Synthetic routes to Bis-Calix [n]areness : a thesis presented in partial fulfilment of the requirements for the degree of Masterate of Science in Chemistry at Massey University

The literature procedures for the targeted syntheses of p-tert-butylcalix[4]arene, p-tert-butylcalix[5]arene, p-tert-butylcalix[6]arene, p-tert-butylcalix[7]arene, and p-tert-butylcalix[8]arene have been repeated successfully. In the case of p-tert-butylcalix[4]arene, alterations led to a less capricious procedure, synthesis of the pure product directly and in higher yield. The residual xylene and toluene solutions from the targeted p-tert-butylcalix[8]arene preparation were utilised to obtain workable quantities of the rare calix[5]- and calix[7]arenes, a protocol that is far simpler and less time-consuming than the low-yielding targeted synthesis of these compounds. Dealkylation of p-tert-butylcalix[n]arenes is best accomplished at 30°C in 0.16-0.05 molL−¹ toluene solution. The insolubility of calix[8]arene in all common organic solvents is expected to limit its synthetic use. Two new protocols have been devised for the highly selective mono-O-alkylation of calixarenes 4 through 8. This work represents the realisation of the first selective functionalisation methods that are applicable to the calixarene family, and also the first selective functionalisation of a calix[7]arene. These findings will lead to more efficient synthesis of multiple calixarenes (cf. Chapter 3) and may allow for a better understanding of the reasons for selectivity in calixarene-O-alkylations. We have been able to synthesise a variety of bis-calixarenes by two different routes. Glaser-Hay coupling allowed the synthesis of symmetrical diyne bridged bis-calix[4, 6 and 8]arenes in high yield. Extension of the first general mono-O-alkylation procedure for calixarenes has made it possible to synthesise hom o-bis-calixarenes in good yield in one step from the parent calixarenes. The unexpected formation of monobromoxylyl calixarenes allows the prospect of the synthesis of hetero-bis-calixarenes under more forcing conditions. Most importantly this allows us to further explore the chemistry of bis-calixarenes by making them readily available (in large quantities) for more elaborate syntheses

CubeSat Constellation for Interplanetary Market Intelligence and Private Claims in Space

Mission Objectives Deployment of Beacons, each rendezvous with NEAs\u27 Small-Body Orbit Data Collection comprising a universal cadastre Sensors/Instrumentation: Geolocations and In-Space Activity Capture Integration with Service Providers through API Cooperation with Domestic and International Regulatory Agencie

The Zumbrota

My thesis is a creative project that consists of a craft introduction and Act I of my novel, The Zumbrota. In part one, the craft introduction, I look at the history of the serial detective in crime fiction and examine how serial detectives fit into the discussion of round and flat characters as defined by E.M. Forster and James Wood. Through the discussion of serial detectives as round and flat characters, I ultimately examine the fundamental differences between literary and genre fiction. Then in part two, readers go back to 1940 as my detective, Wes Grizzly, uncovers a conspiracy between mobsters and Nazis to undermine America’s recovering economy. The Zumbrota is my love letter to the detective genre, a grand tradition that goes back almost two centuries

Kinetics determination of soybean oil transesterification in the design of a continuous biodiesel production process

One-step batch transesterification consisting of three stepwise reversible reactions of pure soybean oil with methanol was conducted at two different mixing speeds (600 and 300 rpm) to produce soybean oil fatty acid methyl esters (biodiesel). In both batch reactions, sodium methoxide (1.09 wt% based on soybean oil) was used as the catalyst, the reaction temperature was 60oC, and the methanol-to-oil molar ratio was 6:1. The objectives were to determine and/or investigate: 1) the mechanism and order of the reaction, 2) the reaction rate constants, 3) the effect of changes in mixing intensity on the reaction rate, 4) the comparison of the reaction mechanism and kinetic rate constants calculated with established literature references (for validation), and 5) how to interpret and utilize the kinetics analysis in the design of a continuous pilot-scale biodiesel production process. The kinetics analysis from the experiment showed that a second-order kinetic mechanism provided a good fit for the reaction. Kinetic rate constants at both mixing speeds were calculated and ranged from -3.10 x 10-3 - 0.028 (wt% min)-1 for the triglyceride, monoglyceride, and diglyceride forward reactions. The rate constants were slightly higher at the 600 rpm mixing speed. Higher mixing intensity also resulted in an increased purity of methyl esters (95.2 wt %). At both mixing speeds, monoglycerides showed the smallest percent elimination of all reaction intermediates at approximately 30%. The rate constants calculated for monoglycerides were the lowest as well. The monoglyceride rate constant of 0.0149 (wt% min)-1 was used in the design of a continuous process in a 100 gallon vessel, which is a scale of operation that could be easily adopted by a cooperative of oil seed producers or geographically isolated plant-oil producing villages. This Honors thesis was a component of a Biological and Agricultural Engineering team Senior Design project which consisted of designing a continuous biodiesel process from production to purification

Sleep disturbance at pre-deployment is a significant predictor of post-deployment re-experiencing symptoms.

Background: Insomnia is common in service members and associated with many mental and physical health problems. Recently, longitudinal data have been used to assess the impact of disturbed sleep on mental health outcomes. These studies have consistently shown relationships between sleep disturbance and development of mental illness. Objective: The present study examined the longitudinal relationship between sleep disturbance and PTSD symptomatology in a cohort of Marines and Navy Corpsmen deployed to Iraq and Afghanistan (n = 2,404) assessed prior to deployment, as well as at -3 and 6 months post-deployment. Additionally, we aimed to investigate the extent to which these relationships are moderated by combat-stress severity, and to what extent these findings are replicated in a second, separate cohort of Marines and Navy corpsmen (n = 938) assessed with identical measures prior to deployment and within 3 months of return. Method: The present study employed latent variable path models to examine the relationships between pre-deployment sleep disturbance and post-deployment re-experiencing symptoms. Initial cross-lagged path models were conducted on discovery and replication samples to validate the hypothesized predictive relationships. Follow up moderation path models were then conducted to include the effect of combat-stress severity on these relationships. Results: Initial cross-lagged models supported a significant relationship between pre-deployment sleep disturbance and future re-experiencing PTSD symptoms at all time points. Initial moderation models showed a small moderator effect of combat-stress severity, though the main predictive relationship between pre-deployment sleep disturbance and PTSD symptoms remained significant. The moderator effect was not significant in the replication sample. Conclusions: The results of this study support pre-deployment sleep disturbance as a risk factor for development of post-deployment PTSD symptoms. Interventions aimed at normalizing sleep may be important in preventive measures for PTSD

Exploring the feasibility and effectiveness of a childcare physical activity (Play) policy: Rationale and protocol for a pilot, cluster-randomized controlled trial

Background: Young children are prone to low levels of physical activity in childcare. This environment, inclusive of equipment, policies, and staff, has been identified as influencing young children’s activity behaviours. To date, no study has examined the feasibility and effectiveness of such policies in Canadian childcare centres, while the provision of physical activity policies in other countries has shown some promise for improving the activity levels of young children. As such, the primary objective of the Childcare PhysicaL ActivitY (PLAY) Policy study is to examine the feasibility of an evidence-based, stakeholder-informed, written physical activity and sedentary time policy for centre-based childcare (i.e., at the institutional level). The secondary objectives are to examine the impact of policy implementation on the physical activity levels and sedentary time of young children, subsequent environmental changes in childcare centres, and childcare providers’ self-efficacy to implement a physical activity policy. This study will examine both policy implementation and individual (behavioural) outcomes. Methods/Design: The Childcare PLAY Policy study, a pilot, cluster-randomized controlled trial, involves the random allocation of childcare centres to either the experimental (n = 4) or control (n = 4) group. Childcare centres in the experimental group will adopt a written physical activity policy for eight weeks (at which time they will be asked to stop enforcing the policy). Physical activity levels and sedentary time in childcare will be assessed via ActiGraph™ accelerometers with measurements at baseline (i.e., week 0), mid-intervention (i.e., week 4), immediately post-intervention (i.e., week 9), and at six-month follow-up. Policy implementation and feasibility will be assessed using surveys and interviews with childcare staff. The Environment and Policy Assessment and Observation Self-Report tool will capture potential changes to the childcare setting. Finally, childcare providers’ self-efficacy will be captured via a study-specific questionnaire. A nested evaluation of the impact of policy implementation on young children’s physical activity levels will be completed. A linear mixed effects models will be used to assess intervention effects on the primary and secondary outcomes. Descriptive statistics and thematic analysis will be employed to assess the feasibility of policy implementation. Discussion: The Childcare PLAY Policy study aims to address the low levels of physical activity and high sedentary time observed in childcare centres by providing direction to childcare staff via a written set of evidence-informed standards to encourage young children’s activity and reduce sedentary time. The findings of this work will highlight specific aspects of the policy that worked and will inform modifications that may be needed to enhance scalability. Policy-based approaches to increasing physical activity affordances in childcare may inform future regulations and programming within this environment

Implementation Adherence and Perspectives of the Childcare PhysicaL ActivitY (PLAY) Policy: A Process Evaluation

The Childcare PhysicaL ActivitY (PLAY) policy was an evidence-informed, eight-item institutional-level policy document targeting children’s physical activity, outdoor play, and sedentary time. Nine childcare centers in London, Ontario, participated in this cluster, randomized controlled trial. Early Childhood Educators allocated to the experimental group, from five childcare centers in London, Ontario, implemented the policy for young children (18 months to 4 years) for 8 weeks and documented adherence to each policy item (i.e., dose) in daily logs. Program evaluation surveys (n = 21) and interviews (n = 10) were completed postintervention to assess Early Childhood Educators’ perspectives of feasibility, context, enjoyment, communication between researchers and childcare staff, and likelihood of future implementation. Descriptive statistics were calculated, and thematic analysis was conducted. Adherence to policy items ranged from 16.5% (for delivery of shorter, more frequent outdoor periods) to 85.9% (for delivery of unstructured/child-directed play). Participants reported effective communication between the research team and childcare centers (0 = not at all effective to 5 = very effective; M = 4.20; SD = 0.83) but noted that they were unlikely to continue the implementation of more frequent outdoor periods (0 = not at all likely to 5 = extremely likely; M = 2.19; SD = 1.21). Interview themes included weather as a prominent barrier and the use of verbal prompts as a solution for implementing the policy. As this was a small and short-term intervention, this pilot study offers important insight on larger scale policy interventions aimed at increasing physical activity and minimizing sedentary time among children enrolled in childcare

Impact of the childcare physical activity (Play) policy on young children’s physical activity and sedentary time: A pilot clustered randomized controlled trial

Background: The importance of daily physical activity is crucial for healthy development during the early years. Currently, a formal written physical activity policy is lacking in Canadian childcare centers, but holds promise for offering consistent physical activity opportunities. With eight recom-mendations, the Childcare PLAY policy is an evidence-informed, institutional-level document, target-ing children’s physical activity, outdoor play, and sedentary time. The purpose of this study was to examine the impact of the Childcare Physical Activity (PLAY) policy on the physical activity and sedentary time of young children (18 months–4 years) in childcare. Methods: Nine childcare centers in London, Ontario participated in the cluster, randomized controlled trial. The centers in the control condition (n = 4) continued their typical daily routines, while the centers in the intervention condition (n = 5) implemented the PLAY policy for eight weeks. To assess physical activity levels, toddlers and preschoolers wore ActiGraph wGT3X-BT accelerometers for five consecutive days during childcare hours, at baseline, mid-and post-intervention, and at the six-month follow-up. Raw accelerometry data were converted to 15 s epochs, and age-and device-specific cut-points were applied. The participants with two or more days of at least 5 h/day of wear-time at baseline, and at one additional time point, were included in the linear mixed-effects models. An adjusted alpha (p \u3c 0.017) was used to account for multiple comparison bias. Results: A total of 148 children (31.92 ± 7.41 months) had valid accelerometry data. The intervention resulted in a significant increase in light physical activity among the participants in the experimental group at the six-month follow-up (+1.07 min/h, an 11.16% increase; p = 0.0017). The intervention did not have a statistically significant effect on the total physical activity, moderate-to-vigorous physical activity, or sedentary time. Conclusions: The findings indicate that the Childcare PLAY policy was effective at increasing the toddlers’ and preschoolers’ light physical activ-ity. This pilot intervention appears promising for supporting some improved movement behaviors among children in childcare settings; however, additional investigations are needed to explore the feasibility and effectiveness with larger and more-diverse samples

Data-driven neuropathological staging and subtyping of TDP-43 proteinopathies

TAR DNA-binding protein-43 (TDP-43) accumulation is the primary pathology underlying several neurodegenerative diseases. Charting the progression and heterogeneity of TDP-43 accumulation is necessary to better characterize TDP-43 proteinopathies, but current TDP-43 staging systems are heuristic and assume each syndrome is homogeneous. Here, we use data-driven disease progression modelling to derive a fine-grained empirical staging system for the classification and differentiation of frontotemporal lobar degeneration due to TDP-43 (FTLD-TDP, n = 126), amyotrophic lateral sclerosis (ALS, n = 141) and limbic-predominant age-related TDP-43 encephalopathy neuropathologic change (LATE-NC) with and without Alzheimer’s disease (n = 304). The data-driven staging of ALS and FTLD-TDP complement and extend previously described human-defined staging schema for ALS and behavioural variant frontotemporal dementia. In LATE-NC individuals, progression along data-driven stages was positively associated with age, but negatively associated with age in individuals with FTLD-TDP. Using only regional TDP-43 severity, our data driven model distinguished individuals diagnosed with ALS, FTLD-TDP or LATE-NC with a cross-validated accuracy of 85.9%, with misclassifications associated with mixed pathological diagnosis, age and genetic mutations. Adding age and SuStaIn stage to this model increased accuracy to 92.3%. Our model differentiates LATE-NC from FTLD-TDP, though some overlap was observed between late-stage LATE-NC and early-stage FTLD-TDP. We further tested for the presence of subtypes with distinct regional TDP-43 progression patterns within each diagnostic group, identifying two distinct cortical-predominant and brainstem-predominant subtypes within FTLD-TDP and a further two subcortical-predominant and corticolimbic-predominant subtypes within ALS. The FTLD-TDP subtypes exhibited differing proportions of TDP-43 type, while there was a trend for age differing between ALS subtypes. Interestingly, a negative relationship between age and SuStaIn stage was seen in the brainstem/subcortical-predominant subtype of each proteinopathy. No subtypes were observed for the LATE-NC group, despite aggregating individuals with and without Alzheimer’s disease and a larger sample size for this group. Overall, we provide an empirical pathological TDP-43 staging system for ALS, FTLD-TDP and LATE-NC, which yielded accurate classification. We further demonstrate that there is substantial heterogeneity amongst ALS and FTLD-TDP progression patterns that warrants further investigation in larger cross-cohort studies