer adsorption properties was determined. To complement the adsorption studies, a streaming potential instrument was built for use in measuring the adsorbed layer thickness of nonionic polymers on SiO₂. The research concluded with an examination of the effect of thermally induced insolubility on adsorption of a hydrogen-bonding polymer. Functional group effects were studied by measuring the adsorption isotherms of poly(2-ethyl-2-oxazoline), PEOX, poly(ethylene oxide), PEO, poly(vinyl alcohol), PVOH, and poly(ethylene imine), PEI, which was modified such that a 1,3-butanediol substituent replaced its imine hydrogens, on SiO₂, TiO₂, and Al₂O₃. PEOX and PEO, relatively basic polymers compared to PVOH were observed to adsorb only on the most acidic metal oxide, SiO₂. PVOH, however, was observed to adsorb on all three metal oxides, but to a lesser degree on SiO2 as compared to the more basic PEOX and PEO. These initial results were indicative of hydrogen-bonding mechanisms, a form of acid-base interaction. The most significant observation in the adsorption studies was that the linear hydroxyl modified PEI materials and their dendritic analogs adsorb on the metal oxides both above and below the i.e.p. This indicates that both electrostatic and hydogen-bonding mechanisms are driving the adsorption. The dendritic polymers, particularly a 4th generation dendrimer based on diaminopropane with a molecular weight of 16,640 g/mol adsorbed at a higher level when compared to the 41.3K g/mol PVOH and 30K g/mol PEOX. In addition to the dual adsorption mechanism, it was determined that the dendritic architecture appears to facilitate adsorption, as does the presence of the hydrophobic endgroup. The level of adsorption for all of the hydroxyl containing linear PEI and dendritic materials on the three metal oxides was high enough for them to be considered as anchor blocks in a copolymer steric stabilizer. The streaming potential instrument used to measure the adsorbed layer thickness on SiO₂. Adsorbed layer thickness of PEOX Mw = 10K and 30K g/mol were measured at approximately 1nm and 4.4 nm, respectively. In the case of the PEOX Mw = 30K g/mol homopolymer, the measured layer thickness was higher than that for a 23K g/mol PEO homopolymer. The degree of polymerization of the PEO is approximately 525, while for the PEOX it was only 300. This result was not expected. Finally, adsorption of PEOX was studied at the cloud point to determine whether insolubility could promote adsorption, while hydrogen-bonding, the room temperature driving force for adsorption, would decrease. Adsorption isotherm measurements were performed at 72 °C, and 75 °C, as the cloud point of the 30K PEOX was determined to be 73 °C. It was apparent that the adsorption decreased as temperature increased, indicating that without hydrogen bonding, thermally induced insolubility does not drive adsorption. / Ph. D.

Accurate interatomic energies and forces enable high-quality molecular dynamics simulations, torsion scans, potential energy surface mapping, and geometry optimization. Machine learning algorithms have enabled rapid estimates of energies and forces with high accuracy. Further development of machine learning algorithms holds promise for producing general potentials that support dozens of atomic species. I present my own Transformer Interatomic Potential (TrIP): a chemically sound potential based on the SE(3)-Transformer. TrIP's species-agnostic architecture--using continuous atomic representation and homogenous graph convolutions--encourages parameter sharing between atomic species for more general representations of chemical environments, keeps a reasonable number of parameters, serves as a form of regularization, and is a step towards accurate universal interatomic potentials. I introduce physical bias in the form of Ziegler-Biersack-Littmark-screened nuclear repulsion and constrained atomization energies to improve qualitative behavior for near and far interaction. TrIP achieves state-of-the-art accuracies on the COMP6 benchmark with an energy prediction error of just 1.02 kcal/mol MAE, outperforming all other models. An energy scan of a water molecule shows improved short- and long-range interactions compared to other neural network potentials, demonstrating its physical realism compared to other models. TrIP also shows stability in molecular dynamics simulations with a reasonable exploration of Ramachandran space.

A retarding potential analyzer (RPA) is an instrument that, when mounted on a satellite in low-Earth orbit, makes in-situ measurements of ion density, temperature and speed relative to the satellite frame. The instrument works by changing the voltage on one of a set of grids and measuring a corresponding current generated by ions flowing through the grid, generating a function of current vs. voltage called an I-V curve. Traditionally, the size and power requirements of retarding potential analyzers has limited their use to larger satellites. In this thesis, the electrical design and basic testing of a retarding potential analyzer for use on resource- limited cubesat platforms are described. The mechanical design of the retarding potential analyzer is first described, and the requirements of the electrical design are presented. The electrical requirements are based on both the characteristics of the ionosphereic flight environment, and on the size and power requirements typical of the small cubesat platforms for which the instrument is intended. The electrical hardware is then described in detail. The digital design is reviewed as well, including the instrument's operating modes, command and data structure, and timing scheme. Test data showing the basic functionality of the instrument are then presented. Bench tests validate the design by confirming its ability to control voltages and measure small currents. End-to-end tests were also performed in a vacuum chamber to mimic the ionospheric environment. These data are presented to show the ability of the RPA to meet or exceed its design specifications. / Master of Science

Control of underactuated mechanical systems is of interest as it allows for control authority over all of a system's degrees of freedom without requiring actuation of the full system. In addition to this, open-loop control of a system provides the advantage of applying to systems with unmeasurable states or where sensor integration is not feasible. Vibrational control is an open-loop control strategy that uses high-frequency, high-amplitude forcing to control underactuated mechanical systems. This thesis is concerned with exploring two underactuated mechanical systems that are controlled using vibrational inputs. The first system, a 3 degrees of freedom (DOFs) 2-link mechanism with 1 actuated DOF which is an example of a vibrational control system with 1 input and 2 unactuated DOFs, is used to review analytical results of stability analysis using the averaged potential. Theoretical and numerical results are presented for the achievable stable configurations of the system and the effects of changing the physical parameters on the achievable stable configurations are studied. The primary contribution of this effort is the development of an experimental apparatus where vibrational control is implemented. The second system is a 4DOF system composed of a 2DOF spherical pendulum supported by an actuated 2DOF cart used to study the effects of multiple vibrational inputs acting on a system. Theoretical and numerical analysis results are presented for three variants of harmonic forcing applied to the two actuated degrees of freedom: 1) identical input waveforms, except for the amplitudes, 2) identical input waveforms, except for the amplitudes and a phase shift, and 3) identical input waveforms, but at different frequencies and amplitudes. The equilibrium sets under open-loop vibrational forcing are determined for all three cases. A general closed-loop vibrational control scheme is presented using proportional feedback of the unactuated coordinates superposed with the zero-mean, $T$-periodic vibrational input. / M.S. / Underactuated mechanical systems are systems where the driven degrees of freedom are fewer than the total degrees of freedom of the system. These systems can be controlled using vibrational control which is an open-loop control strategy that uses high-frequency, high-amplitude forcing to control the states of a system. An open-loop control strategy is one in which there are no measurements of the system states required in the control scheme. This allows for control of systems where sensor integration is not feasible. This thesis is concerned with exploring vibrational control of two underactuated mechanical systems. The stability of the equilibrium sets of these systems is assessed using the averaged potential, which is an energy-like quantity used to determine stability of equilibria of systems with high-frequency inputs. Theoretical and numerical results are presented for both systems and the effects of physical parameters and variants of harmonic forcing on the achievable stable configurations of the systems are studied. The two main contributions of the thesis are the development of an experimental apparatus where vibrational control is physically implemented for one system and the outline of the closed-loop vibrational control scheme.

An electrophysiology research laboratory at the Wake Forest University School of Medicine in the Physiology/Pharmacology Department currently carries out memory research by recording neural signals from laboratory animals with a wire tethering the animal to nearby signal conditioning and recording equipment. A wireless neural signal recording system is desirable because it removes the cumbersome wires from the animal, allowing it to roam more freely. The result is an animal that is more able to behave as it would in its natural habitat, thus opening the possibility of testing procedures that are not possible with wired recording systems. While there are wireless neural recording systems in existence, this thesis presents a new approach to recording neural signals wirelessly. The firings of neurons in the hippocampus are manifested as action potentials or voltage "spikes" on the order of 100 to 400uV in magnitude. Though the information content of the neural signal is riding on these action potentials, the spikes comprise a small fraction of the complete neural signal. A unique feature of the neural signal transceiver presented in this thesis is its ability to digitally isolate and transmit the action potentials, leaving out the remaining, unimportant part of the neural signal. This approach to recording neural signals makes efficient use of the limited bandwidth available with portable short range wireless devices. This thesis will present the spike isolating neural transmitter, which was built using commercially available electronic components. Then, the proper function of assembly language code written for a PIC18F458 microcontroller will be demonstrated. Finally, a discussion of the performance of the neural signal transmitter will be provided. / Master of Science

Protonated epoxides feature prominently in organic chemistry as reactive intermediates. Gas-phase calculations studying the structure and ring-opening energetics of protonated ethylene oxide, propylene oxide and 2-methyl-1,2-epoxypropane were performed at the B3LYP and MP2 levels (both with the 6-311++G** basis set). Structural analyses were performed for 10 protonated epoxides using B3LYP, MP2, and CCSD/6-311++G** calculations. Protonated 2-methyl-1,2-epoxypropane was the most problematic species studied, where relative to CCSD, B3LYP consistently overestimates the C2-O bond length. The difficulty for DFT methods in modeling the protonated isobutylene oxide is due to the weakness of this C2-O bond. Protonated epoxides featuring more symmetrical charge distribution and cyclic homologues featuring less ring strain are treated with greater accuracy by B3LYP. Ion-pair separation (IPS) of THF-solvated fluorenyl, diphenylmethyl, and trityl lithium was studied computationally. Minimum-energy equilibrium geometries of explicit mono, bis and tris-solvated contact ion pairs (CIPs) and tetrakis-sovlated solvent separated ion pair (SSIPs) were modeled at B3LYP/6-31G*. Associative transition structures linking the tris-solvated CIPs and tetrakis-solvated SIPs were also located. In vacuum, B3LYP/6-31G* ΔHIPS values are 6-8 kcal/mol less exothermic than the experimentally-determined values in THF solution. Incorporation of secondary solvation in the form of Onsager and PCM single-point calculations showed an increase in exothermicity of IPS. Application of a continuum solvation model (Onsager) during optimization at the B3LYP/6-31G* level of theory produced significant changes in the Cα-Li contact distances in the SSIPs. An increase in of ion pair separation exothermicity was observed upon using both PCM and Onsager solvation models, highlighting the importance of both explicit and implicit solvation in modeling of ion pair separation. / Ph. D.

No / Purpose To determine the usefulness of a battery of potential vision tests (PVTs) including potential acuity meter (PAM), laser interferometer (LI), critical flicker/fusion frequency (CFF), superilluminated pinhole at distance (SPHd) and near (SPHn), and optimal reading speed (ORS) by their independence of the effects of cataracts and sensitivity to macular disease (MD). Setting Department of Optometry, University of Bradford, Bradford and Leeds General Infirmary, Leeds, United Kingdom. Methods Potential vision test measurements were determined in 76 patients with age-related cataract and no other eye disease, 52 patients with MD and clear ocular media, and 28 patients with normal, healthy eyes. Results Potential vision tests were independent of the degrading effects of cataract up to a visual acuity (VA) level of 20/200 or worse (CFF), 20/125 (ORS and SPH), and 20/40 (PAM and LI). A high degree of association was found between PVT scores and distance VA in the MD group for SPHd (r2 = 0.93), SPHn (r2 = 0.89), and PAM (r2 = 0.71). A moderate correlation was found for LI (r2 = 0.55), CFF (r2 = 0.50), and ORS (r2 = 0.45). Conclusions Potential acuity meter and LI showed very limited independence to moderate/dense cataracts and inaccurate predictions in patients with MD. Superilluminated pinhole was relatively unaffected by moderate/dense cataract and yet provided accurate predictions in the presence of MD and clear ocular media. Critical flicker/fusion frequency showed the greatest ability to bypass cataracts, although its ability to predict VA in patients with early MD was limited. The ORS was relatively unaffected by moderate/dense cataract, but its poor ability to predict VA in MD may limit its clinical suitability as a PVT.

The DSM-IV characterizes dissociation as “disruption in the usually integrated functions of consciousness, memory, identity, or perception of the environment” (American Psychiatric Association, 1994, p. 477) and it has been tenuously linked with trauma, but “lacks a single, coherent referent … that all investigators in the field embrace” (Cardena, 1994). It is known that dissociation is a spectrum (Bernstein and Putnam, 1986; Shor, Orne, and O’Connell, 1962; Spiegel, 1963; Tellegen and Atkinson, 1974), and low levels of dissociation can be a part of normal functioning, allowing us to do two things at once (Butler, Duran and Jasiukitis, 1996), but higher levels can interfere with daily functioning. The present study used survey techniques to investigate the link between dissociation and trauma. Survey results showed a significant correlation between trauma and dissociation. The current investigation also used the high temporal and spatial resolution of electroencephalographic techniques to identify the neurophysiological correlates of dissociation. Specifically, the current investigation recorded early and late event-related potentials in participants who rated high and low in dissociation while they viewed affective pictures in order to determine if there were electrophysiological differences in responses to emotional stimuli. Electroencephalographic results were nonsignificant, but trends indicated that high dissociators showed a heightened response to affective photos at P1 and the late positive potential compared with low dissociators. If the results are thought to be reliable, the trends may indicate that high dissociators were not actively dissociating during the task, and because high dissociators have usually experienced trauma, they are more sensitive to emotional stimuli. Further research is needed to support these theories.

O P300 auditivo é um potencial evocado que reflete a atividade neurofisiológica das habilidades cognitivas auditivas de atenção, memória, discriminação e tomada de decisão. A possibilidade de correlacionar aspectos do comportamento auditivo a fenômenos fisiológicos observáveis tem despertado o interesse de profissionais de diversas áreas interessados no estudo das disfunções auditivas. Por ser um procedimento novo, os métodos de análise e interpretação dos resultados ainda não estão padronizados e, portanto, devem ser explorados e discutidos visando maior segurança para aplicação clínica e científica. Este estudo investigou a estabilidade na análise e interpretação do P300 auditivo seguindo um conjunto de regras (critério) pré-determinadas. Para isso, quatro profissionais da área audiológica analisaram, em 2 momentos diferentes, 70 traçados de P300 de crianças e adolescentes saudáveis entre 8 e 18 anos de idade, seguindo as mesmas regras para a identificação das ondas (N1, P2, N2 e P3) e marcação de suas medidas de latência. As medidas de latência da onda P300 foram submetidas a análises qualitativa e quantitativa. A análise qualitativa investigou os tipos de erros cometidos pelo examinador no uso do critério de determinação do P300 (5,9% do total de 560 medidas obtidas). Os erros mais freqüentes no uso do critério foram: não identificar o P300 como a maior onda logo após o complexo N1-P2-N2 e identificar uma “falsa" onda P300. A análise quantitativa investigou a variabilidade da medida da latência do P300 atribuível ao examinador. Os resultados mostraram que não houve diferença significante entre as análises inter e intra-examinador, tendo sido encontradas correlações significantes entre as medidas de latência, indicando boa fidedignidade no teste-reteste e alta concordância entre os examinadores no modo como analisaram os traçados das ondas. O critério usado neste estudo demonstrou ser útil na determinação do P300, podendo ser sugerido com segurança para uso clínico e científico. / The P300 auditory is an evoked potential which reflects the neurophysiological activity of auditory cognitive abilities: attention, memory, discrimination and making decision as well. The possibility of correlation between aspects of auditory behavior and observable physiological phenomena has increased the interest in the study of auditory dysfunctions among professionals of various fields. Due the fact that the P300 is a recent procedure, the methods of its analysis and interpretation have not been standardized yet. Therefore, they must be explored and debated aiming more security for clinical and scientific application. In this study it was investigated the stability in the analysis and interpretation of P300 auditory, according to a pre-determined set of rules. Four audiologists analyzed twice 70 records of P300 of healthy children and adolescents between 8 and 18 years of age, identifying the waves (N1, P2, N2, P3) and their latencies according to the pre-determined set of rule. The P300 latency measurements were submitted to quantitative and qualitative analysis. The qualitative analysis looked into types of errors made by the examiner during the P300 identification (5.9% in a total of 560 measurements). The no-identification of the P300 as the highest wave following the complex N1-P2-N2, likewise the “wrong" identification of P300 wave were the most frequent mistakes. In the quantitative analysis we investigated the variability of the P300 latency measurements attributable to the examiner. The results showed that there were no significant differences between the inter- and intra-examiner analyses. Significant correlations were found between the measurements, showing a good test-retest reliability and high concordance among the examiners in the way they analyzed the wave records. We conclude that the rules used in this study are useful to the identification of the P300 in both clinical and scientific situations.