Catalyst and substrate effects in enantioselective C–H insertion reactions of α-diazosulfones

This thesis describes a systematic investigation of the mechanistic and synthetic aspects of intramolecular reactions of a series of α-diazo-β-oxo sulfone derivatives using copper and, to a lesser extent, rhodium catalysts. The key reaction pathways explored were C–H insertion and cyclopropanation, with hydride transfer competing in certain instances. Significantly, up to 98% ee has been achieved in the C–H insertion processes using copper-NaBARF-bisoxazoline catalysts, with the presence of the additive NaBARF critical to the efficiency of the transformations. This novel synthetic methodology provides access to a diverse range of enantioenriched heterocyclic compounds including thiopyrans, sulfolanes, β- and γ-lactams, in addition to carbocycles such as fused cyclopropanes. The synthesis of the α-diazosulfones required for subsequent investigations is initially described. Of the twenty seven diazo sulfones described, nineteen are novel and are fully characterised in this work. The discussion is subsequently focused on a study of the copper and rhodium catalysed reactions of the α-diazosulfones with Chapter Four concentrated on highly enantioselective C–H insertion to form thiopyrans and sufolanes, Chapter Five focused on C–H insertion to form fused sulfolanes, Chapter Six focused on C–H insertion in sulfonyl α-diazoamides where both lactam formation and / or thiopyran / sulfolane formation can result from competing C–H insertion pathways, while Chapter Seven focuses on cyclopropanation to yield fused cyclopropane derviatives. One of the key outcomes of this work is an insight into the steric and / or electronic factors on both the substrate and the catalyst which control regio-, diastereo- and enantioselectivity patterns in these synthetically powerful transformations. Full experimental details for the synthesis and spectral characterisation of the compounds are included at the end of each Chapter, with details of chiral stationary phase HPLC analysis and assignment of absolute stereochemistry included in the appendix.

Effects of photodynamic therapy with topical and systemic aminolevulinic acid on ultraviolet induced tumors in hairless mice

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Effects of emotional salience and semantic domain on cross-form priming

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

The effects of crystallization on the pulsations of white dwarf stars

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

The effects of stenting and endothelial denudation on experimental aneurysm healing and gene expression following endovascular treatment

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Effects of concealed conduction on AV nodal function

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Effects of Prenatal and Early Postnatal Exposure to Aversive Stimuli on Fearfulness and Exploratory Behavior in Bobwhite Qauil Neonates (Colinus virginianus)

Neophobia, the fear of novelty, is a behavioral trait found across a number of animal species, including humans. Neophobic individuals perceive novel environments and stimuli to have aversive properties, and exhibit fearful behaviors when presented with non-familiar situations. The present study examined how early life exposure to aversive novel stimuli could reduce neophobia in bobwhite quail chicks. Experiment 1 exposed chicks to a novel auditory tone previously shown to be aversive to naïve chicks (Suarez, 2012) for 24 hours immediately after hatching, then subsequently tested them in the presence of the tone within a novel maze task. Postnatally exposed chicks demonstrated decreased fearfulness compared to naïve chicks, and behaved more similarly to chicks tested in the presence of a known attractive auditory stimulus (a bobwhite maternal assembly call vocalization). Experiment 2 exposed chicks to the novel auditory tone for 24 hours prenatally, then subsequently tested them within a novel maze task. Prenatally exposed chicks showed decreased fearfulness to a similar degree as those postnatally exposed, revealing that both prenatal and postnatal exposure methods are capable of decreasing fear of auditory stimuli. Experiment 3 exposed chicks to a novel visual stimulus for 24 hours postnatally, then subsequently tested them within a novel emergence box / T-maze apparatus. Chicks exposed to the visual stimulus showed decreased fearfulness compared to naïve chicks, thereby demonstrating the utility of this method across sense modalities. Experiment 4 assessed whether early postnatal exposure to one novel stimulus could generalize and serve to decrease fear of novelty when chicks were tested in the presence of markedly different stimuli. By combining the methods of Experiments 1 and 3, this experiment revealed that chicks exposed to one type of stimulus (auditory or visual) demonstrated decreased fear when subsequently tested in the presence of the opposite type of novel stimulus. These results suggest that experience with novel stimuli can moderate the extent to which neophobia will develop during early development.

Non-Consumptive Effects of Predators in Coral Reef Communities and the Indirect Consequences of Marine Protected Areas

Predators exert strong direct and indirect effects on ecological communities by intimidating their prey. Non-consumptive effects (NCEs) of predators are important features of many ecosystems and have changed the way we understand predator-prey interactions, but are not well understood in some systems. For my dissertation research I combined a variety of approaches to examine the effect of predation risk on herbivore foraging and reproductive behaviors in a coral reef ecosystem. In the first part of my dissertation, I investigated how diet and territoriality of herbivorous fish varied across multiple reefs with different levels of predator biomass in the Florida Keys National Marine Sanctuary. I show that both predator and damselfish abundance impacted diet diversity within populations for two herbivores in different ways. Additionally, reef protection and the associated recovery of large predators appeared to shape the trade-off reef herbivores made between territory size and quality. In the second part of my dissertation, I investigated context-dependent causal linkages between predation risk, herbivore foraging behavior and resource consumption in multiple field experiments. I found that reef complexity, predator hunting mode, light availability and prey hunger influenced prey perception of threat and their willingness to feed. This research argues for more emphasis on the role of predation risk in affecting individual herbivore foraging behavior in order to understand the implications of human-mediated predator removal and recovery in coral reef ecosystems.

Effects of Altered Prenatal Sensory Stimulation on Postnatal Contingency Learning in Bobwhite Quail Neonates (Colinus Virginianus)

Preterm infants are exposed to high levels of modified early sensory experience in the Neonatal Intensive Care Unit (NICU). Reports that preterm infants show deficits in contingency detection and learning when compared to full-term infants (Gekoski, Fagen, & Pearlman, 1984; Haley, Weinberg, & Grunau, 2006) suggest that their exposure to atypical amounts or types of sensory stimulation might contribute to deficits in these critical skills. Experimental modifications of sensory experience are severely limited with human fetuses and preterm infants, and previous studies with precocial bird embryos that develop in ovo have proven useful to assess the effects of modified perinatal sensory experience on subsequent perceptual and cognitive development. In the current study, I assessed whether increasing amounts of prenatal auditory or visual stimulation can interfere with quail neonates’ contingency detection and contingency learning in the days following hatching. Results revealed that augmented prenatal visual stimulation prior to hatching does not disrupt the ability of bobwhite chicks to recognize and prefer information learned in a contingent fashion, whereas augmented prenatal auditory stimulation disrupted the ability of chicks to benefit from contingently presented information. These results suggest that specific types of augmented prenatal stimulation that embryos receive during late prenatal period can impair the ability to learn and remember contingently presented information. These results provide testable developmental hypotheses, with the goal of improving the developmental care and management of preterm neonates in the NICU setting.

The Validity of Broad and Narrow Personality Traits For Predicting Job Performance: The Differential Effects of Time

Research into the dynamicity of job performance criteria has found evidence suggesting the presence of rank-order changes to job performance scores across time as well as intraindividual trajectories in job performance scores across time. These findings have influenced a large body of research into (a) the dynamicity of validities of individual differences predictors of job performance and (b) the relationship between individual differences predictors of job performance and intraindividual trajectories of job performance. In the present dissertation, I addressed these issues within the context of the Five Factor Model of personality. The Five Factor Model is arranged hierarchically, with five broad higher-order factors subsuming a number of more narrowly tailored personality facets. Research has debated the relative merits of broad versus narrow traits for predicting job performance, but the entire body of research has addressed the issue from a static perspective -- by examining the relative magnitude of validities of global factors versus their facets. While research along these lines has been enlightening, theoretical perspectives suggest that the validities of global factors versus their facets may differ in their stability across time. Thus, research is needed to not only compare the relative magnitude of validities of global factors versus their facets at a single point in time, but also to compare the relative stability of validities of global factors versus their facets across time. Also necessary to advance cumulative knowledge concerning intraindividual performance trajectories is research into broad vs. narrow traits for predicting such trajectories. In the present dissertation, I addressed these issues using a four-year longitudinal design. The results indicated that the validities of global conscientiousness were stable across time, while the validities of conscientiousness facets were more likely to fluctuate. However, the validities of emotional stability and extraversion facets were no more likely to fluctuate across time than those of the factors. Finally, while some personality factors and facets predicted performance intercepts (i.e., performance at the first measurement occasion), my results failed to indicate a significant effect of any personality variable on performance growth. Implications for research and practice are discussed.

The Effects of Paternal and Maternal Nurturance and Involvement on Young Adult Academic Outcomes

The present study examines how mothering and fathering impact child academic outcomes in divorced and intact families, and if there are unique influences of mothering and fathering variables for sons and daughters. An ethnically diverse sample of 1,714 university students from Florida International University (n=1371) and Florida State University (n=343) responded to measures on a questionnaire that included the Nurturant Fathering and Mothering Scales (Finley & Schwartz, 2004; Schwartz & Finley, 2005; Finley & Schwartz, 2006), the Mother and Father Involvement Scales (Finley, Mira, & Schwartz, 2008), demographic measures, and academic outcome measures. In intact families, mothering and fathering variables were significantly correlated with each other, and positively correlated with child academic outcomes including grades, GPA, academic satisfaction, and academic importance. In divorced families, mothering and fathering variables were not correlated with each other. Furthermore, when analyzing divorced families, significant effects were found for both parent and child gender. Mothering variables were found to have the greatest positive impact for sons’ academic outcomes. Maternal nurturance and maternal involvement were correlated positively with academic outcomes for sons from divorced families and accounted for 3-4% of the unique variance explained. Consistently, desired mother involvement, how much involvement the child wished they had received, was negatively correlated with academic outcomes for sons from divorced families and accounted for 10-15% of the unique variance explained. This means that when the amount of maternal involvement that sons in divorced families received matched or exceeded their desired level of involvement, sons had more positive academic outcomes including grades, GPA, satisfaction with academics and academic importance. This suggests that in intact family forms, nurturant and involved mothering and fathering have a positive effect on academic outcomes for sons and daughters. In divorced family forms, the effects of fathering on child academic outcomes were not significant. Therefore, in divorced families, the positive effects fathering on academic outcomes of sons and daughters drop out, and mothers are uniquely important for sons’ academic success.

The Effects of Advanced Practice Nurses (APNs) as Intensivists in a Surgical Intensive Care Unit (SICU) on Patient Outcomes, Healthcare Charges, and APN Intensivist Services in the SICU

Intensive Care Units (ICUs) account for over 10 percent of all US hospital beds, have over 4.4 million patient admissions yearly, approximately 360,000 deaths, and account for close to 30% of acute care hospital costs. The need for critical care services has increased due to an aging population and medical advances that extend life. The result is efforts to improve patient outcomes, optimize financial performance, and implement models of ICU care that enhance quality of care and reduce health care costs. This retrospective chart review study examined the dose effect of APN Intensivists in a surgical intensive care unit (SICU) on differences in patient outcomes, healthcare charges, SICU length of stay, charges for APN intensivist services, and frequency of APNs special initiatives when the SICU was staffed by differing levels of APN Intensivist staffing over four time periods (T1-T4) between 2009 and 2011. The sample consisted of 816 randomly selected (204 per T1-T4) patient chart data. Study findings indicated reported ventilator associated pneumonia (VAP) rates, ventilator days, catheter days and catheter associated urinary tract infection (CAUTI) rates increased at T4 (when there was the lowest number of APN Intensivists), and there was increased pressure ulcer incidence in first two quarters of T4. There was no statistically significant difference in post-surgical glycemic control (M = 142.84, SD= 40.00), t (223) = 1.40, p = .17, and no statistically significant difference in the SICU length of stay among the time-periods (M= 3.27, SD = 3.32), t (202) = 1.02, p= .31. Charges for APN services increased over the 4 time periods from $11,268 at T1 to $51,727 at T4 when a system to capture APN billing was put into place. The number of new APN initiatives declined in T4 as the number of APN Intensivists declined. Study results suggest a dose effect of APN Intensivists on important patient health outcomes and on the number of APNs initiatives to prevent health complications in the SICU.

Cognitive behavior therapy for anxiety disorders in youth: Treatment specificity and mediation effects

The present study investigated the efficacies of Individual CBT (ICBT), Parent Relationship Skill Training (RLST, which targets increasing parental acceptance of youth and increasing autonomy granting) and Parent Reinforcement Skills Training (RLST, which targets increasing parental positive reinforcement and decreasing negative reinforcement). The specific aims were to examine treatment specificity and mediation effects of parenting variables. ICBT was used as a baseline comparison condition. The sample consisted of 253 youth (ages 5-16 years; M = 9.38; SD = 2.42) and their parents. To examine treatment outcome and specificity, the data were analyzed using analysis of variance within a structural equation modeling framework. Mediation was analyzed via structural equation modeling using MPlus. Results indicated that ICBT, RLST, and RFST produced positive treatment outcomes across all indices of change (i.e., clinically significant improvement, anxiety symptom reduction) and across all informants (i.e., youths and parents). RLST was associated with incremental reduction in youth anxiety symptoms beyond ICBT, as per youth report. Treatment specificity effects were found for participants in RFST in terms of parental reinforcement, as per parent report only. Treatment mediation was not found for any of the hypothesized parenting variables (i.e., parental acceptance, parental autonomy granting, parental reinforcement). The results support the use of CBT involving only the youth and the parent and youth together for treating youth anxiety. The findings’ implications are further discussed in terms of the need to conduct further meditational treatment outcome designs in order to continue to advance theory and research in youth anxiety treatment.

The Effects on Students' Self-Efficacy Beliefs Regarding Their Comprehension of American Literature When Aesthetic Reading and Reader Response Strategy are Implemented

High-stakes testing and accountability have infiltrated the education system in the United States; the top priority for all teachers must be student progress on standardized tests. This has resulted in the predominance of reading for test-taking, (efferent reading), in the English, language arts, and reading classrooms. Authentic uses of print activities, like aesthetic reading, that encourage students to engage individually with a text, have been pushed aside. During a 3-week time period, regular level, English 3/American literature students in a Title I magnet high school, participated in this quasi-experimental study (N = 62). It measured the effects of an intervention of reading American literature texts aesthetically and writing aesthetically-evoked reader responses on students’ self-efficacy beliefs regarding their comprehension of American literature. One trained teacher and the researcher participated in the study: student participants were pre- and post- tested using the Confidence in Reading American Literature Survey which examined their self-efficacy beliefs regarding their comprehension of American literature. Several statistical analyses were performed. The results of the linear regression analyses partially supported a positive relationship between aesthetically-evoked reader responses and students’ self-efficacy beliefs regarding their comprehension of American literature. Additionally, the results of the 2 (sex) x 2 (treatment) ANCOVAs conducted to test group differences in self-efficacy beliefs regarding the comprehension of American literature between treatment and control groups indicated a main effect for treatment (but not sex; nor was there a significant sex x treatment interaction), suggesting the treatment was partially effective in increasing students’ self-efficacy beliefs. Seven of the twelve ANCOVAs indicated a statistically significant increase in the treatment group’s adjusted group mean self-efficacy belief scores as a result of being exposed to the intervention. In six of these seven analyses, increases in self-efficacy beliefs occurred in tasks that required three or more higher-order levels of thinking/learning. The results are discussed in terms of theoretical, empirical and practical significance. Future research is recommended to extend the intervention beyond the narrow confines of a Title I magnet school to settings where the intervention could be tested longitudinally, e. g., honors and gifted students, elementary and middle schools.

Two-Path All-pass Based Half-Band Infinite Impulse Response Decimation Filters and the Effects of Their Non-Linear Phase Response on ECG Signal Acquisition

This paper is based on the novel use of a very high fidelity decimation filter chain for Electrocardiogram (ECG) signal acquisition and data conversion. The multiplier-free and multi-stage structure of the proposed filters lower the power dissipation while minimizing the circuit area which are crucial design constraints to the wireless noninvasive wearable health monitoring products due to the scarce operational resources in their electronic implementation. The decimation ratio of the presented filter is 128, working in tandem with a 1-bit 3rd order Sigma Delta (ΣΔ) modulator which achieves 0.04 dB passband ripples and -74 dB stopband attenuation. The work reported here investigates the non-linear phase effects of the proposed decimation filters on the ECG signal by carrying out a comparative study after phase correction. It concludes that the enhanced phase linearity is not crucial for ECG acquisition and data conversion applications since the signal distortion of the acquired signal, due to phase non-linearity, is insignificant for both original and phase compensated filters. To the best of the authors’ knowledge, being free of signal distortion is essential as this might lead to misdiagnosis as stated in the state of the art. This article demonstrates that with their minimal power consumption and minimal signal distortion features, the proposed decimation filters can effectively be employed in biosignal data processing units.