M. Tech. Chemical Engineering. / Discusses the objectives of the research project are to: 1. Develop a cost effective technique for modifying the surface groups of ACs with a view to induce selectivity properties towards PGMs. 2. Characterize the chemically treated ACs. 3. Determine adsorption capacities and selectivity of Amine treated ACs by performing batch adsorption tests. 3. Investigate the adsorption of Pt (IV) in a Continuous stirred tank reactor. The data generated according to the project objectives will assist in obtaining the following informations. 1. Adsorption isotherms - Find the maximum adsorption capacity of ACs for different solution concentrations, and temperature. Determine the effect of base metals on adsorption and hence extend the adsorption isotherm equation from single component to a multi-component adsorption isotherm. 2. Kinetics data - Determine the rate of change of metals in solution with time at various initial concentration, temperature and acid strength. 3. Characterization of modified ACs - Determine surfaces morphology of ACs using SEM-EDS.

The abuse of stimulant drugs, such as methamphetamine (METH), has become a major source of public concern in New Zealand. Specific medications for treating METH addiction are not available at present. The newly discovered trace amine- associated receptor 1 (TAAR1) constitutes a novel receptor target for medication development in neuropsychiatry. TAAR1 regulates monoamine systems in the brain, especially dopamine, and is activated directly by psychomotor stimulants, including METH. This study examined the effects of the newly developed TAAR1 partial agonist, RO5203648, in rat models of METH abuse. In experiment 1 rats were administered different doses of RO5203648 (0, 1.67, 5mg/kg i.p.) followed by METH (0, 0.75, 2mg/kg i.p.). Locomotor activity was monitored via automated video tracking system in an open field. The results revealed that RO5203648 dose- dependently reduced acute METH-induced stimulation and prevented long-term sensitization following chronic exposure. Paradoxically, in experiment 2, RO5203648 and METH treatment increased c-Fos protein expression in the nucleus accumbens and dorsal striatum. In experiment 3 rats were trained to consistently self-administer METH (0.5mg/kg/infusion) and were then pre-treated with RO5203648 (0, 3, 10mg/kg i.p.). The data showed that RO5203648 drastically reduced METH intake. Next, RO5203648 was substituted (0.25, 0.5, 1.0 mg/kg/infusion) for METH in the same paradigm. Remarkably, RO5203648 exhibited no reinforcing efficacy compared with METH. Taken together, these observations showed that RO5203648 is able to attenuate METH-related behaviours, including locomotor stimulation, sensitization and self-administration, and highlight the great potential of TAAR1-based medications for the treatment of METH addiction.

Absorption-stripping with aqueous, concentrated piperazine (PZ) is a viable retrofit technology for post-combustion CO2 capture from coal-fired power plants. The rate of thermal degradation and oxidation of PZ was investigated over a range of temperature, CO2 loading, and PZ concentration. At 135 to 175 °C, degradation is first order in PZ with an activation energy of 183.5 kJ/mole. At 150 °C, the first order rate constant, k1, for thermal degradation of 8 m PZ with 0.3 mol CO2/mol alkalinity is 6.12 × 10-9 s-1. After 20 weeks of degradation at 165 °C, 74% and 63%, respectively, of the nitrogen and carbon lost in the form of PZ and CO2 was recovered in quantifiable degradation products. N-formylpiperazine, ammonium, and N-(2-aminoethyl) piperazine account for 57% and 45% of nitrogen and carbon lost, respectively. Thermal degradation of PZ likely proceeds through SN2 substitution reactions. In the suspected first step of the mechanism, 1-[2-[(2-aminoethyl) amino]ethyl] PZ is formed from a ring opening SN2 reaction of PZ with H+PZ. Formate was found to be generated during thermal degradation from CO2 or CO2-containing molecules. An analysis of k1 values was applied to a variety of amines screened for thermal stability in order to predict a maximum recommended stripper temperature. Morpholine, piperidine, PZ, and PZ derivatives were found to be the most stable with an allowable stripper temperature above 160 °C. Long-chain alkyl amines or alkanolamines such as N-(2-hydroxyethyl)ethylenediamine and diethanolamine were found to be the most unstable with an allowable stripper temperature below 120 °C. Iron (Fe2+) and stainless steel metals (Fe2+, Ni2+, and Cr3+) were found to be only weak catalysts for oxidation of PZ, while oxidation was rapidly catalyzed by copper (Cu2+). In a system with Fe2+ or SSM, 5 kPa O2 in the inlet flue gas, a 55 °C absorber, and one-third residence time with O2, the maximum loss rate of PZ is expected to 0.23 mol PZ/kg solvent in one year of operation. Under the same conditions but with Cu2+ present, the loss rate of PZ is predicted to be 1.23 mole PZ/kg solvent in one year of operation. Inhibitor A was found to be effective at decreasing PZ loss catalyzed by Cu2+. Ethylenediamine, carboxylate ions, and amides were the only identified oxidation products. Total organic carbon analysis and overall mass balances indicate a large concentration of unidentified oxidation products. / text

The solvent 7 molal (m) methyldiethanolamine (MDEA)/2 m piperazine (PZ) presents an attractive option to industry standard solvents including monoethanolamine (MEA) for carbon dioxide (CO₂) capture in coal-fired power plant flue gas scrubbing applications. The solvent was tested under thermal and oxidizing conditions, including temperature cycling in the Integrated Solvent Degradation Apparatus (ISDA), to measure rates of degradation for comparison to other solvents. Unloaded 7 m MDEA/2 m PZ was generally thermally stable up to 150 °C, exhibiting very low loss rates. However, at a loading of 0.25 mol CO2/mol alkalinity, loss rates of 0.17 ± 0.21 and 0.24 ± 0.06 mM/hr, respectively, for MDEA and PZ were measured. No amine loss was observed in the unloaded blend. Thermal degradation was modeled as first-order in [MDEAH⁺], and a universal Ea for amine loss was estimated at 104 kJ/mol. An oxidative degradation model for 7 m MDEA was developed based on the ISDA data. From the model, the rate of amine loss in 7 m MDEA/2 m PZ was estimated at 1.3 X 10⁵ kg/yr, based on a 500 MW power plant and 90% CO₂ capture. In terms of amine loss, the solvent can be ranked with other cycled solvents from greatest to least as follows: 7 m MDEA>7 m MDEA/2 m PZ>8 m PZ. Thermal degradation pathways and mechanisms for 7 m MDEA/2 m PZ include SN2 substitution reactions to form diethanolamine (DEA), methylaminoethanol (MAE), 1-methylpiperazine (1-MPZ), and 1,4-dimethylpiperazine (1,4-DMPZ). The formation of the amino acids bicine and hydroxyethyl sarcosine (HES) has been directly tied to the formation of DEA and MAE, respectively, through oxidation. As a result of the construction and operation of the ISDA for cycling of solvents from an oxidative reactor to a thermal reactor, several practical findings related to solvent degradation were made. The ISDA results demonstrated that increasing dissolved oxygen in solvents leaving the absorber will increase the rate of oxidation. A simple N2 gas stripping method was tested and resulted in a reduction to 1/5th the high temperature oxidation rate associated with dissolved oxygen present in the higher temperature regions of an absorber/stripper system. The ISDA experiments also demonstrated the need to minimize entrained gas bubbles in absorber/stripper systems to control oxidation. When the ISDA was modified to intercept entrained gas bubbles, the oxidation rate was reduced 2 to 3X. / text

The chemical structure of polyether amines (PEA), mainly electron donating multiple oxygen and nitrogen atoms as well as active hydrogen atoms, make such compounds actively participating in the formation of hydrogen bonds with surrounding molecules. Hydrophobic polypropylene glycol functionality gives PEA's properties of multi-headed surfactants having hydrophilic amine groups. These groups have a strong affinity for water molecules, ice and hydrate crystals. Such PEA compounds have been known for several years. However, the hydrate inhibition properties of PEA’s were only discovered about twelve years ago. The first discovery stimulated more research in laboratories and led to practical applications for hydrate inhibition in gas fields. An interesting property of PEAs is their synergistic effect on hydrate inhibition when applied concurrently with polymeric kinetic hydrate inhibitors (KHI) or thermodynamic inhibitors (THI). The combination inhibitors are better inhibitors than a single component one. Quaternized polyether diamines are efficient antiagglomerant (AA) hydrate inhibitors while different derivatization can produce dual functionality compounds, i.e. corrosion inhibitors/gas hydrate inhibitors (CI/GHI). With all of this versatility, PEAs found application for hydrate inhibition in oil and gas fields onshore and offshore in production, flowlines and completion. The PEAs have an excellent record in protecting gas-producing wells from plugging with hydrates. (Final corrected copy of ICGH paper 5347)

No description available.

Green chemistry principles served as a guide for three industrially-relevant projects. In the first project, silylamines were applied as reversible ionic liquids for carbon dioxide capture from post-combustion flue gas streams. The effect of silylamine structure was thoroughly researched to develop a comprehensive library of silylamines and an accompanying set of structure-property relationships. The proposed solvent systems have the potential to present significant energy savings, as design has focused on their use in a non-aqueous, solvent-free environment. The second project also dealt extensively with carbon dioxide capture, as a reversible, in-situ protecting group for amines. Three strategies for the reversible protection of amines using carbon dioxide were developed and evaluated. Further, a chemoselective reaction was performed using carbon dioxide to protect a reactive amine and consequentially direct reactivity elsewhere within the same molecule. The carbon dioxide-protection technology developed has significant impact in multi-step industrial syntheses, as reversible, in-situ protection with carbon dioxide could eliminate the need for separate protection and deprotection unit operations. Lastly, a study was performed on the thermal degradation and stabilization of PVC in the presence of both plasticizers and thermal stabilizers. The study combined both model compound experiments as well as work with bulk PVC blends to gain a holistic understanding of the processes that take place during the degradation and stabilization of PVC. A bio-based plasticizer was investigated as a replacement for petroleum-based phthalate plasticizers. Additionally, two novel thermal stabilizers for PVC were presented and evaluated.

Le plomb est un métal lourd bien connu pour sa toxicité pour l'homme et pour l'environnement, donc une méthode d'analyse précise et peu coûteuse est très souhaitable pour déterminer la teneur en plomb de divers spécimens. Ces dernières années, une attention particulière a été portée au développement de nouveaux capteurs électrochimiques pour quantifier les ions des métaux toxiques au niveau de trace. Le choix d'un matériau d'électrode et sa fonctionnalisation sont cruciaux pour le processus d'analyse. Le but principal de ce projet de recherche est de fonctionnaliser une électrode de papier carbone pour la détermination du plomb dans une solution aqueuse. À cet effet, le papier carbone activé, a été modifié avec de l'acide benzylphosphonique à partir de la réduction électrochimique des cations diazonium correspondants générés in-situ. La présence de la couche greffée a été confirmée et caractérisée par voltampérométrie cyclique, spectroscopie du photoélectron-X et par spectroscopie d'impédance électrochimique. Ainsi les groupements benzylphosphoniques, liés de manière covalente à la surface de l'électrode complexent les ions Pb2+ de la solution. La quantité de plomb complexée est déterminée par l'intégration de l'aire sous le pic d'oxydation ou de réduction d'un voltammogramme cyclique. Ces matériaux fonctionnels présentent une limite de détection de l'ordre de 0,034 µg.L-1 (S/N = 3) pour le plomb en solution. La détermination électrochimique du plomb a été examinée en variant différents paramètres tels que l'effet du pH de la solution d'immersion, l'effet du temps de préconcentration et aussi l'effet de la concentration du plomb en solution. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Électrochimie, diazonium, amine, phosphate, modification, carbone, métaux lourds, eau.

Phenelzine (PLZ) is a monoamine oxidase (MAO) inhibitor that also inhibits the activity of GABA-transaminase (GABA-T), causing significant and long-lasting increases in brain GABA levels. Inhibition of MAO prior to PLZ administration has been shown to prevent the GABAergic effects of the drug, strongly suggesting that a metabolite of PLZ formed by the action of MAO is responsible for the GABAergic effects. While PLZ has been used clinically for decades for its antidepressant and antipanic effects, it has more recently been shown to be neuroprotective in an animal model of ischemia. The aim of the experiments described in this thesis was to identify the active metabolite of PLZ, and to determine the neurochemical mechanisms by which PLZ and this metabolite exert their neuroprotective effects (with a particular focus on degenerative mechanisms observed in cerebral ischemia and Alzheimers disease (AD)). The development of an analytical assay for -phenylethylidenehydrazine (PEH) was a major breakthrough in this project and permitted the positive identification of this compound as the active metabolite of PLZ. Further experiments demonstrated that PLZ and PEH could be neuroprotective in cerebral ischemia and AD not only by reducing excitotoxicity via increased GABAergic transmission, but also by (a) increasing brain ornithine, which could potentially lead to a decrease in glutamate synthesis and/or a decrease in polyamines (whose metabolism produces toxic aldehydes); (b) inhibiting the activity of human semicarbazide-sensitive amine oxidase (SSAO), an enzyme whose activity is increased in AD producing excessive amounts of the toxic aldehyde formaldehyde (FA); (c) by sequestering FA in vitro, forming a non-reactive hydrazone product. Since PEH appears to mediate or share the neurochemical effects of PLZ, two propargylated analogs of PEH were synthesized and tested for their potential as PEH prodrugs. Surprisingly these analogs were not particularly effective prodrugs in vivo, but they possessed an interesting neurochemical properties on their own (the ability to elevate brain levels of glycine), and warrant further investigation as potential antipsychotic agents. Together, these results suggest that PLZ and its active metabolite, PEH, should be further investigated for their neuroprotective potential in cerebral ischemia and in AD. / Neurochemistry

Several members of the lysyl oxidase family of copper-dependent amine oxidases have been implicated in tumor development. The Iysyl oxidase (LOX) and LOX-like 2 (LOXL2) genes have been mapped to chromosomal regions affected by loss of heterozygosity (LOH) in several cancers, including those of the colon and esophagus. Indeed, there have been numerous reports of reduced LOX and a few reports of reduced LOXL2 expression in various cancers. Identification of microsatellite markers within the LOX locus and the LOXL2 gene allowed for evaluation ofthe status of these gene alleles in colon and esophageal tumors. There was significant LOH of the LOX locus in colon tumors that was accompanied by reduced mRNA expression and a spectrum of alterations and mutations affecting the LOX gene. This study demonstrated, for the first time, that genetic events, namely LOH, deletions and mutations ofthe LOX gene, were responsible, at least partly, for the reduction of LOX gene expression. There was also significant LOH of the LOXL2 gene in both colon and esophageal tumors. However, instead of a reduction of LOXL2 expression, there was increased expression that correlated with less differentiated tumors and absent elastosis, both indicators of poor prognosis. Further studies indicated that both LOX and LOXL2 are absent in non-invasive tumor cell lines but re-expressed in invasive cell lines, likely as part of the thelial-mesenchymal transition that occurs in the last steps of tumorigenesis to facilitate metastasis. The results presented and research strategy outlined in this dissertation will define the importance of LOXL2 amine oxidase activity and protein interactions in the critical but poorly understood process oftumor cell migration and invasion.