Blood contacting devices are frequently limited by complications such as surface-induced thrombosis. This thesis investigated the feasibility of using a family of recombinant elastin-like polypeptides (ELPs), namely ELP1, ELP2 and ELP4 that differ by molecular weight and sequence length, as potential thromboresistant coatings. The ELP coatings were prepared by physical adsorption onto the surface of Mylar, with surface modification confirmed by goniometry, X-ray photoelectron spectroscopy (XPS), and chemical force microscopy (CFM). Both surface wettability and hydrophilic adhesion force increased as the ELP sequence length decreased. The ELP adsorption process monitored by using quartz crystal microbalance with dissipation (QCM-D) showed that the ELPs adsorbed within a monolayer. Additionally, ELP surface coverage was found to increase with the polypeptide sequence length. The QCM-D studies also revealed that the longer polypeptides (ELP2 and ELP4) exhibited higher specific dissipation values indicating that they established adsorbed layers with greater structural flexibility and associated water content compared to ELP1. Exposure of the ELP coatings to flowing reconstituted blood demonstrated that both the ELP2 and ELP4 coatings reduced the quantity of adsorbed fibrinogen (Fg), with the ELP4 coating resulting in the lowest levels of adherent platelets. Energy dissipation versus frequency shift plots obtained from QCM-D studies indicated that adsorbed Fg on the ELP4 coating maintained a softer, more flexible film then on the other ELPs. The ELP4 coating also demonstrated an altered binding activity for GPIIb/IIIa where only the AGDV motif in the adsorbed Fg gamma-chain appeared to be exposed and bioactive. Conversely, on the other ELP coatings both the AGDV and RGD motifs (found within the Fg alpha-chain) were available for binding, suggesting that a different Fg conformational state exists on the ELP1 and ELP2 coatings. Moreover, both the ELP2 and ELP4 coatings displayed minimal bulk platelet reactivity following extended whole blood shear exposure (up to an hour) compared to Mylar. This was not observed with the ELP1 coating. Overall, the results suggest that the structural flexibility and associated water content of the ELP coatings appear to be important criteria influencing their thrombogenicity, with ELP4 displaying the most favourable blood-material response compared to ELP1 and ELP2.

In this work, transparent and rigid organogels suitable for intravitreal drug delivery applications were produced with pharmaceutical/food grade polar and amphiphilic solvents with HLB values ranging from 0-19. Maximum sterol solubility was obtained with solvents with approximately HLB=6. Solvents with high sterol solubility also required higher sterol concentrations to produce a gel. However, the strength of all the organogels increased with increasing sterol concentration. Furthermore, DSC and SAXS data suggest that the structure of all the organogels was similar. An in vitro release of dexamethasone was performed over a 5.5 month period using novel organogel- dexamethasone implants. The release of dexamethasone varied from 2 to 5.5 months (or more) depending on the organogel used for the implant. These multiple-month release in vitro profiles are comparable and/or exceed the release of commercially available and FDA approved dexamethasone delivery system Ozurdex (~2 month dexamethasone release).

Deflocculation is a common upset event in biological wastewater treatment plants and causes significant problems in biosolids discharge and environmental management. However, fundamental understanding of deflocculation is limited. The overall objective of this work was to explore the fundamentals for deflocculation under transients of short-term low dissolved oxygen (DO). The investigation was carried out in a sequence of batch and continuous experiments on activated sludge, followed by batch experiments on E. coli suspensions. Both batch and continuous experiments on activated sludge demonstrated deflocculation of bioflocs under the transients of low DO (< 0.5 mg/L). Under the short-term low DO (in hours), turbidity increased by 20 times in the batch system and by 1-2 times in the continuous system, concentrations of suspended solids increased by 1-2 times, number of small particles (< 12.5 mm) increased by 2 times, more soluble EPS (proteins and humic substances) were released into supernatant or treated effluents, the removal efficiency of organic compounds was reduced by 50-70%. A 40% of increase in bulk K+ but a 30% of decrease in bulk Ca2+ under the DO limitation were observed in the batch experiments. There were significant increases in bulk K+ and decreases in bulk Ca2+ in the continuous experiments. Reversible changes were observed within 24 hours once the DO stress was removed. Floc strength of the remaining bioflocs after deflocculation increased. Deflocculation under the short-term low DO was consistent with an erosion process. The addition of selected chemicals (i.e., Ca2+, tetraethylammonium chloride, glibenclamide, and valinomycin) did not prevent deflocculation under the short-term low DO. It is proposed that a DO stress causes an efflux of cellular K+ but an influx of extracellular Ca2+, resulting in a decreasing ratio of Ca2+/K+ in extracellular solution and thereby causing deflocculation. The E. coli tests supported that increasing bulk K+ under the DO limit was due to the release of cellular K+ and was a stress response to the DO limitation.

Constraint-based models of metabolism seldom incorporate capacity constraints on intracellular fluxes due to the lack of experimental data. This can sometimes lead to inaccurate growth phenotype predictions. Meanwhile, other forms of data such as fitness profiling data from growth competition experiments have been demonstrated to contain valuable information for elucidating key aspects of the underlying metabolic network. Hence, the optimal capacity constraint identification (OCCI) algorithm is developed to reconcile constraint-based models of metabolism with fitness profiling data by identifying a set of flux capacity constraints that optimally fits a wide array of strains. OCCI is able to identify capacity constraints with considerable accuracy by matching 1,155 in silico-generated growth rates using a simplified model of Escherichia coli central carbon metabolism. Capacity constraints identified using experimental fitness profiles with OCCI generated novel hypotheses, while integrating thermodynamics-based metabolic flux analysis allowed prediction of metabolite concentrations.

Xylan is one of the major hemicelluloses present in plant cell wall matrix, where it is closely associated with other cell wall components, cellulose and lignin. Xylan has enormous potential as a renewable biopolymer and recently, research in the direction of isolation and utilization of xylan is gaining lot of research attention. Extraction of xylan from the plant cell walls involves the hydrolysis of xylan and its transfer from the plant cell wall matrix to the hydrolyzing media. Current process of extraction involves prolonged heating of the biomass with the hydrolysis media at high temperature and/or pressure that leads to molecular degradation of xylan and limits its high potential polymeric applications. In this research, microwave assisted alkaline extraction of polymeric xylan from birch wood is investigated as an alternative to the time intensive conventional extraction. The hypothesis to be tested is that the microwave’s selective heating ability leads to the generation of hot spots through its interaction with the alkali present in the fibers and the resulting "explosion effect" loosen the recalcitrant fiber structure network thereby facilitating the hydrolysis of xylan and its dissolution before undergoing significant degradation. Effect of microwave extraction on the yield of xylan and wood solubilization, physico-chemical properties of wood fibers and of isolated xylan were investigated in comparison with conventional extraction. Low power input microwave (110 W) alkaline extraction was found to be an efficient alternative to the conventional extraction. FTIR and chemical composition of wood fibers after extraction demonstrated an increased removal of xylan from the wood fibre using microwave extraction. SEM, X-ray microtomography, and X-ray crystallinity studies of wood fibers demonstrated a porous and loosened fibre structure after microwave extraction confirming the hypothesis. Molecular weight of the isolated xylan using microwave extraction was found to be higher compared to the xylan isolated using conventional extraction indicating less molecular degradation. About 75% of xylan present in birch wood could be extracted using a low power input microwave heating under optimized extraction conditions of 8wt% NaOH solution, 1:8 (g:mL) solid to liquid ratio, and 25 minutes of extraction time.

Although many commercial chemicals can dissociate, the study of the biological and environmental fate of ionogenic organic chemicals (IOCs) is still in its infancy. Uptake of the veterinary drug diclofenac in vultures and cattle was successfully simulated with a newly developed physiologically-based pharmacokinetic model for IOCs, lending credence to diclofenac’s proposed role in South Asian vulture population declines. Proteins and phospholipids rather than total lipids control the tissue distribution of diclofenac. A method was developed to simultaneously extract neutral and acidic pesticides and benzotriazoles from water samples with recoveries ranging 70-100%. This method was applied to samples from a laboratory calibration experiment of the Polar Organic Chemical Integrative Sampler. The sampler had higher uptake for neutral and acidic pesticides when filled with triphasic sorbent admixture and OASIS MAS sorbent, respectively. While either sorbent can also be applied for methylated benzotriazoles, neither is capable of quantitatively sampling all three compound groups.

This thesis was the report of the research done on the near-critical water gasification (NCWG) as an application for activated sludge treatment. The research started with the use of model compounds and binary mixtures of these compounds as feeds for the NCWG. High gasification yields were obtained using a commercial catalyst (Raney nickel), and it was found that interactions between model compounds in the binary mixtures resulted in lowering the gasification efficiencies. The research then shifted to the use of actual activated sludge samples and the search for novel catalysts for that application. Almost 70% of the sludge was gasified in the presence of the high amounts of Raney nickel. Hydrogen was the main product in the gas phase. However, Raney nickel lost half its activity after only 8 minutes of exposure to supercritical water. For some model compounds, novel catalysts formulated in our laboratories had better activities than the commercial ones. This was not the case for the NCWG of activated sludge.

This thesis was the report of the research done on the near-critical water gasification (NCWG) as an application for activated sludge treatment. The research started with the use of model compounds and binary mixtures of these compounds as feeds for the NCWG. High gasification yields were obtained using a commercial catalyst (Raney nickel), and it was found that interactions between model compounds in the binary mixtures resulted in lowering the gasification efficiencies. The research then shifted to the use of actual activated sludge samples and the search for novel catalysts for that application. Almost 70% of the sludge was gasified in the presence of the high amounts of Raney nickel. Hydrogen was the main product in the gas phase. However, Raney nickel lost half its activity after only 8 minutes of exposure to supercritical water. For some model compounds, novel catalysts formulated in our laboratories had better activities than the commercial ones. This was not the case for the NCWG of activated sludge.

Methods of chemical hazard ranking and toxic impact assessment estimate fate and toxicity assuming the chemical exists in dissolved and particulate phases and, for metals, that all dissolved species are equally bioavailable. This treatment of metals, similar to organic chemicals, introduced a significant error in their estimates of hazard ranking since metal bioavailability and ecotoxicity are related to truly dissolved phase and specifically free metal ion within it. My thesis addressed this concern by developing a new method that introduced Bioavailability Factor (BF) to the calculation of Comparative Toxicity Potentials (CTPs) for hazard ranking of chemicals; also known as Characterization Factors for use in Life Cycle Impact Assessment (LCIA). First, the metal speciation/complexation was incorporated into fate calculations by loosely coupling commercial geochemical metal speciation model, WHAM, with a multimedia fate model, USEtoxTM, which is originally designed to calculate CTPs for organic chemicals. Second, Biotic Ligand Model (BLM) was used to calculate the bioavailability-corrected adverse toxic effects of metals. This new method was applied to assess the implications of choosing environmental characteristics, notably freshwater chemistry, by calculating BFs and CTPs of several cationic metals (e.g., Cd, Cu, Co, Pb, Ni and Zn) using 12 European, 24 Canadian ecoregions, several distinct freshwater-types selected from large river and lake systems world-wide. The newly estimated metal CTPs (i.e., ecotoxicity potentials) are up to ~1000 times lower than previous values used in LCIA. Notably the model results showed that the absolute values of CTPs, and their relative ranking amongst chemicals, are a product of the characteristics of a receiving environment. Hence it is crucial to select a generic freshwater archetype on which this analysis should be based. Finally, the new model framework was extended to apply within the Unit World Model (UWM) framework to estimate critical loads (CLs) of cationic metals to surface aquatic systems.

Boronsubphthalocyanines (BsubPcs) are a class of organic semiconducting materials which are relatively underdeveloped in their synthetic methods and organic semiconducting applications. A comprehensive investigation of these materials is explored in a rigorous and strategic manner progressing through each stage of the materials development cycle: materials selection from computational screening, organic/organometallic synthesis of target materials using known methods or by the development of new synthetic methods, physical and chemical analysis of new materials, and device implementation in organic light emitting diodes and organic photovoltaic cells. The result is the formation of new compositions of BsubPc specifically engineered for application as organic semiconductors in devices. Specifically, phenoxy-boronsubphthalocyanine derivatives are investigated starting with a computational study of their molecular orbitals – a property that dictates their function (donor or acceptor behaviour) in organic electronic devices. The nature of the axial phenoxylate is found to vary the energy level of the frontier molecular orbitals minimally, by up to ~0.4 eV while the nature of the BsubPc periphery can shift the energy levels of the frontier molecular orbitals by >1 eV. The differential sensitivity of the axial phenoxylate and the BsubPc periphery becomes a key design element allowing controlled adjustments of the frontier molecular orbitals by peripheral modification and isolating the design physical chemical properties essential to device fabrication to the axial phenoxylate. Subsequently, an investigation into the solubility and sublimability of these materials is performed, which leads to their investigation in OLED and OPV devices. The success from the phenoxy-BsubPcs study has led to the exploration of new chemistry to expand the available axial nucleophiles beyond phenoxylates. Previously unattainable sulphur and nitrogen nucleophiles are synthesised using two methods (1) the condensation of Cl-BsubPc with phthalimides and (2) the activation of Cl-BsubPc using aluminum chloride to access thiols and anilines. The phthalimido-BsubPcs synthesized from this method are incorporated in OLEDs.