The chemical modification of polymer blends by reactive processing

The primary objective of this research was to examine the concepts of the chemical modification of polymer blends by reactive processing using interlinking agents (multi-functional, activated vinyl compounds; trimethylolpropane triacrylates {TRIS} and divinylbenzene {DVD}) to target in-situ interpolymer formation between immiscible polymers in PS/EPDM blends via peroxide-initiated free radical reactions during melt mixing. From a comprehensive survey of previous studies of compatibility enhancement in polystyrene blends, it was recognised that reactive processing offers opportunities for technological success that have not yet been fully realised; learning from this study is expected to assist in the development and application of this potential. In an experimental-scale operation for the simultaneous melt blending and reactive processing of both polymers, involving manual injection of precise reactive agent/free radical initiator mixtures directly into molten polymer within an internal mixer, torque changes were distinct, quantifiable and rationalised by ongoing physical and chemical effects. EPDM content of PS/EPDM blends was the prime determinant of torque increases on addition of TRIS, itself liable to self-polymerisation at high additions, with little indication of PS reaction in initial reactively processed blends with TRIS, though blend compatibility, from visual assessment of morphology by SEM, was nevertheless improved. Suitable operating windows were defined for the optimisation of reactive blending, for use once routes to encourage PS reaction could be identified. The effectiveness of PS modification by reactive processing with interlinking agents was increased by the selection of process conditions to target specific reaction routes, assessed by spectroscopy (FT-IR and NMR) and thermal analysis (DSC) coupled dichloromethane extraction and fractionation of PS. Initiator concentration was crucial in balancing desired PS modification and interlinking agent self-polymerisation, most particularly with TRIS. Pre-addition of initiator to PS was beneficial in the enhancement of TRIS binding to PS and minimisation of modifier polymerisation; believed to arise from direct formation of polystyryl radicals for addition to active unsaturation in TRIS. DVB was found to be a "compatible" modifier for PS, but its efficacy was not quantified. Application of routes for PS reaction in PS/EPDM blends was successful for in-situ formation of interpolymer (shown by sequential solvent extraction combined with FT-IR and DSC analysis); the predominant outcome depending on the degree of reaction of each component, with optimum "between-phase" interpolymer formed under conditions selected for equalisation of differing component reactivities and avoidance of competitive processes. This was achieved for combined addition of TRIS+DVB at optimum initiator concentrations with initiator pre-addition to PS. Improvements in blend compatibility (by tensiles, SEM and thermal analysis) were shown in all cases with significant interpolymer formation, though physical benefits were not; morphology and other reactive effects were also important factors. Interpolymer from specific "between-phase" reaction of blend components and interlinking agent was vital for the realisation of positive performance on compatibilisation by the chemical modification of polymer blends by reactive processing.

Antibody detection of Burkholderia pseudommallei and Burkholderia mallei

Monoclonal and polyclonaI antibodies have been produced for use in immunological assays for the detection of Burkholderia pseudomallei and Burkholderia mallei. Monoclonal antibodies recognising a high molecular weight polysaccharide material found in some strains of both species have been shown to be effective in recognising B. pseudomallei and B. mallei and distinguishing them from other organisms. The high molecular weight polysaccharide material is thought to be the capsule of B. pseudomallei and B. mallei and may have important links with virulence. B. pseudomallei and B. mallei are known to be closely related, sharing many epitopes, but antigenic variation has been demonstrated within both the species. The lipopolysaccharide from strains of B. pseudomal/ei and B. mallei has been isolated and the silver stain profiles found to be visually very similar. A monoclonal antibody raised to B. mallei LPS has been found to recognise both B. mallei and B. pseudomallei strains. However, in a small number of B. pseudomallei strains a visually atypical LPS profile has been demonstrated. A monoclonal ant ibody rai sed against this atypical LPS showed no recognition of the typical LPS profile of either B. mallei or B. pseudomallei. This atypical LPS structure has not been reported and may be immunologically distinct from the typical LPS. Molecular biology and antibody engineering techniques have been used in an attempt to produce single-chain antibody fragments reactive to B. pseudomallei. Sequencing of one of the single-chain antibody fragments produced showed high homology with murine immunoglobulin genes, but none of the single-chain antibody fragments were found to be specific to B. pselldomallei.

Improving the function of islet and beta-cell grafts

Background: Human islet transplantation would offer a less invasive and more physiological alternative than whole pancreas transplantation and insulin injections respectively for the treatment of diabetes mellitus if islet graft survival can be improved. Initial recipient post-transplant insulin independence declines to <10% after 5 years. Factors contributing to graft failure include enzymatic disruption of the islet microenvironment during isolation, diabetogenic effects of immunosuppressants and metabolic stress resulting from slow revascularisation. Aims: To investigate the effect of co-culture in both static (SC) and rotational culture (RC) of BRINBDII beta-cells (Dl1) and human umbilical vein endothelial cells (HUVEC) on Dl1 insulin secretion; and the effect of a thiazolidinedione (TZD) on DII function and HUVEC proliferation. To assess the effect of culture media, SC, RC and a TZD on human islet morphology, insulin secretion and VEGF production. To initiate in vivo protocol development for assessment of revascularisation of human islet grafts. Methods: D11 cells were cultured +/-TZD and co-cultured with HUVEC +/-TZD in SC and RC. Dl1 insulin secretion was induced by static incubation with low glucose (1.67mM), high glucose (l6.7mM: and high glucose with 10mM theophylline (G+T) and determined by ELISA. HUVEC were cultured +/-TZD in SC and RC and proliferation was assessed by ATP luminescence assay and VEGF ELISA. D II and HUVEC morphology was determined by immunocytochemistry. Human islets were cultured in SC and RC in various media +/-TZD. Insulin secretion was determined as above and VEGF production by fluorescence immunocytochemistry (FI) and ELISA. Revascularisation of islet grafts was assessed by vascular corrosion cast and FI. Results: Dll cultures showed significantly increased insulin secretion in response to 16.7mM and G+T over basal; this was enhanced by RC and further improved by adding 10mM TZD. Untreated Dll/HUVEC co-cultures displayed significantly increased insulin secretion in response to 16.7mM and G+T over basal, again enhanced by RC and improved with 10mM TZD. 10mM TZD significantly increased HUVEC proliferation over control. Human islets maintained in medium 199 (mI99) in SC and RC exhibited comparable maintenance of morphology and insulin secretory profiles compared to islets maintained in RPMI, endothelial growth media and dedicated islet medium Miami# I. All cultures showed significantly increased insulin secretion in response to 16.7mM and G+T over basal; this was enhanced by RC and in certain instances further improved by adding 25mM TZD. TZD increased VEGF production and release as determined by ELISA. Post-implant vascular corrosion casts of mouse kidneys analysed by x-ray micro tomography indicates a possible TZD enhancement of microvessel growth via VEGF upregulation. Conclusions: D II /HUVEC co-culture in SC or RC does not alter the morphology of either cell type and supports D 11 function. TZD improves 0 I I and D I I/HUVEC SC and RC co-culture insulin secretion while increasing HUVEC proliferation. Human islet RC supports islet functional viability and structural integrity compared to SC while the addition of TZD occasionally further improves secretagogue induced insulin secretion. Expensive, 'dedicated' islet media showed no advantage over ml99 in terms of maintaining islet morphology or function. TZD upregulates VEGF in islets as shown by ELISA and suggested by x-ray micro tomography analysis of vascular corrosion casts. Maintenance of islets in RC and treatment with TZD prior to transplant may improve the functional viability and revascularisation rate of islet grafts.

Fast reconstruction of harmonic functions from Cauchy data using the Dirichlet-to-Neumann map and integral equations

We propose and investigate a method for the stable determination of a harmonic function from knowledge of its value and its normal derivative on a part of the boundary of the (bounded) solution domain (Cauchy problem). We reformulate the Cauchy problem as an operator equation on the boundary using the Dirichlet-to-Neumann map. To discretize the obtained operator, we modify and employ a method denoted as Classic II given in [J. Helsing, Faster convergence and higher accuracy for the Dirichlet–Neumann map, J. Comput. Phys. 228 (2009), pp. 2578–2576, Section 3], which is based on Fredholm integral equations and Nyström discretization schemes. Then, for stability reasons, to solve the discretized integral equation we use the method of smoothing projection introduced in [J. Helsing and B.T. Johansson, Fast reconstruction of harmonic functions from Cauchy data using integral equation techniques, Inverse Probl. Sci. Eng. 18 (2010), pp. 381–399, Section 7], which makes it possible to solve the discretized operator equation in a stable way with minor computational cost and high accuracy. With this approach, for sufficiently smooth Cauchy data, the normal derivative can also be accurately computed on the part of the boundary where no data is initially given.

In situ studies of titania-supported Au shell-Pd core nanoparticles for the selective aerobic oxidation of crotyl alcohol

The thermal evolution of titania-supported Au shell–Pd core bimetallic nanoparticles, prepared via colloidal routes, has been investigated by in situ XPS, DRIFTS, EXAFS and XRD and ex situ HRTEM. As-prepared nanoparticles are terminated by a thin (∼5 layer) Au shell, encapsulating approximately 20 nm diameter cuboctahedral palladium cores, with the ensemble stabilised by citrate ligands. The net gold composition was 40 atom%. Annealing in vacuo or under inert atmosphere rapidly pyrolyses the citrate ligands, but induces only limited Au/Pd intermixing and particle growth <300 °C. Higher temperatures promote more dramatic alloying, accompanied by significant sintering and surface roughening. These changes are mirrored by the nanoparticle catalysed liquid phase selective aerobic oxidation of crotyl alcohol to crotonaldehyde; palladium surface segregation enhances both activity and selectivity, with the most active surface alloy attainable containing ∼40 atom% Au.

Refractive index sensitivity characteristics near the dispersion turning point of the multimode microfiber-based Mach–Zehnder interferometer

The turning point of the refractive index (RI) sensitivity based on the multimode microfiber (MMMF) in-line Mach–Zehnder interferometer (MZI) is observed. By tracking the resonant wavelength shift of the MZI generated between the HE11 and HE12 modes in the MMMF, the surrounding RI (SRI) could be detected. Theoretical analysis demonstrates that the RI sensitivity will reach ±∞ on either side of the turning point due to the group effective RI difference (퐺) approaching zero. Significantly, the positive sensitivity exists in a very wide fiber diameter range, while the negative sensitivity can be achieved in a narrow diameter range of only 0.3 μm. Meanwhile, the experimental sensitivities and variation trend at different diameters exhibit high consistency with the theoretical results. High RI sensitivity of 10777.8 nm/RIU (RI unit) at the fiber diameter of 4.6 μm and the RI around 1.3334 is realized. The discovery of the sensitivity turning points has great significance on trace detection due to the possibility of ultrahigh RI sensitivity.

A new non-contact optical device for ocular biometry

Background: A new commercially available device (IOLMaster, Zeiss Instruments) provides high resolution non-contact measurements of axial length (using partial coherent interferometry), anterior chamber depth, and corneal radius (using image analysis). The study evaluates the validity and repeatability of these measurements and compares the findings with those obtained from instrumentation currently used in clinical practice. Method: Measurements were taken on 52 subjects (104 eyes) aged 18-40 years with a range of mean spherical refractive error from +7.0 D to -9.50 D. IOLMaster measurements of anterior chamber depth and axial length were compared with A-scan applanation ultrasonography (Storz Omega) and those for corneal radius with a Javal-Schiötz keratometer (Topcon) and an EyeSys corneal videokeratoscope. Results: Axial length: the difference between IOLMaster and ultrasound measures was insignificant (0.02 (SD 0.32) mm, p = 0.47) with no bias across the range sampled (22.40-27.99 mm). Anterior chamber depth: significantly shorter depths than ultrasound were found with the IOLMaster (-0.06 (0.25) mm, p <0.02) with no bias across the range sampled (2.85-4.40 mm). Corneal radius: IOLMaster measurements matched more closely those of the keratometer than those of the videokeratoscope (mean difference -0.03 v -0.06 mm respectively), but were more variable (95% confidence 0.13 v 0.07 mm). The repeatability of all the above IOLMaster biometric measures was found to be of a high order with no significant bias across the measurement ranges sampled. Conclusions: The validity and repeatability of measurements provided by the IOLMaster will augment future studies in ocular biometry.

Neuronal network dynamics during epileptogenesis in the medial temporal lobe

Epilepsy is one of the most common neurological disorders, a large fraction of which is resistant to pharmacotherapy. In this light, understanding the mechanisms of epilepsy and its intractable forms in particular could create new targets for pharmacotherapeutic intervention. The current project explores the dynamic changes in neuronal network function in the chronic temporal lobe epilepsy (TLE) in rat and human brain in vitro. I focused on the process of establishment of epilepsy (epileptogenesis) in the temporal lobe. Rhythmic behaviour of the hippocampal neuronal networks in healthy animals was explored using spontaneous oscillations in the gamma frequency band (SγO). The use of an improved brain slice preparation technique resulted in the natural occurence (in the absence of pharmacological stimulation) of rhythmic activity, which was then pharmacologically characterised and compared to other models of gamma oscillations (KA- and CCh-induced oscillations) using local field potential recording technique. The results showed that SγO differed from pharmacologically driven models, suggesting higher physiological relevance of SγO. Network activity was also explored in the medial entorhinal cortex (mEC), where spontaneous slow wave oscillations (SWO) were detected. To investigate the course of chronic TLE establishment, a refined Li-pilocarpine-based model of epilepsy (RISE) was developed. The model significantly reduced animal mortality and demonstrated reduced intensity, yet high morbidy with almost 70% mean success rate of developing spontaneous recurrent seizures. We used SγO to characterize changes in the hippocampal neuronal networks throughout the epileptogenesis. The results showed that the network remained largely intact, demonstrating the subtle nature of the RISE model. Despite this, a reduction in network activity was detected during the so-called latent (no seizure) period, which was hypothesized to occur due to network fragmentation and an abnormal function of kainate receptors (KAr). We therefore explored the function of KAr by challenging SγO with kainic acid (KA). The results demonstrated a remarkable decrease in KAr response during the latent period, suggesting KAr dysfunction or altered expression, which will be further investigated using a variety of electrophysiological and immunocytochemical methods. The entorhinal cortex, together with the hippocampus, is known to play an important role in the TLE. Considering this, we investigated neuronal network function of the mEC during epileptogenesis using SWO. The results demonstrated a striking difference in AMPAr function, with possible receptor upregulation or abnormal composition in the early development of epilepsy. Alterations in receptor function inevitably lead to changes in the network function, which may play an important role in the development of epilepsy. Preliminary investigations were made using slices of human brain tissue taken following surgery for intratctable epilepsy. Initial results showed that oscillogenesis could be induced in human brain slices and that such network activity was pharmacologically similar to that observed in rodent brain. Overall, our findings suggest that excitatory glutamatergic transmission is heavily involved in the process of epileptogenesis. Together with other types of receptors, KAr and AMPAr contribute to epilepsy establishment and may be the key to uncovering its mechanism.

Using a mixed design study to develop a breast screening intervention among Chinese women in the UK

Breast cancer is the most common cancer among Chinese women living in the UK. However the literature suggests that Chinese women are less likely to attend breast screening than white British women. No studies have been conducted to explore reasons for low attendance among this specific population. The purpose of this thesis was to understand the psycho-social factors related to breast cancer prevention and screening among Chinese women in the UK, and then to inform a breast screening intervention design. Three studies were conducted. The first was a systematic review of interventions to increase breast screening among Chinese women living in Western countries. The second and third studies used focus groups to explore Chinese women’s beliefs about breast cancer prevention and screening practices among older and younger generations. Finally, Intervention Mapping was used to synthesise the findings of the focus groups with those of the systematic review to design an empirical and theoretical evidence based breast screening intervention directed at Chinese women who are non-adherent to the NHS Breast Screening Programme. The qualitative findings revealed that older participants held a more holistic view of health maintenance, and had less knowledge about breast cancer and its causes than younger participants. They showed positive attitudes to breast screening and most had responded to receiving a mammography invitation. Language was a key barrier to older participants using medical care and obtaining health-related information. Younger participants expressed high dissatisfaction with health care in UK and showed a strong ‘neo-fatalistic’ view of breast cancer prevention, believing the main cause of breast cancer to be genetic predisposition. The synthesis of findings suggest that healthcare providers need to take Chinese cultural and language concerns, but also the differences between generations, into account when designing and implementing breast screening services and educational programmes which target Chinese women.

Spray drying lactoferrin produces inhalable antimicrobial particles

The use of antimicrobial peptides and proteins as potential therapeutic agents in the management of multi-drug resistant infections is considered an attractive concept especially since such compounds should theoretically have low immunogenicity, high bioavailability with negligible toxicity. In this study we investigated the potential of developing a dry powder inhaler formulation of lactoferrin (a multifunctional iron binding protein). To achieve this, the protein was spray dried from a water only feedstock with suitably adjusted spray drying parameters. The particle size, degree of crystallinity, moisture content and yield of the spray dried powders along with the minimum bactericidal concentration (MBC) against Pseudomonas aeruginosa strain PAO1, were assessed. Dry powder inhaler formulations were prepared, and in vitro assessment studies using the multistage impinger were carried out to assess the aerosolisation performance of the formulations. Data obtained indicate that spray dried lactoferrin retains activity against biofilms and may be successfully employed in the treatment of chronic airway infections.

Two-B or not two-B? Design patterns for hybrid metaheuristics

Real world search problems, characterised by nonlinearity, noise and multidimensionality, are often best solved by hybrid algorithms. Techniques embodying different necessary features are triggered at specific iterations, in response to the current state of the problem space. In the existing literature, this alternation is managed either statically (through pre-programmed policies) or dynamically, at the cost of high coupling with algorithm inner representation. We extract two design patterns for hybrid metaheuristic search algorithms, the All-Seeing Eye and the Commentator patterns, which we argue should be replaced by the more flexible and loosely coupled Simple Black Box (Two-B) and Utility-based Black Box (Three-B) patterns that we propose here. We recommend the Two-B pattern for purely fitness based hybridisations and the Three-B pattern for more generic search quality evaluation based hybridisations.

Ornamental plants as climatic indicators of arthropod vectors

The importance and risk of vector-borne diseases (eg. leishmaniasis, West Nile Virus, Lyme borreliosis) is going to increase in the European temperate areas due to climate change. Our previous studies have shown that the potential distribution of Leishmania infantum and some Phlebotomus (sand fly) species – a parasite of leishmaniasis, and its vectors – may be expanded even to the southern coastline of the Baltic Sea by the end of the 21st century. The lowland areas of the Carpathian Basin and the main part of Hungary are projected to be suitable for the studied sand fly vectors in the near future. It is important to find some indicator plants to examine whether the sand flies are able to live in a certain climate at a certain time. We studied several Mediterranean and Sub-Mediterranean plant species, and we found that the aggregated distribution of three ligneous species (Juniperus oxycedrus L., Quercus ilex L. and Pinus brutia Ten.) shows high correlation with the union distribution of five sand flies (Phlebotomus ariasi Tonn., Ph. neglectus Tonn., Ph. perfiliewi Parrot, Ph. perniciosus Newst. and Ph. tobbi Adler, Theodor et Lourie). Since these Mediterranean species are highly tolerant of the edaphic characteristics of the planting site, they may prove to be good indicators. The present and upcoming climate of Hungary is seen to be suitable for the selected indicator plant species, and it draws attention to and verifies the potential of the expansion of sand flies, which has been proved by some recent observations of the vectors in Southern Hungary.

Ornamental plants as climatic indicators of arthropod vectors

The importance and risk of vector-borne diseases (e.g., leishmaniasis, West Nile Virus, Lyme borreliosis) is going to increase in the European temperate areas due to climate change. Our previous studies have shown that the potential distribution of Leishmania infantum and some Phlebotomus (sand fly) species – a parasite of leishmaniasis, and its vectors – may be expanded even to the southern coastline of the Baltic Sea by the end of the 21st century. The lowland areas of the Carpathian Basin and the main part of Hungary are projected to be suitable for the studied sand fly vectors in the near future. It is important to find some indicator plants to examine whether the sand flies are able to live in a certain climate at a certain time. We studied several Mediterranean and Sub-Mediterranean plant species, and we found that the aggregated distribution of three ligneous species (Juniperus oxycedrus L., Quercus ilex L. and Pinus brutia Ten.) shows high correlation with the union distribution of five sand flies (Phlebotomus ariasi Tonn., Ph. neglectus Tonn., Ph. perfiliewi Parrot, Ph. perniciosus Newst. and Ph. tobbi Adler, Theodor et Lourie). Since these Mediterranean species are highly tolerant of the edaphic characteristics of the planting site, they may prove to be good indicators. The present and upcoming climate of Hungary is seen to be suitable for the selected indicator plant species, and it draws attention to and verifies the potential of the expansion of sand flies, which has been proved by some recent observations of the vectors in Southern Hungary.

Cognitive competence and life course change in multi-problem adolescents

The dissertation reports on two studies. The purpose of Study I was to develop and evaluate a measure of cognitive competence (the Critical Problem Solving Skills Scale – Qualitative Extension) using Relational Data Analysis (RDA) with a multi-ethnic, adolescent sample. My study builds on previous work that has been conducted to provide evidence for the reliability and validity of the RDA framework in evaluating youth development programs (Kurtines et al., 2008). Inter-coder percent agreement among the TOC and TCC coders for each of the category levels was moderate to high, with a range of .76 to .94. The Fleiss' kappa across all category levels was from substantial agreement to almost perfect agreement, with a range of .72 to .91. The correlation between the TOC and the TCC demonstrated medium to high correlation, with a range of r(40)=.68, p<.001 to r(40)=.79, p<.001. Study II reports an investigation of a positive youth development program using an Outcome Mediation Cascade (OMC) evaluation model, an integrated model for evaluating the empirical intersection between intervention and developmental processes. The Changing Lives Program (CLP) is a community supported positive youth development intervention implemented in a practice setting as a selective/indicated program for multi-ethnic, multi-problem at risk youth in urban alternative high schools in the Miami Dade County Public Schools (M-DCPS). The 259 participants for this study were drawn from the CLP's archival data file. The study used a structural equation modeling approach to construct and evaluate the hypothesized model. Findings indicated that the hypothesized model fit the data (χ2 (7) = 5.651, p = .83; RMSEA = .00; CFI = 1.00; WRMR = .319). My study built on previous research using the OMC evaluation model (Eichas, 2010), and the findings are consistent with the hypothesis that in addition to having effects on targeted positive outcomes, PYD interventions are likely to have progressive cascading effects on untargeted problem outcomes that operate through effects on positive outcomes.

Field programmable gate array based target detection and gesture recognition

The move from Standard Definition (SD) to High Definition (HD) represents a six times increases in data, which needs to be processed. With expanding resolutions and evolving compression, there is a need for high performance with flexible architectures to allow for quick upgrade ability. The technology advances in image display resolutions, advanced compression techniques, and video intelligence. Software implementation of these systems can attain accuracy with tradeoffs among processing performance (to achieve specified frame rates, working on large image data sets), power and cost constraints. There is a need for new architectures to be in pace with the fast innovations in video and imaging. It contains dedicated hardware implementation of the pixel and frame rate processes on Field Programmable Gate Array (FPGA) to achieve the real-time performance. ^ The following outlines the contributions of the dissertation. (1) We develop a target detection system by applying a novel running average mean threshold (RAMT) approach to globalize the threshold required for background subtraction. This approach adapts the threshold automatically to different environments (indoor and outdoor) and different targets (humans and vehicles). For low power consumption and better performance, we design the complete system on FPGA. (2) We introduce a safe distance factor and develop an algorithm for occlusion occurrence detection during target tracking. A novel mean-threshold is calculated by motion-position analysis. (3) A new strategy for gesture recognition is developed using Combinational Neural Networks (CNN) based on a tree structure. Analysis of the method is done on American Sign Language (ASL) gestures. We introduce novel point of interests approach to reduce the feature vector size and gradient threshold approach for accurate classification. (4) We design a gesture recognition system using a hardware/ software co-simulation neural network for high speed and low memory storage requirements provided by the FPGA. We develop an innovative maximum distant algorithm which uses only 0.39% of the image as the feature vector to train and test the system design. Database set gestures involved in different applications may vary. Therefore, it is highly essential to keep the feature vector as low as possible while maintaining the same accuracy and performance^