http://hdl.handle.net/1974/767 Wed, 19 Jun 2013 02:12:59 GMT 2013-06-19T02:12:59Z http://hdl.handle.net/1974/8081 Title: HYDROXYPHENOL INTERACTIONS WITH IRON AND ALUMINUM OXIDE COLLOIDS BY CHEMICAL FORCE SPECTROMETRY Authors: ABD. RAHMAN AZMI, ALYZA AZZURA Abstract: Tannins and humic substances commonly referred to as natural organic matter (NOM), constitute an important component of natural water and soil systems. These species contain numerous phenol and carboxyl functional groups whose reactivity is strongly dependent on both the quantity and location of these moieties on the aromatic ring. In the realistic environmental conditions, both phenolic and carboxylic functional groups are adsorbed on a variety of colloidal metal oxide surfaces. Unfortunately, due to the complexity of humic-based substances, experimental data involving mineral-humate interactions are difficult to interpret. Here, we aim to develop a more detailed understanding of mineral-NOM interactions in aquatic systems, using self-assembled monolayers (SAMs) of simple organic acids having functional groups similar to those found in humic substances. SAMs of 4-(12-mercaptododecyl)benzene-1,2-diol (o-hydroxyphenol-terminated), 5-(12-mercaptododecyl)benzene-1,3-diol (m-hydroxyphenol-terminated), bis(11-thioundecyl) hydrogen phosphate (monoprotic phosphate) and 11-thioundecyl dihydrogen phosphate (diprotic phosphate) were prepared and deposited on a Au(111) surface. The composition of elements present on the surface were determined by X-ray Photoelectron Spectroscopy (XPS) and the orientation of monolayers on the Au(111) surface was explored by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) Chemical force spectrometry has been used to determine the surface pKa of the monolayers and further used to explore the role of phenolic groups in the surface complexation of NOM by monitoring adhesion forces between iron and aluminum oxide sample and hydroxyphenol-terminated Atomic Force Microscopy (AFM) modified tip. The results are discussed in the context of hydrogen bonding between corresponding species. The system in which there are multiple hydroxyl groups ortho to the carboxylic groups or adjacent to one another on the benzene ring results in significantly different force-distance profiles when interacting with the hydroxyphenol tip. Description: Thesis (Ph.D, Chemistry) -- Queen's University, 2013-06-18 00:22:06.646 Tue, 18 Jun 2013 04:00:00 GMT http://hdl.handle.net/1974/8081 2013-06-18T04:00:00Z http://hdl.handle.net/1974/8036 Title: ORGANOHALOGENATED PERSISTENT ORGANIC POLLUTANTS IN AMERICAN EEL (ANGUILLA ROSTRATA) CAPTURED IN EASTERN CANADA Authors: Byer, Jonathan D Abstract: Recruitment of American eels (Anguilla rostrata) to Lake Ontario has declined rapidly over the past few decades. The commercial yellow eel fishery in Lake Ontario was closed in 2004 due to a lack of eel abundance. Researchers have been attempting to ascertain the reasons for the decline, although thus far, without definitive answers. In this thesis, the question of chemical contamination is addressed as it relates to female eel spawner quality. Spatial concentration trends of halogenated persistent organic pollutants (POPs) are described in eels collected from across eastern Canada, as well as temporal concentration trends in eels collected from a historically important area of northeastern Lake Ontario, Canada. Chlorinated POPs in eels, namely, organochlorinated pesticides, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans are all significantly less than historic values which peaked in the 1960-70s. Measured concentrations of chlorinated POPs in eels from Lake Ontario have decreased by up to 3-fold over the past three decades, and exceeded toxicity thresholds historically for surrogate species (European eel and lake trout). Thus, chlorinated POPs may have had an effect on spawner quality. Concentrations of legacy POPs in eels were dependent on their origin, with eels from highly urbanized and industrialized areas having significantly higher concentrations than eels captured in less developed regions. Similar trends were observed for polybrominated diphenyl ethers and chlorinated norbornene flame retardants. A number of emerging brominated compounds were also measured in these eels by non-target analysis including bromophenols, bromobenzenes, and bromoanisoles. This thesis demonstrates that eels are an ideal species to investigate local sources of pollution, and provide chemical data that may be used in the future, when more toxicity information is available for eels, to assess the health risks posed by accumulated chemical contaminants. Description: Thesis (Ph.D, Chemistry) -- Queen's University, 2013-05-23 09:27:59.593 Thu, 23 May 2013 04:00:00 GMT http://hdl.handle.net/1974/8036 2013-05-23T04:00:00Z http://hdl.handle.net/1974/7983 Title: Design, Synthesis, and Application of Stimuli-Responsive Block Copolymers Authors: Rabnawaz, MUHAMMAD Abstract: This thesis reports the preparation of novel multi-responsive and multiply stimulable triblock copolymers. The resultant polymers were used to coat cotton fabrics and glass to render them amphiphobic. Further, a method was developed for the preparation of poly(ethylene glycol)-block-poly(hydroxyethyl methacrylate) (PEG-b-PHEMA) via anionic polymerization. The multi-responsive copolymer refers to poly(ethylene glycol)-orthonitrobenzyl-poly[2-(perfluorooctyl)ethyl methacrylate)-block-poly(2-cinnamoloxyethyl methacrylate) (PEG-ONB-PFOEMA-b-PCEMA, or P1). P1 was synthesized via atom transfer radical polymerization (ATRP) of FOEMA and a precursory monomer of CEMA using a PEG macroinitiator. The copolymer was multi-responsive or dual light-responsive because the ONB junction cleaves and PCEMA block becomes crosslinked upon UV photolysis. The multiply stimulable copolymers are a series of poly(ethylene glycol)-disulfide-poly[2-(perfluorooctyl)ethyl methacrylate)-block-poly(2-cinnamoloxyethyl methacrylate) (PEG-S2-PFOEMA-b-PCEMA) copolymers. These polymers were synthesized by the end-coupling Py-S2-PFOEMA-b-PHEMA and PEG-SH, and subsequent cinnamation of the PHEMA block. These polymers are multiply stimulable because the S2 junction and PCEMA block respond to different stimulations, such as reducing agents and light, respectively. These synthetic strategies will advance the field of stimuli-responsive polymers by providing novel functional polymers for the generation of durable self-cleaning surfaces. The above polymers form micelles in water or water/organic solvent mixtures because of the water-soluble PEG blocks. Polymer-coated cotton was obtained by immersing cotton in micellar copolymer solutions before subsequent drying and annealing treatment. Upon photolysis, the PEG block was cleaved and the PCEMA anchoring layer became crosslinked. Such a crosslinked and stable layer was rendered amphiphobic because of the exposed PFOEMA block. A similar coating can be obtained from P2. Two types of stimulations including photolysis and reduction treatment need to be applied to yield amphiphobic textiles. This coating strategy is unique and environmentally friendly because the water- and oil-repellent coatings were prepared from an aqueous solution for the first time. In a further study, a novel and long-sought method was developed for the anionic polymerization of PEG-b-PHEMA. A PEG-DPE macroinitiator was synthesized and subsequently converted into an active initiator by reaction with sec-butyl lithium. Consequently, the active initiator underwent polymerization with HEMA-TMS to yield PEG-b-P(HEMA-TMS). Upon post-polymerization modification, PEG-b-PHEMA was obtained with a low polydispersity of 1.08. Description: Thesis (Ph.D, Chemistry) -- Queen's University, 2013-04-29 12:25:54.593 Mon, 29 Apr 2013 04:00:00 GMT http://hdl.handle.net/1974/7983 2013-04-29T04:00:00Z http://hdl.handle.net/1974/7921 Title: QUALITY AND DURABILITY OF RUBBERIZED ASPHALT CEMENT AND WARM RUBBERIZED ASPHALT CEMENT Authors: ADHIKARI, THAM Abstract: This thesis discusses and documents findings from an investigation of performance-based testing of asphalt cement (AC), warm mixed asphalt cement, asphalt rubber (AR), and warm asphalt rubber. A number of control, warm, and asphalt rubber binders from Ontario construction contracts were investigated for their compliance with conventional Superpave® test methods such as rolling thin film (RTFO), pressure aging vessel (PAV), dynamic shear rheometer (DSR), and bending beam rheometer (BBR), as well as additional specification tests such as extended BBR and double edge notched tension test. The quality and durability of those binders were determined. Quality means the ability of asphalt binder to reach a set of specific properties whereas durability is the measure of how well asphalt retains its original characteristics when exposed to normal weathering and aging process. One warm AC and two field-blended asphalt rubber samples showed high levels of physical hardening which can lead to premature and early cracking. The warm asphalt cement lost 8 °C when stored isothermally for three days at low temperatures according to Ontario’s extended bending beam rheometer (BBR) protocol (LS-308). The two asphalt rubber samples lost 10 °C and 12 °C following the same conditioning. Many of the studied asphalt samples showed deficient strain tolerance as measured in Ontario’s double-edge-notched tension (DENT) test (LS-299). In a study of warm rubberized asphalt cement with improved properties, a number of compositions were prepared with soft Cold Lake AC and a small quantity of naphthenic oil. These binders showed little chemical and physical hardening and reasonable critical crack tip opening displacements (CTOD). Strain tolerance was much improved by co-blending with a high vinyl type styrene-butadiene-styrene (SBS) polymer and a small amount of sulfur. Description: Thesis (Master, Chemistry) -- Queen's University, 2013-04-24 22:54:20.07 Thu, 25 Apr 2013 04:00:00 GMT http://hdl.handle.net/1974/7921 2013-04-25T04:00:00Z