The relations between mismatched parent-adolescent autonomy beliefs, and psychological adjustment and parenting self-efficacy were investigated among 89 immigrant Chinese Canadian families with early adolescents. Hierarchical regression analyses assessed whether interactions between parents’ autonomy beliefs and adolescents’ autonomy beliefs predicted psychological adjustment and parenting self-efficacy. Parent-adolescent conflict intensity was evaluated as a mediator of these relations. Parental warmth was evaluated as a moderator of the relations between autonomy beliefs and adolescent psychological adjustment. When adolescents held early expectations for autonomy, mothers who held later expectations for autonomy reported lower parenting self-efficacy. When fathers perceived high decision making independence, adolescents who perceived low decision making independence reported fewer depressive symptoms. Conflict intensity did not mediate these relations. Although parental warmth did not moderate in the predicted manner, fathers' warmth moderated the relation between fathers’ expectations for autonomy and adolescent self-esteem. Implications for healthy adolescent autonomy among immigrant Chinese Canadian families are discussed.

The structure of liquid water and adsorbed leucine at solid surfaces of tunable hydropho¬bicity has been examined by molecular dynamics simulation. The results have been used to extend models of water ordering at superhydrophobic surfaces to create a general model of density-dependent ordering of water and adsorbates at hydrophobic interfaces. In this model, interfacial water structures can be classified according to two hydrophobic regimes, a non-wetting structure and a semi-wetting structure, distinguished by the orientation of interfacial water molecules. We propose that the emergence of the wetting-type order is strongly dependent on the density profile across the interfacial region. Leucine adsorbed at the same surfaces also shows two patterns of adsorption, distinguished by the proportion of time the molecule adopts an orientation parallel to the surface. These patterns correspond to the non-wetting and semi-wetting regimes of water and also arise from the density structure of water in the interfacial region.

As astronomers continue to examine fainter objects and farther back in time, they require increasingly large telescopes due to the fundamental diffraction of optical elements. Therefore several of the next generation optical telescopes will employ extremely large primary mirrors. However to realistically construct mirrors of these magnitudes they will need to be assembled as a collection of many smaller mirrors. This mirror segmentation leads to the additional challenge of aligning the smaller mirror elements with respect to one another, and maintain that alignment in the presence of disturbances on the optical surface and its supporting structure. To achieve this alignment and disturbance rejection, a complex active control system will be required. There are several possible solutions to the control problem ranging from fully decentralized control to a global control scheme. However since many of these segmented mirrors will be comprised of hundreds of mirror elements a global control scheme quickly becomes an intractable solution. On the other extreme, a highly scalable decentralized scheme is realizable, however, would lack any global sense of the system. Therefore an appealing solution is a scalable distributed network of controllers, where individual controllers 'act locally' yet 'think globally'. This is achieved by coupling adjacent controller to one another, forming a lattice across the spatial extents of the system.

The current dogma states that the medial perforant path (MPP) and lateral perforant path (LPP) inputs to the hippocampal dentate gyrus can be differentiated electrophysiologically using the response to paired-pulse stimuli. Stimulation at 50 ms intervals produces paired-pulse depression (PPD) in the MPP, whereas these same stimuli produce paired-pulse facilitation (PPF) in the LPP (McNaughton 1980). Several years of practical experience in our laboratory has led us to question the utility of paired-pulse administration as a reliable means to differentiate the perforant path subdivisions in vitro. Using field recordings in male Sprague Dawley rats, we demonstrate both subdivisions of the perforant pathway show predominantly PPF at low stimulus intensities. Activation of the LPP registered significantly greater net PPF (24.97±4.08%) relative to the MPP (13.76±3.86%) at the 50 ms interpulse interval. These results were independent of the position in the dorsoventral axis from which the hippocampal slice was obtained but elevating the calcium concentration (2mM to 4mM) or decreasing the temperature (300C to 230C) reduced the paired-pulse ratio. Increasing the magnitude of the applied stimulus could result in PPD in both paths in a manner that was correlated with the emergence of population spikes (r> -0.90). Partial blockade of AMPA receptors reduced the ability of high stimulus intensities to induce PPD and restored PPF in most cases. A comparison of field excitatory postsynaptic potential (fEPSP) characteristics demonstrated MPP waveforms could be differentiated by their significantly shorter peak latency and half-width times, greater total decay time, and the presence of a more reliable bi-exponential decay phase function relative to LPP waveforms. This research helps to refine our view of functional differences between the MPP and LPP, revealing more subtle differences in paired-pulse plasticity and distinct fEPSP waveform parameters as reliable features to distinguish these pathways.

The effects of ethanol on the brain are far reaching. However, the effect of ethanol on synaptic plasticity has not yet been fully explored. Although it has been established that ethanol inhibits long-term potentiation (LTP) in the CA1 of the hippocampus, before our study, it was unclear whether long-term depression (LTD) was attenuated or enhanced by ethanol. We found that different concentrations of ethanol attenuated LTD in the CA1 (CA1-LTD) at younger ages. At more mature ages, CA1-LTD was completely blocked by ethanol. In contrast to this, LTD in the dentate gyrus (DG-LTD) was not significantly affected by ethanol concentrations up to 100 mM at any age group tested. These results suggest there are mechanistic differences in LTD induction in the DG and CA1, using the same induction protocol and that CA1-LTD is ethanol sensitive but DG-LTD is not.

The ecological implications of altering the hydrologic regime, or hydroperiod, of a wetland system include major changes to both ecosystem structure and function. Wetland systems are generally sinks of nutrients such as phosphorus, nitrogen and carbon, which are important to water quality. Changes in the hydroperiod such as the inundation or drainage of a wetland system alter wetland function and may switch the system from functioning as a nutrient sink to a source. In this study, I explored the effects from the introduction of a seasonal inundation regime to the Begbie Lake wetland system. Begbie Lake is hydrologically connected to the Sooke Lake reservoir, the main drinking water supply for Greater Victoria, British Columbia. In 2002, the dam on the Sooke Lake reservoir was raised by 6 m, which led to the seasonal inundation of the Begbie Lake wetland system in 2005 and 2006. In 2005, the Begbie Lake wetland system was inundated for 57 days, from April through May. In 2006, the wetland was inundated for 123 days, from January through May. The seasonal inundation resulted in the release of phosphorus, nitrogen and carbon from the wetland system into Begbie Lake and the Sooke Lake reservoir. Nutrients such as phosphorus and nitrogen are especially important in drinking water reservoirs, where increases in concentrations often lead to increased algal biomass and possibly a shift toward cyanobacteria-dominated phytoplankton communities. Organic carbon in source water is correlated with disinfection by-product production during treatment, increases in bacterial biomass within distribution systems, and decreases in the efficacy of water treatment. The response to inundation of the wetland system, in terms of the release of key water quality nutrients into Begbie Lake was assessed. Water chemistry data collected from 2005 and 2006 were compared to pre-inundation baseline data (2003 and 2004) over the growing season. Phosphorus, nitrogen and organic carbon concentrations above the flooded wetland soils increased significantly during the inundation periods. Following drawdown, the total phosphorus concentration in Begbie Lake increased signi cantly. Total nitrogen and total organic carbon concentrations in Begbie Lake did not increase over this same period; the microbial mineralization and reduction of nitrogen and organic carbon, as well as the export of these nutrients into the Sooke Lake reservoir, are proposed as in uencing the observations. The inundation of the Begbie Lake wetland system also resulted in the export of large amounts of nitrogen and organic carbon to the Sooke Lake reservoir. The increase in the duration and extent of inundation in 2006 resulted in higher contributions from the Begbie Lake wetland system. The export of nitrogen increased from 3.8 kg in 2005 to 4.4 kg in 2006. Carbon export increased from 77.7 kg in 2005 to 171.1 kg in 2006. The export of high amounts of phosphorus were not observed during the study. While phosphorus concentrations increased above wetland soils, the data suggest that much of the phosphorus remained cycling within Begbie Lake.

Surface-enhanced Raman scattering (SERS) constitutes a spectroscopy of rapidly growing importance. To understand and control the enhancing surface is key for optimizing SERS. In this work, progressively more ordered substrates for SERS are investigated: gold clusters, scratched gold films, nanohole arrays in a copper film and nanoscale gratings in a gold film. Gold clusters constitute the most random SERS substrate: samples were prepared by alternating vapour deposition of gold and plasma-induced polymerization of styrene gas. The relationships between sample preparation parameters, gold-cluster morphology, and SERS intensity were elucidated. Using Wilson’s notation, vibrations were assigned to all bands between 250 and 1750 cm-1 in the ordinary Raman and SERS spectra of polystyrene. The orientation of polystyrene’s phenyl ring, relative to the gold surface, was determined. It has been suggested that reactions involving silver catalyze polystyrene degradation during SERS, but we found that silver is not necessary for the degradation to occur. Of intermediate order are scratched gold films. Polarization-dependent SERS was studied for scratched gold films placed in-situ and under electrochemical control. A quantitative method for evaluating the polarization dependence was developed. In addition, we established that polarization effects may be used to selectively remove solution-phase interference signals from the SERS spectrum of an adsorbed analyte. Nanohole arrays and nanoscale gratings, made by focused ion beam (FIB) milling, constitute the most ordered SERS substrates. SERS was observed for oxazine 720 molecules adsorbed on a copper film pierced by nanohole arrays. Each of the arrays had a different hole-periodicity, and the effect of this periodicity on SERS intensity was examined. Electric fieldstrength perpendicular to the surface of the metal was calculated for each array using the finite-difference time-domain (FDTD) method, and the array with the greatest calculated value matched the array that gave the greatest experimentally observed SERS intensity. Finally, SERS was observed for oxazine 720 molecules adsorbed on a gold film through which nanoscale gratings were milled. We varied the width of the grooves and the width of the metal lines between them, and we examined the resulting effect on SERS intensity.

Asymmetric hydrophosphination, the addition of a P-H bond across a C-C double bond, is an attractive potential route to chiral phosphines, which have important applications in many other types of asymmetric catalysis. However, a highly active and stereoselective catalyst for this reaction has yet to be identified. The ruthenium indenyl complex [RuCl(η5-indenyl)(PPh3)2] (1) was investigated as a potential catalyst for hydrophosphination through an exploration of the steps involved in this process: substrate coordination, P-H bond activation, and P-C bond formation. Substitution of triphenylphosphine ligands at the metal centre of 1 by alkyl- and aryl-substituted secondary phosphines (PR2H: R = Cy (a), Pri (b), Et (c), Ph (d) or Tolp (e)) gave predominantly the monosubstituted secondary phosphine complexes [RuCl(η5-indenyl)(PR2H)(PPh3)] (3a-e). Hydride ([RuH(η5-indenyl)(PR2H)(PPh3)] (6a,d)) and cationic nitrile ([Ru(η5-indenyl)(NCR')(PR2H)(PPh3)][PF6] (7a,d: R' = CH=CH2; 8a-b,d: R = CH3)) derivatives of 3 were prepared and in all cases the potentially reactive P-H bond of the secondary phosphine ligand did not interfere with the chemical transformation. Deprotonation of the P-H bond of the bulky dialkylphosphine-substituted chloro complexes 3a-b with KOBut gave five-coordinate, planar terminal phosphido complexes [Ru(η5-indenyl)(PR2)(PPh3)] (10a-b) that contain a unique Ru-PR2 π-bond. The analogous phosphido complexes 10d-e, containing less bulky aryl substituents at phosphorus, were found to be unstable at room temperature and were observed only by low temperature 31P{1H} NMR spectroscopy. Phosphido complexes 10a-b were found to be highly P-basic, capable of deprotonating the C-H bond of acetonitrile (pKa = 24) to give the metallated acetonitrile complex [Ru(CH2CN)(η5-indenyl)(PR2H)(PPh3)] (9a-b), and to be very P-nucleophilic, reacting with iodomethane (MeI) to give a new P-C bond in [RuI(η5-indenyl)(PCy2Me)(PPh3)] (17a). As might be expected, the addition of donor ligands to low-coordinate 10a-b was found to disrupt the Ru-PR2 π-bond to give six-coordinate terminal phosphido complexes [Ru(η5-indenyl)(L)(PR2H)(PPh3)], with pyramidal, instead of planar, geometry at phosphorus. These additions are irreversible in the case of CO (19a-b) or PCy2H (21a), while pyridine (23a-b) or NCPh (24a-b) adducts were shown by 31P{1H} NMR spectroscopy to be in equilibrium with 10a-b and the uncoordinated ligand. The addition of known substrates for transition metal-mediated hydrophosphination, phenylacetylene and acrylonitrile, to 10a-b resulted in a [2+2] cycloaddition of the unsaturated C-C bond at the Ru-PR2 π-bond to give metallacyclic complexes [Ru(η5-indenyl)(κ2-PhC=CHPR2)(PPh3)] (27a-b) and [Ru(η5-indenyl)(κ2-NCCHCH2PR2)(PPh3)] (32a-b) respectively. Surprisingly the addition of simple non-activated olefins (i.e. ethylene, 1-hexene, or norbornene), which were not previously known to be active substrates for this reaction, also gave [2+2] cycloaddition products. These cycloaddition reactions were found to be 100% regioselective, and are also stereoselective in the case of substituted alkenes (>96%). Experimental evidence suggests that these P-C bond forming reactions proceed via a concerted [2+2] cycloaddition pathway.

The Confocal Scanning Laser Holography (CSLH) microscope non-intrusively measures the three-dimensional (3D) temperature and composition of a solid, fluid, or plasma. A unique reconstruction algorithm uses phase-shift data from the recorded holograms and boundary conditions of the specimen to measure the 3D temperature. The CSLH microscope uniquely combines holography with a scanning confocal microscope to determine the phase-shift in a hologram and to reconstruct the 3D temperature. The confocal aspect of the microscope reduces optical aberrations in the hologram and increases sensitivity to a temperature at a scan position in the specimen. The optical design maintains a stationary focal point on the pinhole aperture within the confocal optics during scanning. The CSLH microscope uses a focused laser beam instead of a collimated beam to probe the specimen. The advantage of the focused probe beam over the collimated beam is that different phase-shift data is obtained for each scan position of the probe beam. Another advantage is preventing rotational scanning of the laser about the specimen or rotating the specimen, increasing the number of practical applications. This limits the scan angle to the cone angle of the probe beam only. Reconstruction of the 3D temperature given restricted scanning from a single viewing window places a burden on the reconstruction algorithm to produce low reconstruction error. Three-dimensional reconstruction using methods of tomography prove inaccurate due to the small cone angle. The result is ill-conditioned reconstruction matrices. A unique low reconstruction error algorithm given a single viewpoint window that specifies a particular scanning geometry and requires boundary conditions is derived for the microscope. This research involved the design, building, and evaluation of a specific CSLH microscope intended for fluid flow and heat transfer studies in micro-gravity space based experiments. The fluid specimen used to evaluate the microscope sets a benchmark for resolution, sensitivity, and performance. The reconstruction error is primarily due to measurement error, residual optical aberrations affecting holograms, and vibrations since the reconstruction algorithm error is negligible. Additional knowledge gained includes the understanding of sensitivity to optical alignment as well as methods to accurately determine the phase-shift in a varying fringe contrast hologram. A significant trade-off is that as the cone angle of the probe beam increases, the reconstruction error decreases but the optical aberrations increase. One of the more difficult challenges during scanning is to maintain a fixed focal point on the confocal apertures as the beam is tilted off the optical axis centerline. Further recommended advancements for the microscope are improving the optical lenses to provide pupil planes that are stationary during scanning and the miniaturization of the microscope using diffraction grating lenses instead of glass lenses for more practical applications. Determining the internal temperature of a flame by passing a focused laser beam through the flame is an example of a practical application. The CSLH microscope is uniquely capable of non-intrusively measuring the 3D temperature of a specimen given a single viewpoint window for scanning with applications in the physical and biological sciences.

The relativistic Vlasov-Maxwell system (RVM for short) is a kinetic model that arises in plasma physics and describes the time evolution of an ensemble of charged particles that interact only through their self-induced electromagnetic field. Collisions among the particles are neglected and they are assumed to move at speeds comparable to the speed of light. If the particles are allowed to move in the three dimensional space, then the main open problem concerning this system is to prove (or disprove) that solutions with sufficiently smooth Cauchy data do not develop singularities in finite time. Since the RVM system is essential in the study of dilute hot plasmas, much effort has been directed to the solution of its Cauchy problem. The underlying hyperbolic nature of the Maxwell equations and their nonlinear coupling with the Vlasov equation amount for the challenges imposed by this system. In this thesis, we show that solutions of the RVM system with smooth, compactly supported Cauchy data develop singularities only if the charge density blows-up in finite time. In particular, solutions can not break-down due to shock formations, since in this case scenario the solution would remain bounded while its derivative blows-up. On the other hand, if the transversal component of the displacement current is neglected from the Maxwell equations, then the RVM system reduces to the socalled relativistic Vlasov-Darwin (RVD) system. The latter has useful applications in numeric simulations of collisionless plasma, since the hyperbolic RVM is now reduced to a more tractable elliptic system while preserving a fully coupled magnetic field. As for the RVM system, the main open problem for the RVD system is to prove whether classical solutions with unrestricted Cauchy data exist globally in time. In the second part of this thesis, we show that classical solutions of the RVD system exist provided the Cauchy datum satisfies some suitable smallness assumption. The proof presented here does not require estimates derived from the conservation of the total energy nor those on the transversal component of the electric field. These have been crucial in previous results concerning the RVD system. Instead, we exploit the potential formulation of the model equations. In particular, the Vlasov equation is rewritten in terms of the generalized variables and coupled with the equations satisfied by the scalar and vector Darwin potentials. This allows to use standard estimates for singular integrals and a recursive method to produce the existence of local in time classical solutions. Hence, by means of a bootstrap argument, we show that such solutions can be made global in time provided the Cauchy data is sufficiently small.