The research presented in this dissertation involves the synthesis, characterization, and application of novel anionic and cationic chiral molecular micelles in capillary electrophoresis (CE) for the separation of diverse chiral compounds. Chapter 1 presents brief overview of the surfactants, micelle polymer, CE and micellar electrokinetic chromatography (MEKC). Chapter 2 describes the simultaneous enantioseparation of eight single chiral center â-blockers using two novel leucine and isoleucine based polymeric surfactants. The simultaneous enantioseparation of multichiral center bearing â-blockers, nadolol and labetalol is described in chapter 3. A synergistic approach, using a combination of polysodium N-undecenoxycarbonyl-L-isoleucinate (poly-L-SUCIL) and sulfated â-CD showed dramatic enantioseparation of four stereoisomers of nadolol. On the other hand for labetalol, enantiomeric separation remains unaffected using the dual chiral selector system. Chapter 4 deals with the enantiomeric separation of the binaphthyl derivatives that was found to be influenced by pH, type and concentration of the background electrolyte as well as concentration of the polymeric surfactant. In chapter 5, characterization of five alkenoxy leucine-based surfactants with variations in chain length (C8-C11), polymerization concentration and degree of polymerization showed significant effects on the chiral resolution and efficiency of hydrophobic â-blockers. The synthesis and characterization of two positively charged amino acid derived chiral ionic liquids (ILs) and their corresponding polymers is presented in chapter 6. Chiral separation of two acidic analyte (difficult to resolve with anionic micelles) can be achieved with both monomers and polymers of ILs. In chapter 7, the synthesis and detailed characterization of three pH independent amino acids derived (L-leucinol, L-isoleucinol and L-valinol) sulfated chiral polymeric surfactants is presented. These chiral sulfated surfactants are thoroughly characterized and the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The work clearly demonstrates for the first time the superiority of chiral separation in MEKC coupled to mass spectrometry at low pH. Finally, in chapter 8, six amino acid derived chiral surfactants with carboxylate and sulfate head groups were compared for enantioseparation of broad range of structurally diverse racemic compounds at neutral and basic pH conditions.

Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

This thesis focuses on video watermarking robust against geometric attacks and video compressions. In addition to the requirements for an image watermarking algorithm, a digital video watermarking algorithm has to be robust against advanced video compressions, frame loss, frame swapping, aspect ratio change, frame rate change, intra- and inter-frame filtering, etc. Video compression, especially, the most efficient compression standard, H.264, and geometric attacks, such as rotation and cropping, frame aspect ratio change, and translation, are considered the most challenging attacks for video watermarking algorithms. In this thesis, we first review typical watermarking algorithms robust against geometric attacks and video compressions, and point out their advantages and disadvantages. Then, we propose our robust video watermarking algorithms against Rotation, Scaling and Translation (RST) attacks and MPEG-2 compression based on the logpolar mapping and the phase-only filtering method. Rotation or scaling transformation in the spatial domain results in vertical or horizontal shift in the log-polar mapping (LPM) of the magnitude of the Fourier spectrum of the target frame. Translation has no effect in this domain. This method is very robust to RST attacks and MPEG-2 compression. We also demonstrate that this method can be used as a RST parameters detector to work with other watermarking algorithms to improve their robustness to RST attacks. Furthermore, we propose a new video watermarking algorithm based on the 1D DFT (one-dimensional Discrete Fourier Transform) and 1D projection. This algorithm enhances the robustness to video compression and is able to resist the most advanced video compression, H.264. The 1D DFT for a video sequence along the temporal domain generates an ideal domain, in which the spatial information is still kept and the temporal information is obtained. With detailed analysis and calculation, we choose the frames with highest temporal frequencies to embed the fence-shaped watermark pattern in the Radon transform domain of the selected frames. The performance of the proposed algorithm is evaluated by video compression standards MPEG-2 and H.264; geometric attacks such as rotation, translation, and aspect-ratio changes; and other video processing. The most important advantages of this video watermarking algorithm are its simplicity, practicality and robustness.

For the polar bear (<i>Ursus maritimus</i>), a terrestrial carnivore on the highest trophic level in the Arctic marine ecosystem, periods of nutritional restriction or fasting are a characteristic feature of an annual cycle. The overall objective of my thesis was to examine some of the effects of such a 'feast-or-fast' feeding pattern on the body composition, body size and reproductive performance of this Holarctic ursid. As a reproductive strategy, pregnant polar bears occupy maternity dens for up to 6 months between late summer and spring. While in dens, maternal nutrient stores meet all maintenance energy requirements and sustain the nutritional demands of gestation and early lactation. I quantified the nutritional costs of this prolonged 'reproductive fast' in polar bears and examined the effects of variation in maternal body condition on reproductive performance. While fasting, body mass decreased by 43% and of the change in body energy content 93% was attributable to loss of fat. Bears that were fatter priorto denning produced heavier cubs, which would be more likely to survive. Much of the variation in body condition prior to denning was accounted for by age, older females being in better condition. Using an index of milk quality that was closely related to daily milk energy yield, I investigated the independent effects of maternal body condition and age on lactation. Irrespective of condition, older bears tended to produce higher quality milk. While lactation in polar bears is clearly sensitive to body condition, these results also provide strong support for an age-specific increase in reproductive effort among females. Body size is typically a strong determinant of male reproductive success in polygynous mammals such as polar bears. Consequently, theory predicts that mothers in good condition should invest more in male than female offspring in-order to produce large adult males. An underlying assumption of this theory, however, is that early differences in body size among male offspring, such as those apparent by the end of maternal care, will affect their relative adult body size. I tested the validity of this assumption in polar bears and found that, in comparison to females, variation in body size among 2-year-old males was a weak determinant of adult size. I suggest that, in comparison to females, a longer period of growth after maternal care may predispose the adult size of males to a greater degree of environmentally mediated variation. This lack of persistence in relative body size would limit the ability of mothers to affect the adult size of their male offspring, and thus reduce the effectiveness of sex-biased maternal investment as a reproductive strategy in polar bears. One of the principle physiological adaptations enabling animals to go without food for prolonged periods seems to be a heightened ability to minimize the net catabolism of body protein. I quantified changes in the body composition of free-ranging polar bears during the ice-free season. In contrast to previous studies on fasting bears, catabolism of protein appeared to meet a significant proportion of maintenance energy demands in some individuals. (Abstract shortened by UMI.)

The principle objective of this investigation was to develop an understanding of the biochemical and physiological response of free-ranging adult polar bears (<i>Ursus maritimus</i>) to prolonged fasting. A body condition index was developed from two measures, total body mass and straight-line body length, and was used as a covariate in the analyses of all other data. Protein and amino acid catabolism and urea synthesis were significantly lower in fasting bears when compared to feeding bears, and in fat bears when compared to lean bears. The inference from these results is that the energy metabolism in both states (fasting and fat) is one in which lipid is the predominant fuel for energy and nitrogen is conserved. Nutritional state (feeding versus fasting) had no significant effect on the plasma concentrations of non-esterified fatty acid, glycerol, and ketone bodies, or on the plasma ratio of acyl-carnitine to free carnitine. Furthermore, acetoacetate concentration was below the level of detection (<196 [mu]mol/L) in all bears, and â-hydroxybutyrate concentration never exceeded 291 [mu]mol/L. These results suggest polar bears are able to regulate closely the synthesis, release, and use of lipid metabolites without significant alteration in their plasma concentrations. Fasting polar bears showed no evidence of essential fatty acid (EFA) deficiency; the proportions of the diet-derived EFA linoleic (18:2[omega]6) and á-linolenic (18:3[omega]3) acids in the plasma and adipose tissue of fasting polar bears were greater than that in feeding polar bears. Plasma triiodothyronine concentrations and rectal temperatures were lower in fasting bears captured during summer-fall than in feeding bears, which suggests metabolic rates were decreased during fasting to conserve body fuels. Liver glycogen concentrations were found to be higher in fasting polar bears than in feeding bears. Furthermore, the results from intravenous administration of glucose (glucose tolerance test) to polar bears indicated the rates of insulin secretion and clearance in polar bears were slow relative to rates reported for other mammals. The inference from these results is that polar bears are not as dependent on glucose for energy as are other mammals and, as a consequence, are more lax in regulating their body glucose stores.

Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

One-dimensional and hierarchical nanostructures have acquired tremendous attention in the past decades due to their possible application. In spite of the rapid emergence of new morphologies, the underlying growth mechanism is still not well understood. The lack of effective p-type or n-type doping is another obstacle for many semiconducting nanomaterials. A deeper investigation into these structures and new methods to fabricate devices are of significant impact for nanoscience and nanotechnology. Motivated by a desire to understand the growth mechanism of nanostructures and investigate novel device fabrication method, the research described in this thesis carried out on the synthesis, characterization, and device fabrication of semiconducting nanostructures. The main focus of the research was on ZnO, SnO2, and Zn3P2 for their great capability for fundamental phenomena studying, promising applications in sensors and optoelectronics, and the potential generalization of results to other materials. Within this study the following goals have been achieved: 1) Improved understanding of polar-surface-induced growth mechanism in wurtzite-structured ZnO and generalization of this growth mechanism with the discovery and analysis of rutile ¨Cstructured SnO2, 2) observation of the significance of the transversal growth, which is usually ignored, in interpenetrative ZnO nanowires, 3) rational design and growth control over versatile nanostructures of ZnO and Zn3P2, and 4) conjunction of p-type Zn3P2 and n-type ZnO semiconducting nanostructures for device fabrications. The framework for the research is reviewed first in chapter 1. Chapter 2 gives the detailed experimental setup, synthesis procedure, and common growth mechanism for nanostructure growth. A detailed discussion on the growth of ZnO nanostructures in chapter 3 provides more insight into the polar-surface-induced growth, transversal growth, vapor-solid growth, and vapor-liquid-solid growth during the formation of nanostructures. Polar-surface-induced growth is also confirmed in the growth of SnO2 nanostructures, which is also included in chapter 2. Chapter 3 presents Zn3P2 nanostructures from the newly designed experiment setup and the device fabrication from ZnO and Zn3P2 crossed nanowires.

In this study, we want to realize the influence of temperature and mechanical rubbing on the surface free energy and wettability of liquid crystal(LC) of polyimide(PI) thin films. In different surface conditions, we use the LC that was dropped on to the surface of the sample and become stable to explore the wettability of the surface. We also observe the phenomenon and influence of the LC on the PI with increasing surface temperature. We utilize hot stage and contact angle measuring system to obtain the surface free energy to realize the surface of the PI and measure the contact angle of LC in different temperature to realize the wettability of the PI. We found that the increase of the surface temperature leads to the decrease in the surface free energy of the PI and the contact angle of the FLC on the PI. The increase of the surface temperature causes the stabilization in the surface polar energy and the LC contact angle of the unrubbed PI. But the increase of the surface temperature causes the increase in the surface polar energy and the decrease of the LC contact angle of the rubbed PI. In the anti-parallel-direction to the rubbing direction the rubbed PI exhibits better wettability.

M-plane (101 ¡Â0) ZnO thin films were grown on m-plane sapphire (101 ¡Â0) substrates by RF magnetron sputtering. We varied the RF power, working pressure, and O2/Ar ratio to obtain the best growth conditions. Structural properties were investigated by X-ray diffraction(XRD). XRD measurements showed that the crystal orientation of ZnO films was non-polar m-plane (101 ¡Â0). In addition, photoluminescence (PL) spectrum showed the bandgap energy of ZnO films was about 3.24 eV. PL spectrum showed zinc vacancy signal for films grown in oxygen rich condition. Carrier concentration was measured by hall measurement as well as FTIR spectrometry. The results showed the carrier concentration calculated by optical measurements was higher than hall measurements. One possibility for this could be the band tail at the bottom of conduction band. This band tail can make the effective mass larger and thus influencing the optical carrier concentration.

Mechanical Rubbing still is an useful alignment method in this time. In this study, we investigated the surface wettability of rubbed polyimide(PI) thin film. By using contact angle measurements, we found the surface free energy have strong connection with surface roughness in different rubbing times. We also discussed the wettability of rubbed PI thin film in parallel and anti-parallel of rubbing direction. We found that if we rubbed PI thin film 3 times in 0.3mm depth then the structure of SSFLC is more uniform than the alignment effect of other rubbing times and we found that the values of polar energy in parallel and anti-parallel of rubbing direction are very close. In the other part of study, we degenerated the polyimide before coating. We found that the reflection anisotropic spectrum(RAS) have a blueshift and the rubbing strength will be more influential in the wettability of PI thin film than the film with no degenerate process.