Design of Novel Molecular Micelles for Capillary Electrophoresis

The research presented in this dissertation involves the synthesis, characterization, and application of novel anionic and cationic chiral molecular micelles in capillary electrophoresis (CE) for the separation of diverse chiral compounds. Chapter 1 presents brief overview of the surfactants, micelle polymer, CE and micellar electrokinetic chromatography (MEKC). Chapter 2 describes the simultaneous enantioseparation of eight single chiral center â-blockers using two novel leucine and isoleucine based polymeric surfactants. The simultaneous enantioseparation of multichiral center bearing â-blockers, nadolol and labetalol is described in chapter 3. A synergistic approach, using a combination of polysodium N-undecenoxycarbonyl-L-isoleucinate (poly-L-SUCIL) and sulfated â-CD showed dramatic enantioseparation of four stereoisomers of nadolol. On the other hand for labetalol, enantiomeric separation remains unaffected using the dual chiral selector system. Chapter 4 deals with the enantiomeric separation of the binaphthyl derivatives that was found to be influenced by pH, type and concentration of the background electrolyte as well as concentration of the polymeric surfactant. In chapter 5, characterization of five alkenoxy leucine-based surfactants with variations in chain length (C8-C11), polymerization concentration and degree of polymerization showed significant effects on the chiral resolution and efficiency of hydrophobic â-blockers. The synthesis and characterization of two positively charged amino acid derived chiral ionic liquids (ILs) and their corresponding polymers is presented in chapter 6. Chiral separation of two acidic analyte (difficult to resolve with anionic micelles) can be achieved with both monomers and polymers of ILs. In chapter 7, the synthesis and detailed characterization of three pH independent amino acids derived (L-leucinol, L-isoleucinol and L-valinol) sulfated chiral polymeric surfactants is presented. These chiral sulfated surfactants are thoroughly characterized and the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The work clearly demonstrates for the first time the superiority of chiral separation in MEKC coupled to mass spectrometry at low pH. Finally, in chapter 8, six amino acid derived chiral surfactants with carboxylate and sulfate head groups were compared for enantioseparation of broad range of structurally diverse racemic compounds at neutral and basic pH conditions

Fungal osteomyelitis in a patient with chronic granulomatous disease: Case report and review of the literature

Chronic granulomatous disease (CGD) is the most common of the primary immunodeficiency in children. It is caused by single gene defect resulting in dysfunctional nicotinamide adenine dineucleotide phosphate (NADPH) oxidase complex causing recurrent bacterial and fungal infections. Here we present the case of a 9 year old boy who was a known case of CGD since three years of age. He presented with recent history of fever, left sided pain in the scapular region and difficulty in breathing. Chest imaging revealed developing left upper lobe consolidation and erosion of the 3rd posterior rib. The child underwent video assisted thoracoscopic surgery (VATS) and biopsy of the lesion. Histopathology revealed fungal hyphae which were confirmed to be Aspergillus nidulans on staining. He was successfully treated with voriconazole therapy. We will also review the literature on fungal osteomyelitis in CGD patients

The social construction of Muslim minority groups in Canada

This dissertation explores Canadian mainstream print media's discourse on Muslim minority groups in Canada in the pre- and post-9/11 timeframe. By using critical discourse analysis (CDA) of three Canadian English newspapers as well as focus group discussions, and individual interviews, this study explores the issues of racialization, Islamophobia, and the role of Canadian mainstream print media in the construction of stereotypical images of the Muslim minority groups in Canada. The data reveal the frequent usage of stereotypical racialized terms in three Canadian newspapers (two national and one local) directed toward Muslims in the post-9/11 period cultivated moral panics in Canadian society. Although Muslim were negatively portrayed in these newspapers before 9/11, the situation escalated in the post-9/11 era. Participants in the focus group discussion and individual interviews also stated that the post-9/11 moral panics augmented and perpetuated the negative feelings towards Muslims. An increased trend in racial and religious discrimination against Muslims was observed throughout Canada after the 9/11 incident in New York. The negative portrayal of Muslims stemmed from a lack of understanding of Muslim minority groups, their culture and/or international distortion of Muslims by media personnel, who did not differentiate between the small number of Muslims who engaged in or support terrorist acts, and the majority of Muslims who do not. By neglecting to recognize this conflation of the different perspectives of Muslims on these matters, the selected newspapers contributed to the escalation of moral panics in Canadian society, which resulted in increased negative attitudes towards Muslims

Predictors of vaccination card retention in children 12-59 months old in Karachi, Pakistan

Objective: To determine the factors associated with retaining the vaccination card among care takers of 12-59 months old children in Karachi, Pakistan.Methods: This was an analytical cross-sectional study in Karachi. Households were randomly selected throughout a multistage cluster sampling technique. Data was collected for 504 children of 12- 59 months of age. Questionnaire was administered to caretakers to gather information regarding the children\u27s vaccination status, socio-demographic characteristics and reviewing their vaccination cards. Statistical analysis was done by SPSS 19 using logistic regression.Results: Among 462 vaccinated children, caretakers of 33% provided vaccination cards. Odds of card retention decrease if the caretaker has a large household i.e., \u3e5 people sharing one room (AOR 0.277, 95% CI: 0.096, 0.797) and if the child is of four to five years of age (AOR 0.544, 95% CI: 0.305, 0.970). Gender of the child, and the caretaker\u27s education and access to electronic media were not significant predictors of vaccination card retention in our study.Conclusion: Our study showed that vaccination card retention for children 12-59 months of age was low (33%) in Karachi. There is a need to educate caretakers of young children regarding the importance of keeping vaccination card and to disseminate this information through healthcare providers. Improving vaccination card retention is one of the key measures which will help towards accurately estimating coverage and to inform health policy decisions

High-throughput Protein Sequence Alignment on Multi-core Systems

Rapid evolution in sequencing technologies results in generating data on an enormous scale. A focal and main challenge in analyzing data at such a large scale is the alignment of the DNA/Protein sequences, whereby reads are compared to the reference sequences. To find similar sequences, alignment algorithms are used to align a query sequence with the database. Alignment algorithms can be utilized to classify the source of a sequence, to discover similarities among the organisms, or to deduce a progenitor connection. A wide range of algorithms for alignment has been developed in recent years.In this paper, an accurate method of accelerating such algorithms using GPUs has been investigated. A Swiss-Prot database has been processed using GPU implemented Smith-Waterman Sequence Alignment Algorithm. The first step in the process generates the alignment scores but not the actual alignment. Various available alignment tools like ssearch2 are then utilized to align the output file generated during the first step.The performance of GPU-accelerated implementation as compared to other techniques is then evaluated for performance /throughput improvement. Swiss-Prot database was aligned using various alignment tools. NVIDIA TESLA K40 GPU is being utilized for generating the results for this research. This implementation achieves the performance of 44.3 Giga cell updates per second (GCUPS), which is 22.9 times better than its implementation on GTX 275. Performance is improved as the workload of sequences of equal length is equally distributed among all the threads on Multiprocessors of GPU

Evaluating the Nature of Distractive Driving Factors towards Road Traffic Accident

For past two decades many researchers have been working on quantitative as well as qualitative study of distractive driving using different approaches. Road traffic accidents have been identified as the main source of human casualties and cause of damages to the economy and society, as millions of humans is killed every year in these accidents around the world. National-level studies in Pakistan reveal that a higher percentage of males in the age group from twenty to forty years lose their lives in road traffic accidents when compared with that of females. Due to these factors, it is alarming for a society, which is highly dependent on males such as Pakistan, as these losses put numerous families into the financial crisis that lead to poverty. This study envisaged identifying whether moods and emotions play any role in road traffic accidents of young drivers. The study reviews have shown various gaps in our understanding. For this purpose, qualitative interviews of young drivers who are university going and have met some road accidents in recent years in Pakistan had been conducted. Data from the interviews had been transcribed for analysis while maintaining the anonymity of the participants for confidentiality. Analysis of the transcribed data reveals various factors that contribute to road traffic accidents where major causes are distractions, different weather conditions, sleep deprivation, unsafe lane changes, night-time driving, and these factors are triggered by the behavior when youthful drivers engage in driving for sensation seeking and self-esteem. We conclude that it is just through the appropriation of a systems approach that coordinated countermeasures can be proposed and actualized to relieve driver mistakes caused by distraction

Degradation of the residual strength of concrete: effect of fiber-reinforcement and of rubber aggregates, application to thin bonded cement-based overlays

Ce travail est centré sur l'étude du décollement de couches minces adhérentes à base cimentaire sur un substrat en béton sous chargement mécanique. Comme matériaux de réparation, des mortiers renforcés par des fibres et/ou incorporant des granulats en caoutchouc sont utilisés. Dans ces conditions, l'étude de la durabilité des réparations implique nécessairement celle de la dégradation de la résistance sous chargement de fatigue. Dans ce contexte, des essais de fatigue par traction, contrôlés par l'ouverture de la fissure (CMOD) sont effectués sur des échantillons composites afin d'établir la loi de dégradation de la résistance du mortier renforcé par des fibres et / incorporant des granulats en caoutchouc. Les résultats montrent que, pour une ouverture de fissure maximale donnée, la résistance résiduelle diminue avec le nombre de cycles et ce quelle que soit la nature du composite. La dégradation maximale de la résistance résiduelle se produit dans le cas du mortier non fibré. Pour des grandes ouvertures de fissure, un renfort par des fibres permet de limiter cette dégradation sous un chargement de fatigue. Dans le cas du mortier incorporant des granulats en caoutchouc, la dégradation de la résistance résiduelle est limitée pour les petites ouvertures de fissure. Une association granulats caoutchouc-renforcement par des fibres permet de limiter les dégâts sur une large étendue d'ouvertures de fissure. Cette solution confère au composite un intérêt pour une application durable dans le cas des réparations minces adhérentes à base cimentaire. En tenant compte des principales pathologies rencontrées dans cette application tels que la fissuration de la couche de réparation suivie par le décollement de l'interface, différentes techniques de préparation de la surface du support ont été évaluées. Parmi celles-ci, un traitement de la surface par sablage, facile à mettre en œuvre dans les conditions réelles, a été utilisé. Pour évaluer la performance structurale, des poutres composites constituées d'un rechargement mince sur des substrats dont la surface a été préalablement traitée par sablage ont été soumises à des essais de flexion trois points (monotone et fatigue). Pour le suivi de l'évolution de la fissuration dans le rechargement et du décollement à l'interface, la technique de corrélation d'image 3D est employée. Il en résulte que l'incorporation des granulats caoutchouc dans le matériau de réparation est efficace pour contrôler la fissuration, et par conséquent pour retarder l'initiation du décollement. De plus, le renforcement du matériau de réparation par des fibres est également efficace pour limiter la propagation du décollement en contrôlant l'ouverture de la fissure. Ainsi, l'utilisation simultanée des granulats caoutchouc et des fibres dans le matériau de réparation par couches minces à base cimentaire peut être une solution appropriée pour retarder l'initiation du décollement et également pour limiter sa propagation, autrement dit pour la durabilité de l'application. Les granulats en caoutchouc utilisés étant obtenus par broyage de pneus usagés non réutilisables, cette approche apporte une valeur ajoutée en valorisant un sous produit industriel et en contribuant à la sauvegarde d'un environnement sain.This work is devoted to the study of the debonding of thin bonded cement-based overlays from the concrete substrate under mechanical loading. As repair materials, fiber-reinforced and rubbberized cement-based mortars are used. Under these conditions, assessment of durability of the repairs necessarily involves the study of the degradation of the bridging strength under fatigue loading. In this context, tensile fatigue tests controlled by crack mouth opening displacement (CMOD) are conducted on composite specimens in order to establish the degradation law of fiber-reinforced and/or rubberized mortar. The bridging strength decreases with the number of fatigue cycles for the same maximum crack width, whatever the nature of the composite. The maximum cyclic bridging strength degradation occurs in plain mortar. The cyclic bridging strength degradation for large pre-cracked widths is limited for mortar reinforced with metallic fibers. In case of rubberized mortar, cyclic bridging strength degradation is limited at less pre-cracked width values. A combine use of rubber aggregates and fibers in mortar appeared to be a suitable solution to limit the cyclic bridging strength degradation for a wide range of pre-cracked widths. It confers to the composite an interest for durable application such as cement-based thin bonded overlays. Taking into account the main cause of distress in thin bonded cement-based applications i.e. cracking and interface debonding, different surface preparation techniques were evaluated in this research. Among them, the sandblasting one is usually implemented in actual conditions. In order to investigate the structural performance, composite beams consisting of a thin repair layer on top of sandblasted substrates are subjected to three point bending tests (monotonic and fatigue). For monitoring the evolution of cracking in the repair layer and of debonding at interface, digital 3D image correlation technique is used. It emerges as a conclusion that the rubber aggregates incorporation in repair material is helpful to control micro-cracking, which results in the delay of the debonding initiation. Moreover, a fiber-reinforcement of repair material is also helpful to limit the interface debonding propagation by restraining opening of the crack. So, the dual-use of rubber aggregates and fibers in the repair material of thin bonded cement-based overlays can be a suitable solution to delay the debonding initiation and also to limit the interface debonding propagation. This shows that the synergetic effect provided by the combine use of rubber aggregates and fibers remains valid under fatigue loading also. The used rubber aggregates are obtained by grinding end-of-life tyres. In such conditions, the approach brings an added value, the recycling of this industrial by-product being also a contribution to the maintenance of a clean environment. Incidentally, this approach also helps towards the development of a circular economy

Forecasting selectivity of Au-based partial oxidation catalysts via temperature programmed desorption studies on the Au(111) model catalyst

Includes bibliographical references (leaves 81-86).Cataloged from PDF version of thesis.Thesis (M.S.): Bilkent University, The Department of Chemistry and the Graduate School of Engineering and Science of Bilkent University, 2014.Gold-based heterogeneous catalysts have attracted significant attention due to their selective partial oxidation capabilities which are comparable to that of the industrial homogeneous benchmark catalysts. In the current study, a planar Au(111) single crystal model catalyst surface was utilized to understand the behavior of different organic compounds (alcohols, aldehydes, esters etc.) in conjunction to the partial oxidation reactions. Stability of different organic compounds were investigated on the Clean Au(III) surface. The stability of a particular organic compound on the Au(III) model catalyst surface was found to be closely related to the variety of generated products. Surface sensitive analytical techniques such as Temperature Programmed Desorption (TPD) and Low Energy Electron Diffraction (LEED) were used to investigate the interaction of organic compounds with the clean Au(111) single crystal surfaces under ultrahigh vacuum (UHV) conditions. Organic compounds were dosed onto atomically clean Au(III) surfaces at the liquid nitrogen temperature. All organic compounds desorbed non-dissociatively on the clean Au(111) surface. All organic compounds reveal monolayer and multilayer desorption signals but in the case of aldehydes, desorption is quite different, as they lead to polymerization on the surface with high desorption temperatures. Zeroth order desorption kinetics was observed for multilayers, while 1st order desorption was seen for the monolayer. In most cases, the multilayer feature can be observed with two distinct desorption peaks associated with amorphous and crystalline phases. In this work, it is confirmed that majority of the studied compounds have relatively low adsorption energies on Au(111). The species with lower desorption energies on Au(111) tend to undergo partial oxidation rather than total oxidation. Thus, desorption energy appears as an important descriptor for predicting the extent of oxidation in partial/total oxidation in oxidative coupling reactions.by Shah, Syed Asad Ali.M.S

Pakistan's Relations with the United States and China in the Post-9/11 Era

This paper intends to explore the key elements that contribute to reshaping Pakistan's relations with the United States (US) and China in the post-9/11 era. In addition, the reasons contributing to how the US and China are perceived in Pakistan have been examined. The US and China both use different approaches in their relations with Pakistan. The US makes unilateral decisions, poses economic and security threats to Pakistan in pursuing its objectives, while China makes bilateral decisions and asserts itself as a soft power in its relations with Pakistan. The Pew Research Center's public opinion poll data shows that the US has become increasingly unpopular in Pakistan even after its substantial economic and military aid to Pakistan. China, on the other hand, has been able to win the hearts and minds of Pakistanis even though its economic and military aid to Pakistan in comparison to the US aid package is not nearly as significant. The study also reveals that Pakistan has grave concerns about future developments in the region after the US withdraws its forces from Afghanistan