Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

Developmental Activities That Lead to Dropout and Investment in Sport

Background: Studies suggest that expert performance in sport is the result of long-term engagement in a highly specialized form of training termed deliberate practice. The relationship between accumulated deliberate practice and performance predicts that those who begin deliberate practice at a young age accumulate more practice hours over time and would, therefore, have a significant performance advantage. However, qualitative studies have shown that a large amount of sport-specific practice at a young age may lead to negative consequences, such as dropout, and is not necessarily the only path to expert performance in sport. Studies have yet to investigate the activity context, such as the amount of early sport participation, deliberate play and deliberate practice within which dropout occurs. Purpose: To determine whether the nature and amount of childhood-organized sport, deliberate play and deliberate practice participation influence athletes' subsequent decisions to drop out or invest in organized sport. It was hypothesized that young athletes who drop out will have sampled fewer sports, spent less time in deliberate play activities and spent more time in deliberate practice activities during childhood sport involvement. Participants: The parents of eight current, high-level, male, minor ice hockey players formed an active group. The parents of four high-level, male, minor ice hockey players who had recently withdrawn from competitive hockey formed a dropout group. Data collection: Parents completed a structured retrospective survey designed to assess their sons' involvement in organized sport, deliberate play and deliberate practice activities from ages 6 to 13. Data analysis: A complete data-set was available for ages 6 through 13, resulting in a longitudinal data-set spanning eight years. This eight-year range was divided into three levels of development corresponding to the players' progress through the youth ice hockey system. Level one encompassed ages 6–9, level two included ages 10–11 and level three covered ages 12–13. Descriptive statistics were used to report the ages at which the active and dropout players first engaged in select hockey activities. ANOVA with repeated measures across the three levels of development was used to compare the number of sports the active and dropout players were involved in outside of hockey, the number of hours spent in these sports, and involvement in various hockey-related activities. Findings: Results indicated that both the active and dropout players enjoyed a diverse and playful introduction to sport. Furthermore, the active and dropout players invested similar amounts of time in organized hockey games, organized hockey practices, specialized hockey training activities (e.g. hockey camps) and hockey play. However, analysis revealed that the dropout players began off-ice training at a younger age and invested significantly more hours/year in off-ice training at ages 12–13, indicating that engaging in off-ice training activities at a younger age may have negative implications for long-term ice hockey participation. Conclusion: These results are consistent with previous research that has found that early diversification does not hinder sport-specific skill development and it may, in fact, be preferable to early specialization. The active and dropout players differed in one important aspect of deliberate practice: off-ice training activities. The dropout players began off-ice training at a younger age, and participated in more off-ice training at ages 12 and 13 than their active counterparts. This indicates a form of early specialization and supports the postulate that early involvement in practice activities that are not enjoyable may ultimately undermine the intrinsic motivation to continue in sport. Youth sport programs should not focus on developing athletic fitness through intense and routine training, but rather on sport-specific practice, games and play activities that foster fun and enjoyment.

The adaptive response of humans to exercise: Impact of exercise intensity, fibre-type specific responses and molecular patterns of response

In an attempt to improve the current understanding of the adaptive response to exercise in humans, this dissertation performed a series of studies designed to examine the impact of training intensity and mode on aerobic capacity and performance, fibre-type specific adaptations to training, and individual patterns of response across molecular, morphological and genetic factors. Project #1 determined that training intensity, session dose, baseline VO2max and total training volume do not influence the magnitude of change in VO2max by performing a meta-regression, and meta-analysis of 28 different studies. The intensity of training had no effect on the magnitude of increase in maximal oxygen uptake in young healthy participants, but similar adaptations were achieved with lower training doses following high intensity training. Project # 2 determined the acute molecular response, and training-induced adaptations in aerobic performance, aerobic capacity and muscle phenotype following high-intensity interval training (HIT) or endurance exercise (END). The acute molecular response (fibre recruitment and signal activation) and training-induced adaptations in aerobic capacity, aerobic performance, and muscle phenotype were similar following HIT and END. Project # 3 examined the impact of baseline muscle morphology and molecular characteristics on the training response, and if muscle adaptations are coordinated. The muscle phenotype of individuals who experience the largest improvements (high responders) were lower before training for some muscle characteristics and molecular adaptations were coordinated within individual participants. Project # 4 examined the impact of 2 different intensities of HIT on the expression of nuclear and mitochondrial encoded genes targeted by PGC-1α. A systematic upregulation of nuclear and mitochondrial encoded genes was not present in the early recovery period following acute HIT, but the expression of mitochondrial genes were coordinated at an individual level. Collectively, results from the current dissertation contribute to our understanding of the molecular mechanisms influencing skeletal muscle and whole-body adaptive responses to acute exercise and training in humans.