Entanglement and boundary critical phenomena

We investigate boundary critical phenomena from a quantum-information perspective. Bipartite entanglement in the ground state of one-dimensional quantum systems is quantified using the Renyi entropy S-alpha, which includes the von Neumann entropy (alpha -> 1) and the single-copy entanglement (alpha ->infinity) as special cases. We identify the contribution of the boundaries to the Renyi entropy, and show that there is an entanglement loss along boundary renormalization group (RG) flows. This property, which is intimately related to the Affleck-Ludwig g theorem, is a consequence of majorization relations between the spectra of the reduced density matrix along the boundary RG flows. We also point out that the bulk contribution to the single-copy entanglement is half of that to the von Neumann entropy, whereas the boundary contribution is the same.

Transport phenomena in hydrogel membranes

In this thesis the factors surrounding the permeation of alkali and alkaline earth metal salts through hydrogel membranes are investigated. Although of relevance to aqueous separations in general, it was with their potential application in sensors that this work was particularly concerned. In order to study the effect that the nature of the solute has on the transport process, a single polymer matrix, poly (2-hydroxyethyl methacrylate), was initially studied. The influence of cation variation in the presence of a fixed anion was looked at, followed by the effect of the anion in the presence of a fixed cation. The anion was found to possess the dominant influence and tended to subsume any influence by the cation. This is explained in terms of the structure-making and structure-breaking characteristics of the ions in their solute-water interactions. Analogies in the transport behaviour of the salts are made with the Hofmeister series. The effect of the chemical composition of the polymer backbone on the water structuring in the hydrogel and, consequently, transport through the membrane, was investigated by preparing a series of poly (2-hydroxyethyl methacrylate) copolymer membranes and determining the permeability coefficient of salts with a fixed anion. The results were discussed in terms of the `free-volume' model of permeation and the water structuring of the polymer backbone. The ability of ionophores to selectively modulate the permeation of salts through hydrogel membranes was also examined. The results indicated that a dualsorption model was in operation. Finally, hydrogels were used as membrane overlays on coated wire ion-selective electrodes that employed conventional plasticised-PVC-valinomycin based sensing membranes. The hydrogel overlays were found to affect the access of the analyte but not the underlying electrochemistry.

Physical and Chemical Performance Testing of Ontario Asphalt Pavements

Thermal and fatigue cracking are the two of the major pavement distress phenomena that contribute significantly towards increased premature pavement failures in Ontario. This in turn puts a massive burden on the provincial budgets as the government spends huge sums of money on the repair and rehabilitation of roads every year. Governments therefore need to rethink and re-evaluate their current measures in order to prevent it in future. The main objectives of this study include: the investigation of fatigue distress of 11 contract samples at 10oC, 15oC, 20oC and 25oC and the use of crack-tip-opening-displacement (CTOD) requirements at temperatures other than 15oC; investigation of thermal and fatigue distress of the comparative analysis of 8 Ministry of Transportation (MTO) recovered and straight asphalt samples through double-edge-notched-tension test (DENT) and extended bending beam rheometry (EBBR); chemical testing of all samples though X-ray Fluorescence (XRF) and Fourier transform infrared analysis (FTIR); Dynamic Shear Rheometer (DSR) higher and intermediate temperature grading; and the case study of a local Kingston road. Majority of 11 contract samples showed satisfactory performance at all temperatures except one sample. Study of CTOD at various temperatures found a strong correlation between the two variables. All recovered samples showed poor performance in terms of their ability to resist thermal and fatigue distress relative to their corresponding straight asphalt as evident in DENT test and EBBR results. XRF and FTIR testing of all samples showed the addition of waste engine oil (WEO) to be the root cause of pavement failures. DSR high temperature grading showed superior performance of recovered binders relative to straight asphalt. The local Kingston road showed extensive signs of damage due to thermal and fatigue distress as evident from DENT test, EBBR results and pictures taken in the field. In the light of these facts, the use of waste engine oil and recycled asphalt in pavements should be avoided as these have been shown to cause premature failure in pavements. The DENT test existing CTOD requirements should be implemented at other temperatures in order to prevent the occurrences of premature pavement failures in future.

Chemical Stabilization and Physicochemical Properties of Soils, HR-97, Special Report, 1966

This project was initiated to gain a better understanding of the phenomena which affect the engineering behavior of soils containing colloidal size particles and to find chemical methods of treatment which could improve the engineering performance of such soils.

Chemical Stabilization and Physicochemical Properties of Soils, HR-97, Final Report, 1966

This project was initiated to gain a better understanding of the phenomena which affect the engineering behavior of soils containing colloidal size particles and to find chemical methods of treatment which could improve the engineering performance of such soils.

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.

Computational analysis and physico-chemical characterization of an inclusion compound between praziquantel and methyl-beta-cyclodextrin for use as an alternative in the treatment of schistosomiasis

Schistosomiasis is still an endemic disease in many regions, with 250 million people infected with Schistosoma and about 500,000 deaths per year. Praziquantel (PZQ) is the drug of choice for schistosomiasis treatment, however it is classified as Class II in the Biopharmaceutics Classification System, as its low solubility hinders its performance in biological systems. The use of cyclodextrins is a useful tool to increase the solubility and bioavailability of drugs. The aim of this work was to prepare an inclusion compound of PZQ and methyl-beta-cyclodextrin (MeCD), perform its physico-chemical characterization, and explore its in vitro cytotoxicity. SEM showed a change of the morphological characteristics of PZQ:MeCD crystals, and IR data supported this finding, with changes after interaction with MeCD including effects on the C-H of the aromatic ring, observed at 758 cm(-1). Differential scanning calorimetry measurements revealed that complexation occurred in a 1:1 molar ratio, as evidenced by the lack of a PZQ transition temperature after inclusion into the MeCD cavity. In solution, the PZQ UV spectrum profile in the presence of MeCD was comparable to the PZQ spectrum in a hydrophobic solvent. Phase solubility diagrams showed that there was a 5.5-fold increase in PZQ solubility, and were indicative of a type A(L) isotherm, that was used to determine an association constant (K(a)) of 140.8 M(-1). No cytotoxicity of the PZQ:MeCD inclusion compound was observed in tests using 3T3 cells. The results suggest that the association of PZQ with MeCD could be a good alternative for the treatment of schistosomiasis.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Microelectrical characterisation of diamond films: an attempt to understand the structural influence on electrical transport phenomena

The properties of microelectrical conduction in microwave plasma assisted chemical vapour deposition (MPCVD) diamond films were investigated using an atomic force microscopy probe, giving a morphological map of the electrical conduction with a spatial resolution better than 500 nm. Also, a cathodoluminescence map with a spatial resolution of about 1 mu m was obtained, giving the possibility of correlating the defects involved in the different carrier transport phenomena. Using micro-Raman analysis several bands could be identified. It is found that the defects responsible for the cathodoluminescence (CL) blue band are responsible for the major part of the electrical conduction in diamond films, while the defects localised in < 111 > surfaces, responsible for the green CL emission, could be involved in a less conductive process. (C) 2000 Elsevier Science S.A. All rights reserved.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Microelectrical characterisation of diamond films: an attempt to understand the structural influence on electrical transport phenomena

The properties of microelectrical conduction in microwave plasma assisted chemical vapour deposition (MPCVD) diamond films were investigated using an atomic force microscopy probe, giving a morphological map of the electrical conduction with a spatial resolution better than 500 nm. Also, a cathodoluminescence map with a spatial resolution of about 1 mu m was obtained, giving the possibility of correlating the defects involved in the different carrier transport phenomena. Using micro-Raman analysis several bands could be identified. It is found that the defects responsible for the cathodoluminescence (CL) blue band are responsible for the major part of the electrical conduction in diamond films, while the defects localised in < 111 > surfaces, responsible for the green CL emission, could be involved in a less conductive process. (C) 2000 Elsevier Science S.A. All rights reserved.

Sexual selection in a tropical fruit fly : role of a plant derived chemical in mate choice

The specific mechanisms by which selective pressures affect individuals are often difficult to resolve. In tephritid fruit flies, males respond strongly and positively to certain plant derived chemicals. Sexual selection by female choice has been hypothesized as the mechanism driving this behaviour in certain species, as females preferentially mate with males that have fed on these chemicals. This hypothesis is, to date, based on studies of only very few species and its generality is largely untested. We tested the hypothesis on different spatial scales (small cage and seminatural field-cage) using the monophagous fruit fly, Bactrocera cacuminata. This species is known to respond to methyl eugenol (ME), a chemical found in many plant species and one upon which previous studies have focused. Contrary to expectation, no obvious female choice was apparent in selecting ME-fed males over unfed males as measured by the number of matings achieved over time, copulation duration, or time of copulation initiation. However, the number of matings achieved by ME-fed males was significantly greater than unfed males 16 and 32 days after exposure to ME in small cages (but not in a field-cage). This delayed advantage suggests that ME may not influence the pheromone system of B. cacuminata but may have other consequences, acting on some other fitness consequence (e.g., enhancement of physiology or survival) of male exposure to these chemicals. We discuss the ecological and evolutionary implications of our findings to explore alternate hypotheses to explain the patterns of response of dacine fruit flies to specific plant-derived chemicals.