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Development and application of imprinted polymers for selective adsorption of metal Ions and flavonols in complex SamplesPakade, Vusumzi Emmanuel 18 September 2012 (has links)
Presence of heavy metals in the environment is a worldwide known contamination
problem. Depending on their chemistries and level of contamination, these heavy
metals can have severe effects on the ecosystem, aquatic life and eventually
humans. Researchers have been particularly interested in finding methods for the
removal of these pollutants from the environment. Several methods have been
proposed and some have been used with some degree of success. Methods used
for trace metal removal include, chemical precipitation, chemical reduction,
solvent extraction, micellar ultrafiltration, organic and inorganic ion exchange,
adsorption processes, etc. However, the matrix in which these heavy metals are
present in is sometimes very complex and some of these heavy metals are present
in the environment at very low concentrations, say ppb levels. However, they can
have adverse effects even at such low-level concentrations. The above-mentioned
methods usually suffer from the effects of the matrix and by-products produced
after treatment such as sludge in the case of precipitation. Hence, in this study
molecularly imprinted polymers (MIPs) were used. MIPs are highly cross-linked
polymers prepared with the presence of template molecule. Once the template has
been removed it leaves behind a cavity that can only fit the template, hence MIPs
are very selective for the template molecule. Metals of interest in this study were
uranium (VI) and chromium (VI). Therefore, two separate imprinted polymers
were prepared using chromium and uranium as template molecules for selective
extraction of these oxy-ions from aqueous samples. Beside removal of heavy
metals, the study also focussed on developing MIPs for selective recovery of high
value compounds from plant materials (onion and Moringa oleifera).
Three separate imprinted polymers using chromium, uranium or quercetin
templates were prepared by bulk polymerization method. Functional monomers
used were 4-vinylpyridine; 1-(prop-2-en-1-yl)-4-(pyridin-2-ylmethyl)piperazine
(PPMP) and methacrylic acid; and 4-vinylpyridine for chromium, uranium and
quercetin imprinted polymers, respectively. For all imprinted polymers, ethylene
glycol dimethacrylate (EDMA) and 1,1‘-azobis(cyclohexanecarbonitrile) (ACCN) were used as the cross-linking monomer and initiator, respectively. Control
polymers (CP) or non-imprinted polymers (NIP) for each imprinted polymer were
prepared and treated exactly the same as imprinted polymers but with omission of
respective templates. Following removal of respective templates with appropriate
solutions, various parameters that affect selective adsorption such as solution pH,
initial concentration, aqueous phase volume, sorbent dosage, contact time,
breakthrough volumes etc., were optimized to get optimal adsorption of the
imprinted polymers.
Optimal parameters for Cr (VI) adsorption were as follows: solution pH, 3;
contact time, 120 min; eluent, 20 mL of 0.1 M NaOH; and sorbent amount, 125
mg. Maximum retention capacity of IIP and CP was 37.58 and 25.44 mg g-1,
respectively. The observed selectivity order was as follows, Cr (VI) > SO4
2- > F- >
PO4
3- > NO2
- > NO3
- > Cl-. However, in the presence of high concentrations of
sulphate ions, the selectivity on the CP completely collapsed. For uranium VI
removal, the optimal pH was 4.0-8.0, sorbent amount was 20 mg, contact time
was 20 min and the retention capacity was 120 mg of uranyl ion per g of IIP. The
selectivity order observed was as follows, UO2
2+ > Fe3+ >> Cu2+ > Co2+ > Mn2+ >
Zn2+ ~ Ni2+.
The binding capacity of quercetin MIPs was investigated at 25 and 84°C,
respectively, in batch mode. The slopes for the effect of extraction time revealed
that the mass transfer of the analytes was higher at 84°C than at 25°C. Also, the
binding capacity for the most promising MIP and its corresponding NIP increased
at 84°C but the MIP had higher binding capacity. The increase in binding capacity
for the MIP was from ~30 μmol g-1 at 25°C to ~120 μmol g-1 at 84°C. For the
corresponding NIP, the binding capacity values were ~15 and ~90 μmol g-1, at 25
and 84°C, respectively. A demonstration of MIP selectivity at higher temperature
using standard solutions of selected flavonols showed that the MIP still retained
its selectivity for quercetin. Similar selectivity was observed when preliminary
application studies on aqueous yellow onion extracts were investigated. The study
clearly demonstrated the suitability of the developed imprinted polymers (for chromium, uranium and quercetin) for selective adsorption of Cr (VI), UO2
2+ and
quercetin from their respective complex matrices.
Breakthrough volume of molecular imprinted polymer solid-phase extraction
(MISPE) was investigated using a mixture of myricetin, quercetin and
kaempferol. The breakthrough volumes for quercetin, kaempferol and myricetin
were 22, 27 and 8 mL, respectively. The number of theoretical plates (N) for the
MISPE column corresponding to these volumes were 18, 47 and 4 for quercetin,
kaempferol and myricetin, respectively. Using these results, selectivity of MIP
and its retention capacity was evaluated. The extractions of Moringa leaves and
flowers were carried out using a MISPE cartridge and various solvents were
investigated for the selective elution of quercetin from the MIP sorbents. For
identification and quantification of quercetin and other flavonols, a high
performance liquid chromatography (HPLC) was used. Recoveries of quercetin
from different Moringa extracts ranged from 87 – 92% and this demonstrated that
the MISPE method can be used for the recovery of quercetin and kaempferol from
the Moringa extracts. Amount of quercetin found in Moringa leaves was 1555 mg
kg-1.
All the imprinted and non-imprinted polymers prepared in the study were
characterized with Fourier Transform Infrared (FTIR) spectroscopy. Scanning
electron microscopy (SEM) was used for recording surface morphology of all the
polymers. Surface area and pore size analysis were recorded on Micromeritic
Tristar BET. For quercetin MIP, thermogravimetric analysis (TGA) was also used
in addition to the mentioned techniques.
In additional studies, the concentrations of metals in the soil and, in the leaves and
flowers of Moringa plant grown in South Africa were examined. The
investigation included heavy metals, major and trace nutrient elements. The
analysis of metals was achieved after total digestion of soils or leaves using a
microwave, and the concentrations of metals were determined using inductively
coupled plasma-optical emission spectroscopy (ICP-OES). These results were compared to those obtained from some selected vegetables like spinach, cabbage,
cauliflower, broccoli, and peas. No toxic heavy metals were detected in the leaves
and flowers of Moringa. On average Moringa contained higher concentration of
Ca (18500 mg kg-1) and Mg (5500 mg kg-1) than other vegetables compared with
in the study. Other major nutrients contained in Moringa were much similar to
other vegetables. Besides metals, the concentrations of flavonols (myricetin,
quercetin, kaempferol) determined from Moringa leaves and flowers were also
compared to selected vegetables. Plant and vegetable materials were extracted
under reflux using acidified methanol (1% HCl) solution. Following which, the
flavonols were identified and quantified using reverse phased-high performance
liquid chromatography method equipped with UV detection. Moringa leaves
exhibited highest concentrations of myricetin (1296.6 mg kg-1), quercetin (1362.6
mg kg-1), kaempferol (1933.7 mg kg-1) than vegetables (spinach: myricetin 620.0
mg kg-1, quercetin 17.9 mg kg-1, kaempferol 215.3 mg kg-1).
Lastly, the antioxidant activity of Moringa flowers and leaves were compared to
that of the aforementioned selected vegetables. The antioxidant activity was
studies by analyzing the total phenolic content (TPC), total flavonoid content
(TFC), reducing power, radical scavenging activity, and the 2,2-diphenyl-1-
picrylhydrazyl free radical (DPPH) method. Moring contained almost twice the
TPC and thrice the TFC than the vegetables. Also, Moringa demonstrated higher
reducing power and lower percentage of free radicals remaining (DPPH method).
Hence, Moringa showed to be a good antioxidant source than the selected
vegetables compared with.
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The attenuation of the main zone at the Phosiri Dome, Bushveld ComplexMartin, Lucienne E 16 May 2011 (has links)
MSc, Faculty of Science, University of the Witwatersrand, 1999
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Curvature of Kaehler Manifolds.January 1995 (has links)
by Tsang Yau Shing. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves 79-83). / Contents --- p.1 / Chapter Chapter 0 --- Introduction --- p.1 / Chapter Chapter 1. --- Elliptic Case --- p.4 / Chapter 1.1 --- Existence of energy minimizing maps --- p.6 / Chapter 1.2 --- Complex analyticity of energy minimizing maps --- p.9 / Chapter 1.3 --- Holomorphic deformation of rational curves --- p.15 / Chapter 1.4 --- End of proof and further remarks --- p.25 / Chapter Chapter 2. --- Parabolic Case --- p.30 / Chapter 2.1 --- Construction of non-vanishing holomorphic n-form --- p.32 / Chapter 2.2 --- Construction of functions of minimal degree --- p.50 / Chapter 2.3 --- Construction of biholomorphism using minimal degree functions --- p.53 / Chapter Chapter 3. --- Hyperbolic Case --- p.59 / Chapter 3.1 --- Various types of negative curvature conditions --- p.61 / Chapter 3.2 --- A Bochner type identity --- p.63 / Chapter 3.3 --- Complex analyticity of harmonic maps --- p.66 / Chapter 3.4 --- Bounded symmetric domains --- p.73 / Chapter 3.5 --- "Strong ""rigidity"" and other applications" --- p.76 / Bibliography --- p.79
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The study of some [beta]-diketones as complexing agents for the corrosion prevention of iron and steel.January 1977 (has links)
Kam Tat-ting. / Thesis (M.Phil.)--Chinese University of Hong Kong. / Bibliography: leaves 111-113.
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Optimized Nested Complex Event Processing Using Continuous CachingRay, Medhabi 12 October 2011 (has links)
"Complex Event Processing (CEP) has become increasingly important for tracking and monitoring anomalies and trends in event streams emitted from business processes such as supply chain management to online stores in e-commerce. These monitoring applications submit complex event queries to track sequences of events that match a given pattern. While the state-of-the-art CEP systems mostly focus on the execution of flat sequence queries, we instead support the execution of nested CEP queries specified by the (NEsted Event Language) NEEL. However the iterative execution often results in the repeated recomputation of similar or even identical results for nested sub- expressions as the window slides over the event stream. This work proposes to optimize NEEL execution performance by caching intermediate results. In particular a method of applying selective caching of intermediate results called Continuous Sliding Caching technique has been designed. Then a further optimization of the previous technique which we call the Semantic Caching and the Continuous Semantic Caching have been proposed. Techniques for incrementally loading, purging and exploiting the cache content are described. Our experimental study using real- world stock trades evaluates the performance of our proposed caching strategies for different query types."
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Retention of patients with schizophrenia in complex intervention trials : patterns, issues, and practicesSzymczyńska, Paulina January 2018 (has links)
Background: Inability to retain participants in a clinical trial poses a threat to clinical research as it can lead to a number of issues ultimately affecting generalisability, validity and reliability of the study. Patients with schizophrenia have been reported as particularly difficult to engage and retain in research and psychiatric treatment. This thesis aimed to improve the current understanding of the retention of people with schizophrenia in trials evaluating complex interventions. Methods: This thesis adopted a mixed method design. Quantitative methodology was used to identify the scale of attrition and to explore potential predictors of dropout. This included a systematic review and meta-analysis and a separate meta-analysis of individual patient data. Qualitative methodology was used in two studies to explore the perspectives of both trial staff and former trial participants on the factors important for retention and effective practices and strategies. Results: The results of the systematic review and meta-analysis demonstrated the rates of dropout from studies to be higher than from experimental interventions. Dropout from interventions significantly increased as the number of intervention sessions increased. The individual patient data meta-analysis found retention to be higher at the final follow-up assessment than at the penultimate one. The effect of arm allocation almost reached statistical significance pointing to the possibility of participants in the active arm having higher odds of completing the final follow-up than those in the control arm. Two qualitative studies identified barriers and facilitators to retention related to factors related to participant, researcher, study, and wider context. Some of the identified barriers were specific to schizophrenia. Conclusion: Attrition is a phenomenon that should be anticipated by trialists and prevented with the use of multiple strategies. The extent to which dropout can be minimised depends on a number of factors associated with the participant, researcher, study, and context.
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Synthetic, structural and catalytic studies of novel metal cyclopentadienyl compounds. / CUHK electronic theses & dissertations collectionJanuary 1998 (has links)
by Fuquan Song. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 204-205). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web.
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Model theory of holomorphic functions in an o-minimal settingUtreras Alarcon, Javier Antonio January 2015 (has links)
Given an o-minimal structure on the real field, we consider an elementary extension to a non-archimedean field R, and interpret the algebraically closed field K=R[sqrt(-1)] on this extension. We construct two pregeometries on K: one by considering images under C-definable holomorphic functions, and the other by considering images under proper restrictions of C-definable holomorphic functions together with algebraic functions (i.e. zeros of polynomials).We show that these two pregeometries are the same, generalising a result of A. Wilkie for complex holomorphic functions. We also do some work towards generalising another result of his on local definability of complex holomorphic functions to our non-archimedean setting.
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A Holistic Approach to Sustainability Analysis of Industrial NetworksBeck, Jessica Mareile January 2008 (has links)
Doctor of Philosophy(PhD) / The aim of this thesis is to support the evaluation of sustainable development strategies for industrial networks in the context of industrial ecology (IE). Industrial networks are a group of units which carry out, or contribute to, industrial activity, and are connected by material and energy flows, but also capital and information exchanges. The components of an industrial network encompass resource extraction, processing and refining, forming and assembly, use, disposal, as well as recycling and reprocessing. The motivation behind this research is the realisation that much of the current environmental system analysis focus within IE lacks a structured approach to considering: • system environment • dynamic nature of the system and its environment • economic and social impacts • the effect of uncertainty on analysis outcomes. It is argued in this thesis that current environmental analysis approaches used in IE can be improved in their capacity to capture the complexity of industrial systems, with the objective of promoting sustainable development. While IE emphasises the benefit of a systems approach to identifying environmental strategies in industry, analysis tools have to date not engaged extensively with important aspects such as the influence of system environment and dynamics on the viability of an environmental strategy, or with the economic or social impacts of industrial system development, which are equally important for sustainable development. Nor is the assessment of the effect of uncertainty on analysis outcomes an integral part of environmental analysis tools in IE. This is particularly significant when, in fact, the degree of uncertainty in assumptions and data used increases with the scope, and therefore the abstraction, of the system under consideration. IE will have to engage with the network and contextual complexities to a greater degree if it is to evolve from a concept to the application of its principles in practice. The main contribution of this thesis is therefore the development of a structured approach to analysing industrial networks for the purpose of identifying strategies to encourage sustainable development, while accounting for the complexity of the underlying system as well as the problem context. This analysis is intended to allow the identification of preferred network development pathways and to test the effectiveness of sustainable development strategies. A top-down, prescriptive approach is adopted for this purpose. This approach is chosen as the industrial network analysis is intended to identify how a network should develop, rather than focusing on how it could develop. Industrial networks are systems which are complex in both their structure and behaviour. This thesis also delivers a characterisation of these networks, which serves two purposes – quantifying key elements of structure and behaviour; and using this information to build a foundation for subsequent industrial network analysis. The value of such an approach can be seen in the following example. With a detailed understanding of individual network characteristics, both separately and collectively, it is possible to determine the source of issues, the means available to address them, any barriers that might exist, and the consequences of implementing any strategic interventions. The analysis approach proposed in this thesis is based on multi-criteria decisions analysis (MCDA), which, as a process, combines initial problem structuring and subsequent quantitative analysis stages. The tools employed within MCDA have been employed variously around considerations of sustainable development. Their value in this thesis is their integration within a rigorous analytical framework. Rigorous problem structuring is attractive as it helps elucidate the complexities of the system and its environment and is, by definition, designed to deal with multiple environmental social and economic criteria that would have to be considered to promote sustainable development. For the quantitative analysis, the industrial network analysis draws from existing analysis tools in IE, but predominately from other systems research disciplines, such as process systems engineering (PSE) and supply chain management (SCM). These fields, due to their maturity and practical focus, have invested a lot of research into system design and strategic planning, capturing system dynamics and uncertainty to ensure, within selected system constraints, that a proposed system or changes to a system are viable, and that the system is capable of achieving the stated objectives. Both PSE and SCM rely heavily on optimisation for system design and planning, and achieve good results with it as an analytical tool. The similarity between industrial networks and process systems / supply chains, suggests that an optimisation platform, specifically multi-objective dynamic optimisation, could be employed fruitfully for the analysis of industrial networks. This is the approach taken in this thesis. It is consistent with the “top down” approach advocated previously, which is deemed preferable for the identification and implementation analysis of strategic interventions. This enables the determination of a structure (design) that is “best” able to operate under future conditions (planning) with respect to the chosen sustainable development objectives. However, an analysis is only ever as good as its underlying data and assumptions. The complexity and scope of the industrial network and the challenge of articulating sustainable development target(s) give rise to significant uncertainties. For this reason a framework is developed within this thesis that integrates uncertainty analysis into the overall approach, to obtain insight into the robustness of the analysis results. Quantifying all the uncertainties in an industrial network model can be a daunting task for a modeller, and a decision-maker can be confused by modelling results. Means are therefore suggested to reduce the set of uncertainties that have to be engaged with, by identifying those which impact critically on model outcomes. However, even if uncertainty cannot be reduced, and the implementation of any strategy retains a degree of risk, the uncertainty analysis has the benefit that it forces an analyst to engage in more detail with the network in question, and to be more critical of the underlying assumptions. The analysis approach is applied to two case studies in this thesis: one deals with waste avoidance in an existing wood-products network in a large urban metropolis; the other with the potential for renewable energy generation in a developing economy. Together, these case studies provide a rich tableau within which to demonstrate the full features of the industrial network analysis. These case studies highlight how the context within which the relevant industrial network functions influences greatly the evolution of the network over time; how uncertainty is managed; and what strategies are preferred in each case in order to enhance the contribution of each network to sustainable development. This thesis makes an intellectual contribution in the following areas: • the characterisation of industrial networks to highlight sources of environmental issues, role the characteristics (could) play in the identification of (preferred) sustainable development strategies, and the need to explicitly consider these in a systems analysis. • the synthesis, adaptation and application of existing tools to fulfil the need for analysis tools in IE that can handle both contextual and system complexity, and address the above mentioned issues of lacking consideration of o system environment o dynamic nature of the system and its environment o economic and social impacts o the effect of uncertainty on analysis outcomes. • the development and demonstration of an industrial network analysis approach that o is flexible enough to model any industrial network at the inter-firm level, regardless of form and configuration of materials and products circulated, and depending on the existing network and the proposed strategies. o is able to encompass a wide range of environmental strategies, either individually or in combination depending on what best suits the situation, rather than focusing on any strategy in particular. o ensures long term viability of strategies, rather than short term solutions delivering incremental improvement. • the development of a comprehensive approach to capturing and assessing the effect of uncertainty on solution robustness for industrial network analysis, including the screening to determine the most important parameters, considering valuation and technical uncertainties, including future uncertainty. The industrial network analysis approach presented in this thesis looks more to how a network should develop (according to a set of sustainable development objectives), rather than how it may in actual fact develop. Consequently, the influence of agent interests and behaviour is not considered explicitly. This may be construed as a limitation of the industrial analysis approach. However, it is argued that the “top down” modelling approach favoured here is useful at a policy-making level. Here, for example, government instrumentalities, trade organisations and industry groupings, non-government organisations and community-based organisations are likely to be interested more in the performance of the network as a whole, rather than (necessarily) following the behaviour of individual agents within the network. Future work could well entertain the prospect of a mixed approach, in which the top-down approach of this thesis is complemented by a “bottom-up”, agent-based analysis. In this manner, it would be possible to give an indication of how attainable the identified industrial network development pathways are. Furthermore, the use of government incentives can be explored to assess if network development could approach the preferred development pathway which is identified using the methodology and results articulated in this thesis.
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Hydrated complexes in the earth�s atmosphereSchofield, Daniel Paul, n/a January 2005 (has links)
The interaction between sunlight and our atmosphere is one of the most fundamental processes affecting weather and climate. The majority of the Sun�s radiation is produced in the ultraviolet, visible and near-infrared regions of the electromagnetic spectrum. These spectral regions correspond to the energies of vibrational overtone and electronic transitions. The composition of our atmosphere is complex, and many trace species have a large influence on its chemistry and dynamics. Hydrogen bound hydrated complexes are trace species that could play an important role in the Earth�s atmosphere. However, before this role can be quantified, spectral identification and characterisation of these complexes is essential.
We have developed vibrational local mode Hamiltonians to simulate the absorption spectra of hydrated complexes. To test the approximations made in the vibrational model, we have peformed calculations on the diatomics OH, HF and CO, which can be considered to act as pure local modes. When highly correlated ab initio methods and large basis sets are used to calculate the potential energy and dipole moment curve, the simulated vibrational transitions of the diatomics are in excellent agreement with experiment.
We have derived approximate vibrational Hamiltonians which describe the OH-stretching and HOH-bending modes of vibration in the complexes H₂O�H₂O, H₂O�HO₂ and H₂O�HO. The calculated spectrum of H₂O�H₂O has been used to assess its atmospheric importance, and to succesfully guide experimental efforts to detect H₂O�H₂O in the laboratory and the Earth�s atmosphere. The calculated transition energies and intensities of H₂O�H₂O and H₂O�HO are in good agreement with experimental matrix isolation and gas-phase studies.
To investigate the effect of low frequency modes on OH-stretching overtone spectra we have simulated the spectrum of HOONO. We have derived a Hamiltonian that couples the NOOH-torsional mode to the high frequency OH-stretching and OOH-bending modes. The simulated spectrum is in good agreement with the experimentally observed spectrum. We find that the OH-stretching spectra are perturbed strongly only if the barrier to torsion is low.
We have also investigated changes in the electronic spectrum of hydrated complexes and the corresponding parent monomers. Upon complex formation, the lowest-lying electronic transition in the hydroxyl radical is strongly redshifted outside the region of monomeric absorption.
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