Sleep-Disordered Breathing and Periodic Limb Movements in Narcolepsy with Cataplexy: A Systematic Analysis of 35 Consecutive Patients

Background: Disturbed sleep is a core feature of narcolepsy with cataplexy (NC). Few studies have independently assessed sleep-disordered breathing (SDB) and periodic limb movements (PLMs) in non-homogeneous series of patients with and without cataplexy. We systematically assessed both SDB and PLMs in well-defined NC patients. Methods: We analyzed the clinical and polysomnographic features of 35 consecutive NC patients (mean age 40 ± 16 years, 51% males, 23/23 hypocretin-deficient) to assess the prevalence of SDB (apnea-hypopnea index >5) and PLMs (periodic leg movements in sleep (PLMI) >15) together with their impact on nocturnal sleep and daytime sleepiness using the multiple sleep latency test. Results: 11 (31%) and 14 (40%) patients had SDB and PLMs, respectively. SDB was associated with older age (49 ± 16 vs. 35 ± 13 years, p = 0.02), higher BMI (30 ± 5 vs. 27 ± 6, p = 0.05), and a trend towards higher PLMI (25 ± 20 vs. 12 ± 23, p = 0.052), whereas PLMs with older age (50 ± 16 vs. 33 ± 11 years, p = 0.002) and reduced and fragmented sleep (e.g. sleep efficiency of 82 ± 12% vs. 91 ± 6%, p = 0.015; sleep time of 353 ± 66 vs. 395 ± 28, p = 0.010). SDB and PLMs were also mutually associated (p = 0.007), but not correlated to daytime sleepiness. Conclusions: SDB and PLMs are highly prevalent and associated in NC. Nevertheless, SDB and PLMs are rarely severe, suggesting an overall limited effect on clinical manifestations.

Respiratory-related leg movements and their relationship with periodic leg movements during sleep

STUDY OBJECTIVES: To describe the time structure of leg movements (LM) in obstructive sleep apnea (OSA) syndrome, in order to advance understanding of their clinical significance. LOCATION: Sleep Research Centre, Oasi Institute (IRCCS), Troina, Italy. SETTING: Sleep laboratory. PATIENTS: Eighty-four patients (16 females, 68 males, mean age 55.1 y, range 29-74 y). METHODS: Respiratory-related leg movements (RRLM) and those unrelated to respiratory events (NRLM) were examined within diagnostic polysomnograms alone and together for their distributions within the sleep period and for their periodicity. MEASUREMENTS AND RESULTS: Patients with OSA and RRLM exhibited more periodic leg movements in sleep (PLMS), particularly in NREM sleep. A gradual decrease in number of NRLM across the sleep period was observed in patients with RRLM. This pattern was less clear for RRLM. Frequency histograms of intermovement intervals of all LMs in patients with RRLM showed a prominent first peak at 4 sec, and a second peak at approximately 24 sec coincident with that of PLMS occurring in the absence of OSA. A third peak of lowest amplitude was the broadest with a maximum at approximately 42 sec. In patients lacking RRLM, NRLM were evident with a single peak at 2-4 sec. A stepwise linear regression analysis showed that, after controlling for a diagnosis of restless legs syndrome and apnea-hypopnea index, PLMS remained significantly associated with RRLM. CONCLUSION: The time structure of leg movements occurring in conjunction with respiratory events exhibit features of periodic leg movements in sleep occurring alone, only with a different and longer period. This brings into question the validity, both biologic and clinical, of scoring conventions with their a priori exclusion from consideration as periodic leg movements in sleep.

Effects of a latency period between pre-stimulation and teat cup attachment and periodic vacuum reduction on milking characteristics and teat condition in dairy cows

The goal of the present study was to examine the suitability of a short pre-stimulation (P) for 15 s followed by a latency period (L) of 30 s before cluster attachment for machine milking. In addition we tested the effect of a periodic reduction of the vacuum under the teat (VR) during the massage phase from 43 kPa to 12-15 kPa on milking characteristics and teat tissue condition. The study was carried out in 9 cows in a cross-over design. Animals were milked twice daily, and each of the 4 treatment combinations was used for six subsequent milkings (P+L vs. continuous P, and standard pulsation vs. VR, respectively). Milk flow was recorded during all experimental milkings. Longitudinal ultrasound cross sections of the teat were performed by B-mode ultrasound after the last milking of each treatment at 0, 5, and 15 min after the end of milking, respectively. None of the evaluated milking characteristics (total milk yield, main milking time, peak flow rate, average milk flow) differed between treatments. Teat measures as obtained by ultrasound cross sections showed no significant difference if individual treatments were compared at the three time points individually. However, teat wall thickness (TWT) tended to be smaller in VR vs. non-VR treatments at 5 min after milking (P=0·05). In conclusion, teat preparation consisting of a short stimulation followed by a latency period represents a similarly efficient pre-stimulation as a continuous pre-stimulation. VR seems to reduce the load on the teat tissue during milking and thus reduces the development of oedema and hence a less pronounced increase of TWT while milking characteristics are similar with or without VR.

Health care policy analysis of Medicaid's early and periodic screening, diagnosis, and treatment (EPSDT) benefit in Colorado

The purpose of this thesis is to identify "best practice" recommendations for successful implementation of the EPSDT outreach program at Memorial Health System's Hospital for Children in Colorado Springs through a policy analysis of Medicaid EPSDT services in Colorado. A successful program at Memorial will increase education and awareness of EPSDT services, enrollment, and access to and utilization of health care services for eligible children. Methodology utilized in this study included questionnaires designed for the EPSDT contract administrator and outreach coordinators/workers; analysis of current federal and state policies; and studies conducted at the federal and state level, and by various advocacy groups. The need for this analysis of EPSDT came about in part through an awareness of increasingly high numbers of children in poverty and who are uninsured. Though the percentage of children living in poverty in Colorado is slightly below the national average (see Table 2), according to data analyzed by The Annie E. Casey Foundation, the percentage of children (0-18) living in poverty in Colorado increased from 10% in 2000 to 16% in 2006, a dramatic increase of 60% surpassed by only one other state in the nation (The Annie E. Casey Foundation, 2008). By comparison, the U.S. percentage of children in poverty during the same time frame rose from 17% to 18% (The Annie E. Casey Foundation, 2008). What kind of health care services are available to this vulnerable and growing group of Coloradans, and what are the barriers that affect their enrollment in, access to and utilization of these health care services? Barriers identified included difficulty with the application process; system and process issues; a lack of providers; and a lack of awareness and knowledge of EPSDT. Fiscal restraints and legislation at the federal and state level are also barriers to increasing enrollment and access to services. Outreach services are a critical component of providing EPSDT services, and there were several recommendations regarding outreach and case management that will benefit the program in the future. Through this analysis and identification of a broad range of barriers, a clearer picture emerged of current challenges within the EPSDT program as well as a broad range of strategies and recommendations to address these challenges. Through increased education and advocacy for EPSDT and the services it encompasses; stronger collaboration and cooperation between all groups involved, including providing a Medical Home for all eligible children; and new legislation putting more money and focus on comprehensive health care for low-income uninsured children; enrollment, access to and utilization of developmentally appropriate and quality health care services can be achieved. ^

Periodic time-domain modulation for the electrically tunable control of optical pulse train envelope and repetition rate multiplication

An electrically tunable system for the control of optical pulse sequences is proposed and demonstrated. It is based on the use of an electrooptic modulator for periodic phase modulation followed by a dispersive device to obtain the temporal Talbot effect. The proposed configuration allows for repetition rate multiplication with different multiplication factors and with the simultaneous control of the pulse train envelope by simply changing the electrical signal driving the modulator. Simulated and experimental results for an input optical pulse train of 10 GHz are shown for different multiplication factors and envelope shapes.

Non-periodic driving of coupled oscillators:a spherical swing

Nonlinearly coupled, damped oscillators at 1:1 frequency ratio, one oscillator being driven coherently for efficient excitation, are exemplified by a spherical swing with some phase-mismatch between drive and response. For certain damping range, excitation is found to succeed if it lags behind, but to produce a chaotic attractor if it leads the response. Although a period-doubhng sequence, for damping increasing, leads to the attractor, this is actually born as a hard (as regards amplitude) bifurcation at a zero growth-rate parametric line; as damping decreases, an unstable fixed point crosses an invariant plane to enter as saddle-focus a phase-space domain of physical solutions. A second hard bifurcation occurs at the zero mismatch line, the saddle-focus leaving that domain. Times on the attractor diverge when approaching either fine, leading to exactly one-dimensional and noninvertible limit maps, which are analytically determined.

Transmission of digital chaotic and information-bearing signals in optical communication systems

A new proposal to have secure communications in a system is reported. The basis is the use of a synchronized digital chaotic systems, sending the information signal added to an initial chaos. The received signal is analyzed by another chaos generator located at the receiver and, by a logic boolean function of the chaotic and the received signals, the original information is recovered. One of the most important facts of this system is that the bandwidth needed by the system remain the same with and without chaos.

Optically programmable logic cells as basic units for transmission and synchronization of chaotic signals

We proposed an optical communications system, based on a digital chaotic signal where the synchronization of chaos was the main objective, in some previous papers. In this paper we will extend this work. A way to add the digital data signal to be transmitted onto the chaotic signal and its correct reception, is the main objective. We report some methods to study the main characteristics of the resulting signal. The main problem with any real system is the presence of some retard between the times than the signal is generated at the emitter at the time when this signal is received. Any system using chaotic signals as a method to encrypt need to have the same characteristics in emitter and receiver. It is because that, this control of time is needed. A method to control, in real time the chaotic signals, is reported.

Selected topics in the Hydrodynamics of floating offshore wind turbines: heave damping and second order surge motions

La Energía eléctrica producida mediante tecnología eólica flotante es uno de los recursos más prometedores para reducir la dependencia de energía proveniente de combustibles fósiles. Esta tecnología es de especial interés en países como España, donde la plataforma continental es estrecha y existen pocas áreas para el desarrollo de estructuras fijas. Entre los diferentes conceptos flotantes, esta tesis se ha ocupado de la tipología semisumergible. Estas plataformas pueden experimentar movimientos resonantes en largada y arfada. En largada, dado que el periodo de resonancia es largo estos puede ser inducidos por efectos de segundo orden de deriva lenta que pueden tener una influencia muy significativa en las cargas en los fondeos. En arfada las fuerzas de primer orden pueden inducir grandes movimientos y por tanto la correcta determinación del amortiguamiento es esencial para la analizar la operatividad de la plataforma. Esta tesis ha investigado estos dos efectos, para ello se ha usado como caso base el diseño de una plataforma desarrollada en el proyecto Europeo Hiprwind. La plataforma se compone de 3 columnas cilíndricas unidas mediante montantes estructurales horizontales y diagonales, Los cilindros proporcionan flotabilidad y momentos adrizante. A la base de cada columna se le ha añadido un gran “Heave Plate” o placa de cierre. El diseño es similar a otros diseños previos (Windfloat). Se ha fabricado un modelo a escala de una de las columnas para el estudio detallado del amortiguamiento mediante oscilaciones forzadas. Las dimensiones del modelo (1m diámetro en la placa de cierre) lo hacen, de los conocidos por el candidato, el mayor para el que se han publicado datos. El diseño del cilindro se ha realizado de tal manera que permite la fijación de placas de cierre planas o con refuerzo, ambos modelos se han fabricado y analizado. El modelo con refuerzos es una reproducción exacta del diseño a escala real incluyendo detalles distintivos del mismo, siendo el más importante la placa vertical perimetral. Los ensayos de oscilaciones forzadas se han realizado para un rango de frecuencias, tanto para el disco plano como el reforzado. Se han medido las fuerzas durante los ensayos y se han calculado los coeficientes de amortiguamiento y de masa añadida. Estos coeficientes son necesarios para el cálculo del fondeo mediante simulaciones en el dominio del tiempo. Los coeficientes calculados se han comparado con la literatura existente, con cálculos potenciales y por ultimo con cálculos CFD. Para disponer de información relevante para el diseño estructural de la plataforma se han medido y analizado experimentalmente las presiones en la parte superior e inferior de cada placa de cierre. Para la correcta estimación numérica de las fuerzas de deriva lenta en la plataforma se ha realizado una campaña experimental que incluye ensayos con modelo cautivo de la plataforma completa en olas bicromaticas. Pese a que estos experimentos no reproducen un escenario de oleaje realista, los mismos permiten una verificación del modelo numérico mediante la comparación de fuerzas medidas en el modelo físico y el numérico. Como resultados de esta tesis podemos enumerar las siguientes conclusiones. 1. El amortiguamiento y la masa añadida muestran una pequeña dependencia con la frecuencia pero una gran dependencia con la amplitud del movimiento. siendo coherente con investigaciones existentes. 2. Las medidas con la placa de cierre reforzada con cierre vertical en el borde, muestra un amortiguamiento significativamente menor comparada con la placa plana. Esto implica que para ensayos de canal es necesario incluir estos detalles en el modelo. 3. La masa añadida no muestra grandes variaciones comparando placa plana y placa con refuerzos. 4. Un coeficiente de amortiguamiento del 6% del crítico se puede considerar conservador para el cálculo en el dominio de la frecuencia. Este amortiguamiento es equivalente a un coeficiente de “drag” de 4 en elementos de Morison cuadráticos en las placas de cierre usadas en simulaciones en el dominio del tiempo. 5. Se han encontrado discrepancias en algunos valores de masa añadida y amortiguamiento de la placa plana al comparar con datos publicados. Se han propuesto algunas explicaciones basadas en las diferencias en la relación de espesores, en la distancia a la superficie libre y también relacionadas con efectos de escala. 6. La presión en la placa con refuerzos son similares a las de la placa plana, excepto en la zona del borde donde la placa con refuerzo vertical induce una gran diferencias de presiones entre la cara superior e inferior. 7. La máxima diferencia de presión escala coherentemente con la fuerza equivalente a la aceleración de la masa añadida distribuida sobre la placa. 8. Las masas añadidas calculadas con el código potencial (WADAM) no son suficientemente precisas, Este software no contempla el modelado de placas de pequeño espesor con dipolos, la poca precisión de los resultados aumenta la importancia de este tipo de elementos al realizar simulaciones con códigos potenciales para este tipo de plataformas que incluyen elementos de poco espesor. 9. Respecto al código CFD (Ansys CFX) la precisión de los cálculos es razonable para la placa plana, esta precisión disminuye para la placa con refuerzo vertical en el borde, como era de esperar dado la mayor complejidad del flujo. 10. Respecto al segundo orden, los resultados, en general, muestran que, aunque la tendencia en las fuerzas de segundo orden se captura bien con los códigos numéricos, se observan algunas reducciones en comparación con los datos experimentales. Las diferencias entre simulaciones y datos experimentales son mayores al usar la aproximación de Newman, que usa únicamente resultados de primer orden para el cálculo de las fuerzas de deriva media. 11. Es importante remarcar que las tendencias observadas en los resultados con modelo fijo cambiarn cuando el modelo este libre, el impacto que los errores en las estimaciones de fuerzas segundo orden tienen en el sistema de fondeo dependen de las condiciones ambientales que imponen las cargas ultimas en dichas líneas. En cualquier caso los resultados que se han obtenido en esta investigación confirman que es necesaria y deseable una detallada investigación de los métodos usados en la estimación de las fuerzas no lineales en las turbinas flotantes para que pueda servir de guía en futuros diseños de estos sistemas. Finalmente, el candidato espera que esta investigación pueda beneficiar a la industria eólica offshore en mejorar el diseño hidrodinámico del concepto semisumergible. ABSTRACT Electrical power obtained from floating offshore wind turbines is one of the promising resources which can reduce the fossil fuel energy consumption and cover worldwide energy demands. The concept is the most competitive in countries, such as Spain, where the continental shelf is narrow and does not provide space for fixed structures. Among the different floating structures concepts, this thesis has dealt with the semisubmersible one. Platforms of this kind may experience resonant motions both in surge and heave directions. In surge, since the platform natural period is long, such resonance can be excited with second order slow drift forces and may have substantial influence on mooring loads. In heave, first order forces can induce significant motion, whose damping is a crucial factor for the platform downtime. These two topics have been investigated in this thesis. To this aim, a design developed during HiPRWind EU project, has been selected as reference case study. The platform is composed of three cylindrical legs, linked together by a set of structural braces. The cylinders provide buoyancy and restoring forces and moments. Large circular heave plates have been attached to their bases. The design is similar to other documented in literature (e.g. Windfloat), which implies outcomes could have a general value. A large scale model of one of the legs has been built in order to study heave damping through forced oscillations. The final dimensions of the specimen (one meter diameter discs) make it, to the candidate’s knowledge, the largest for which data has been published. The model design allows for the fitting of either a plain solid heave plate or a flapped reinforced one; both have been built. The latter is a model scale reproduction of the prototype heave plate and includes some distinctive features, the most important being the inclusion of a vertical flap on its perimeter. The forced oscillation tests have been conducted for a range of frequencies and amplitudes, with both the solid plain model and the vertical flap one. Forces have been measured, from which added mass and damping coefficients have been obtained. These are necessary to accurately compute time-domain simulations of mooring design. The coefficients have been compared with literature, and potential flow and CFD predictions. In order to provide information for the structural design of the platform, pressure measurements on the top and bottom side of the heave discs have been recorded and pressure differences analyzed. In addition, in order to conduct a detailed investigation on the numerical estimations of the slow-drift forces of the HiPRWind platform, an experimental campaign involving captive (fixed) model tests of a model of the whole platform in bichromatic waves has been carried out. Although not reproducing the more realistic scenario, these tests allowed a preliminary verification of the numerical model based directly on the forces measured on the structure. The following outcomes can be enumerated: 1. Damping and added mass coefficients show, on one hand, a small dependence with frequency and, on the other hand, a large dependence with the motion amplitude, which is coherent with previously published research. 2. Measurements with the prototype plate, equipped with the vertical flap, show that damping drops significantly when comparing this to the plain one. This implies that, for tank tests of the whole floater and turbine, the prototype plate, equipped with the flap, should be incorporated to the model. 3. Added mass values do not suffer large alterations when comparing the plain plate and the one equipped with a vertical flap. 4. A conservative damping coefficient equal to 6% of the critical damping can be considered adequate for the prototype heave plate for frequency domain analysis. A corresponding drag coefficient equal to 4.0 can be used in time domain simulations to define Morison elements. 5. When comparing to published data, some discrepancies in added mass and damping coefficients for the solid plain plate have been found. Explanations have been suggested, focusing mainly on differences in thickness ratio and distance to the free surface, and eventual scale effects. 6. Pressures on the plate equipped with the vertical flap are similar in magnitude to those of the plain plate, even though substantial differences are present close to the edge, where the flap induces a larger pressure difference in the reinforced case. 7. The maximum pressure difference scales coherently with the force equivalent to the acceleration of the added mass, distributed over the disc surface. 8. Added mass coefficient values predicted with the potential solver (WADAM) are not accurate enough. The used solver does not contemplate modeling thin plates with doublets. The relatively low accuracy of the results highlights the importance of these elements when performing potential flow simulations of offshore platforms which include thin plates. 9. For the full CFD solver (Ansys CFX), the accuracy of the computations is found reasonable for the plain plate. Such accuracy diminishes for the disc equipped with a vertical flap, an expected result considering the greater complexity of the flow. 10. In regards to second order effects, in general, the results showed that, although the main trend in the behavior of the second-order forces is well captured by the numerical predictions, some under prediction of the experimental values is visible. The gap between experimental and numerical results is more pronounced when Newman’s approximation is considered, making use exclusively of the mean drift forces calculated in the first-order solution. 11. It should be observed that the trends observed in the fixed model test may change when the body is free to float, and the impact that eventual errors in the estimation of the second-order forces may have on the mooring system depends on the characteristics of the sea conditions that will ultimately impose the maximum loads on the mooring lines. Nevertheless, the preliminary results obtained in this research do confirm that a more detailed investigation of the methods adopted for the estimation of the nonlinear wave forces on the FOWT would be welcome and may provide some further guidance for the design of such systems. As a final remark, the candidate hopes this research can benefit the offshore wind industry in improving the hydrodynamic design of the semi-submersible concept.

Global instability analysis and control of three-dimensional long open cavity flow

The three-dimensional wall-bounded open cavity may be considered as a simplified geometry found in industrial applications such as leading gear or slotted flats on the airplane. Understanding the three-dimensional complex flow structure that surrounds this particular geometry is therefore of major industrial interest. At the light of the remarkable former investigations in this kind of flows, enough evidences suggest that the lateral walls have a great influence on the flow features and hence on their instability modes. Nevertheless, even though there is a large body of literature on cavity flows, most of them are based on the assumption that the flow is two-dimensional and spanwise-periodic. The flow over realistic open cavity should be considered. This thesis presents an investigation of three-dimensional wall-bounded open cavity with geometric ratio 6:2:1. To this aim, three-dimensional Direct Numerical Simulation (DNS) and global linear instability have been performed. Linear instability analysis reveals that the onset of the first instability in this open cavity is around Recr 1080. The three-dimensional shear layer mode with a complex structure is shown to be the most unstable mode. I t is noteworthy that the flow pattern of this high-frequency shear layer mode is similar to the observed unstable oscillations in supercritical unstable case. DNS of the cavity flow carried out at different Reynolds number from steady state until a nonlinear saturated state is obtained. The comparison of time histories of kinetic energy presents a clearly dominant energetic mode which shifts between low-frequency and highfrequency oscillation. A complete flow patterns from subcritical cases to supercritical case has been put in evidence. The flow structure at the supercritical case Re=1100 resembles typical wake-shedding instability oscillations with a lateral motion existed in the subcritical cases. Also, This flow pattern is similar to the observations in experiments. In order to validate the linear instability analysis results, the topology of the composite flow fields reconstructed by linear superposition of a three-dimensional base flow and its leading three-dimensional global eigenmodes has been studied. The instantaneous wall streamlines of those composited flows display distinguish influence region of each eigenmode. Attention has been focused on the leading high-frequency shear layer mode; the composite flow fields have been fully recognized with respect to the downstream wave shedding. The three-dimensional shear layer mode is shown to give rise to a typical wake-shedding instability with a lateral motions occurring downstream which is in good agreement with the experiment results. Moreover, the spanwise-periodic, open cavity with the same length to depth ratio has been also studied. The most unstable linear mode is different from the real three-dimensional cavity flow, because of the existence of the side walls. Structure sensitivity of the unstable global mode is analyzed in the flow control context. The adjoint-based sensitivity analysis has been employed to localized the receptivity region, where the flow is more sensible to momentum forcing and mass injection. Because of the non-normality of the linearized Navier-Stokes equations, the direct and adjoint field has a large spatial separation. The strongest sensitivity region is locate in the upstream lip of the three-dimensional cavity. This numerical finding is in agreement with experimental observations. Finally, a prototype of passive flow control strategy is applied.

Periodic variation in side-chain polarities of T-cell antigenic peptides correlates with their structure and activity.

We present an analysis that synthesizes information on the sequence, structure, and motifs of antigenic peptides, which previously appeared to be in conflict. Fourier analysis of T-cell antigenic peptides indicates a periodic variation in amino acid polarities of 3-3.6 residues per period, suggesting an amphipathic alpha-helical structure. However, the diffraction patterns of major histocompatibility complex (MHC) molecules indicate that their ligands are in an extended non-alpha-helical conformation. We present two mutually consistent structural explanations for the source of the alpha-helical periodicity, based on an observation that the side chains of MHC-bound peptides generally partition with hydrophobic (hydrophilic) side chains pointing into (out of) the cleft. First, an analysis of haplotype-dependent peptide motifs indicates that the locations of their defining residues tend to force a period 3-4 variation in hydrophobicity along the peptide sequence, in a manner consistent with the spacing of pockets in the MHC. Second, recent crystallographic determination of the structure of a peptide bound to a class II MHC molecule reveals an extended but regularly twisted peptide with a rotation angle of about 130 degrees. We show that similar structures with rotation angles of 100-130 degrees are energetically acceptable and also span the length of the MHC cleft. These results provide a sound physical chemical and structural basis for the existence of a haplotype-independent antigenic motif which can be particularly important in limiting the search time for antigenic peptides.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

'A Kind of Logic, A Kind of Dominant Logic': Navigating Colonialism, Honoring Black Mobility, and Thinking on Moving Through

My thesis thinks through the ways Newtonian logics require linear mobility in order to produce narratives of progress. I argue that this linear mobility, and the resulting logics, potentially erases the chaotic and non-linear motions that are required to navigate a colonial landscape. I suggest that these non-linear movements produce important critiques of the seeming stasis of colonial constructs and highlight the ways these logics must appear neutral and scientific in an attempt to conceal the constant and complex adjustments these frameworks require. In order to make room for these complex motions, I develop a quantum intervention. Specifically, I use quantum physics as a metaphor to think through the significance of black life, the double-consciousness ofland, and the intricate motions of sound. In order to put forth this intervention, I look at news coverage of Hurricane Katrina, Du Bois’s characterization of land in Souls of Black Folks, and the aural mobilities of blackness articulated in an academic discussion and interview about post- humanism.