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.

Considering Efficacy of an Outdoor Environmental Education Program: Facilitating Elementary Students’ Environmental Knowledge, Attitudes, and Behaviours

Various sources have sought to consider the educational interventions that foster changes in perception of and attitudes toward nature, with the ultimate intent of understanding how education can be used to encourage environmentally responsible behaviours. With these in mind, the current study identified an outdoor environmental education program incorporating these empirically supported interventions, and assessed its ability to influence environmental knowledge, attitudes, and behaviours. Specifically, this study considered the following research questions: 1) To what degree can participation in this outdoor education program foster environmental knowledge and encourage pro-environmental attitudes and self-reported pro-environmental behaviours? 2) How is this effect different among students of different genders, and those who have different prior experiences in nature? Two motivational frameworks guided inquiry in the current study: the Value-Belief-Norm Model of Environmentalism (VBN) and the Theory of Planned Behaviour (TPB). The study employed a quantitative survey methodology, combining contemporary data measuring knowledge, attitudes, and behaviours with archived data collected by program staff, reflecting frequency of environmentally responsible behaviour. Further, a single qualitative item was included for which students provided “the first three words that [came] to mind when [they] think of the word nature.” Terms provided before and after the program were compared for differences in theme to detect subtle or underlying changes. Quantitative results indicated no significant change in student knowledge or attitudes through the outdoor environmental education program. However, a significant change in self-reported behaviour was identified from both the contemporary and archived data. This agreement in positive findings across the two data sets, collected using different measures and different participants, lends evidence of the program’s ability to encourage self-reported pro-environmental behaviour. Further, qualitative results showed some change in students’ perceptions of nature through the program, providing direction for future research. These findings suggest that this particular outdoor education program was successful in encouraging students’ self-reported environmentally responsible behaviour. This change was achieved without significant change in knowledge or environmental attitudes, suggesting that external factors not measured in this study might have played a role in affecting behaviour.

WHEN INTERACTING ONLINE LEADS TO TAKING ACTION OFFLINE: EXAMINING THE EFFECTS OF ONLINE PERSUASION ON IS USERS’ PRO-ENVIRONMENTAL BEHAVIOURS

With the increasing attention towards the role of information systems (IS) as a vehicle to address environmental issues, IS researchers and practitioners have strived to leverage advanced Green IS innovations to persuade people to engage in environmentally responsible practices and support pro-environmental initiatives. Yet, existing research reveals that the persuasion effects of Green IS designs remain equivocal. In particular, many design characteristics advocated in Green IS research can produce bi-directional changes in IS users’ attitudes and behaviours. To address this issue, this thesis drew upon the circumplex model of social values (S.H. Schwartz, 1992) to explain when and how online persuasion designs come to affect people’s judgements on resource conservation and environmental protection. Three sets of working propositions and specific hypotheses were developed. Specifically, this research suggests that the use of an IS application can elicit different value primes and draw IS users’ attentions to different motivational functions of engaging in suggested behavioural changes. It is expected that matching online persuasion appeals with IS users’ personal value priorities can increase users’ acceptance of online behavioural suggestions. Second, it is hypothesized that the persuasion effect tends to be weakened, as the system users become aware of the valuematching design in a given IS application. Third, it is proposed that different value primes presented in an IS application can result in different unintended effects on IS users’ global pro-environmental attitudes and motivations. The hypotheses were tested in the two pilot studies and two full-scale online experiments. The study findings generally support the main predictions of the hypotheses. On the one hand, this thesis providesiii empirical evidence that IS design for online persuasion can be instrumental in influencing IS users’ judgements on a range of resource conservation practices. On the other hand, this work explains why the effectiveness of IS-enabled online persuasion attempts needs to be measured not only in terms of the intended changes in a target behavioural domain but also in terms of unintended changes in people’s general environmental orientations. Findings in this research may bring a different perspective on understanding and assessing the influence of Green IS applications on IS users’ judgements and behaviou

Applying life cycle assessment to analyze the environmental sustainability of public transit modes for the City of Toronto

One challenge related to transit planning is selecting the appropriate mode: bus, light rail transit (LRT), regional express rail (RER), or subway. This project uses data from life cycle assessment to develop a tool to measure energy requirements for different modes of transit, on a per passenger-kilometer basis. For each of the four transit modes listed, a range of energy requirements associated with different vehicle models and manufacturers was developed. The tool demonstrated that there are distinct ranges where specific transit modes are the best choice. Diesel buses are the clear best choice from 7-51 passengers, LRTs make the most sense from 201-427 passengers, and subways are the best choice above 918 passengers. There are a number of other passenger loading ranges where more than one transit mode makes sense; in particular, LRT and RER represent very energy-efficient options for ridership ranging from 200 to 900 passengers. The tool developed in the thesis was used to analyze the Bloor-Danforth subway line in Toronto using estimated ridership for weekday morning peak hours. It was found that ridership across the line is for the most part actually insufficient to justify subways over LRTs or RER. This suggests that extensions to the existing Bloor-Danforth line should consider LRT options, which could service the passenger loads at the ends of the line with far greater energy efficiency. It was also clear that additional destinations along the entire transit line are necessary to increase the per passenger-kilometer energy efficiency, as the current pattern of commuting to downtown leaves much of the system underutilized. It is hoped that the tool developed in this thesis can be used as an additional resource in the transit mode decision-making process for many developing transportation systems, including the transit systems across the GTHA.

ENVIRONMENTAL INFLUENCES AND EPIGENETIC MECHANISMS IN RISK FOR DEPRESSION

Genetic and environmental factors interact to influence vulnerability for internalizing psychopathology, including Major Depressive Disorder (MDD). The mechanisms that account for how environmental stress can alter biological systems are not yet well understood yet are critical to develop more accurate models of vulnerability and targeted interventions. Epigenetic influences, and more specifically, DNA methylation, may provide a mechanism by which stress could program gene expression, thereby altering key systems implicated in depression, such as frontal-limbic circuitry and its critical role in emotion regulation. This thesis investigated the role of environmental factors from infancy and throughout the lifespan affecting the serotonergic (5-HT) system in the vulnerability to and treatment of depression and anxiety and potential underlying DNA methylation processes. First, we investigated the contributions of additive genetic vs. environmental factors on an early trait phenotype for depression (negative emotionality) in infants and their stability over time in the first 2 years of life. We provided evidence of the substantial contributions of both genetic and shared environmental factors to this trait, as well as genetically- and environmentally- mediated stability and innovation. Second, we studied how childhood environmental stress is associated with peripheral DNA methylation of the serotonin transporter gene, SLC6A4, as well as long-term trajectories of internalizing behaviours. There was a relationship between childhood psychosocial adversity and SLC6A4 methylation in males, as well as between SLC6A4 methylation and internalizing trajectory in both sexes. Third, we investigated changes in emotion processing and epigenetic modification of the SLC6A4 gene in depressed adolescents before and after Mindfulness-Based Cognitive Therapy (MBCT). The alterations from pre- to post-treatment in connectivity between the ACC and other network regions and SLC6A4 methylation suggested that MBCT may work to optimize the connectivity of brain networks involved in cognitive control of emotion as well as also normalize the relationship between SLC6A4 methylation and activation patterns in frontal-limbic circuitry. Our results from these three studies strengthen the theory that environmental influences are critical in establishing early vulnerability factors for MDD, driving epigenetic processes, and altering brain processes as an individual undergoes treatment, or experiences relapse.