Functional polymers for biomedical application : synthesis and applications

Aromatic and aliphatic diacid chlorides were used to condense naturally occurring diamino acids and their esterified derivatives. It was anticipated the resulting functional polyamides would biodegrade to physiologically acceptable compounds and show pH dependant solubility could be used for biomedical applications ranging from enteric coatings to hydrosoluble drug delivery vehicles capable of targeting areas of low physiological pH. With these applications in mind the polymers were characterised by infra red spectroscopy, gel permeation chromatography and in the case of aqueous soluble polymers by potentiometric titration. Thin films of poly (lysine ethyl ester isophthalamide) plasticised with poly (caprolactone) were cast from DMSO/chloroform solutions and their mechanical properties measured on a Hounsfield Hti tensiometer. Interfacial synthesis was investigated as a synthetic route for the production of linear functional polyamides. High molecular weight polymer was obtained only when esterified diamino acids were condensed with aromatic diacid chlorides. The method was unsuitable for the production of copolymers of free and esterified amino acids with a diacid chloride. A novel miscible mixed solvent single phase reaction was investigated for production of copolymers of esterified and non-esterified amino acids with diacid chlorides. Aliphatic diacid chlorides were unsuitable for condensing diamino acids using this technique because of high rates of hydrolysis. The technique gave high molecular weight homopolymers from esterified diamino acids and aromatic diacid chlorides.

The development and applications of the combined use of NMR and ultrasound

The objective of the research carried out in this report was to observe the first ever in-situ sonochemical reaction in the NMR Spectrometer in the megahertz region of ultrasound. Several reactions were investigated as potential systems for a sonochemical reaction followed by NMR spectroscopy. The primary problem to resolve when applying ultrasound to a chemical reaction is that of heating. Ultrasound causes the liquid to move and produces 'hot spots' resulting in an increase in sample temperature. The problem was confronted by producing a device that would counteract this effect and so remove the need to account for heating. However, the design of the device limited the length of time during which it would function. Longer reaction times were required to enable observations to be carried out in the NMR spectrometer. The fIrst and most obvious reactions attempted were those of the well-known ultrasonic dosimeter. Such a reaction would, theoretically, enable the author to simultaneously observe a reaction and determine the exact power entering the system for direct comparison of results. Unfortunately, in order to monitor the reactions in the NMR spectrometer the reactant concentrations had to be signifIcantly increased, which resulted in a notable increase in reaction time, making the experiment too lengthy to follow in the time allocated. The Diels-Alder Reaction is probably one of the most highly investigated reaction systems in the field of chemistry and it was this to which the author turned her attention. Previous authors have carried out ultrasonic investigations, with considerable success, for the reaction of anthracene with maleic anhydride. It was this reaction in particular that was next attempted. The first ever sonochemically enhanced reaction using a frequency of ultrasound in the megahertz (MHz) region was successfully carried out as bench experiments. Due to the complexity of the component reactants the product would precipitate from the solution and because the reaction could only be monitored by its formation, it was not possible to observe the reaction in the NMR spectrometer. The solvolysis of 2-chloro-2-methylpropane was examined in various solvent systems; the most suitable of which was determined to be aqueous 2-methylpropan-2-ol. The experiment was successfully enhanced by the application of ultrasound and monitored in-situ in the NMR spectrometer. The increase in product formation of an ultrasonic reaction over that of a traditional thermal reaction occurred. A range of 1.4 to 2.9 fold improvement was noted, dependent upon the reaction conditions investigated. An investigation into the effect of sonication upon a large biological molecule, in this case aqueous lysozyme, was carried out. An easily observed effect upon the sample was noted but no explanation for the observed effects could be established.

Flow patterns, performance and scale-up of distillation trays

This work is concerned with the nature of liquid flow across industrial sieve trays operating in the spray, mixed, and the emulsified flow regimes. In order to overcome the practical difficulties of removing many samples from a commercial tray, the mass transfer process was investigated in an air water simulator column by heat transfer analogy. The temperature of the warm water was measured by many thermocouples as the water flowed across the single pass 1.2 m diameter sieve tray. The thermocouples were linked to a mini computer for the storage of the data. The temperature data were then transferred to a main frame computer to generate temperature profiles - analogous to concentration profiles. A comprehensive study of the existing tray efficiency models was carried out using computerised numerical solutions. The calculated results were compared with experimental results published by the Fractionation Research Incorporation (FRl) and the existing models did not show any agreement with the experimental results. Only the Porter and Lockett model showed a reasonable agreement with the experimental results for cenain tray efficiency values. A rectangular active section tray was constructed and tested to establish the channelling effect and the result of its effect on circular tray designs. The developed flow patterns showed predominantly flat profiles and some indication of significant liquid flow through the central region of the tray. This comfirms that the rectangular tray configuration might not be a satisfactory solution for liquid maldistribution on sieve trays. For a typical industrial tray the flow of liquid as it crosses the tray from the inlet to the outlet weir could be affected by the mixing of liquid by the eddy, momentum and the weir shape in the axial or the transverse direction or both. Conventional U-shape profiles were developed when the operating conditions were such that the froth dispersion was in the mixed regime, with good liquid temperature distribution while in the spray regime. For the 12.5 mm hole diameter tray the constant temperature profiles were found to be in the axial direction while in the spray regime and in the transverse direction for the 4.5 mm hole tray. It was observed that the extent of the liquid stagnant zones at the sides of the tray depended on the tray hole diameter and was larger for the 4.5 mm hole tray. The liquid hold-up results show a high liquid hold-up at the areas of the tray with low liquid temperatures, this supports the doubts about the assumptions of constant point efficiency across an operating tray. Liquid flow over the outlet weir showed more liquid flow at the centre of the tray at high liquid loading with low liquid flow at both ends of the weir. The calculated results of the point and tray efficiency model showed a general increase in the calculated point and tray efficiencies with an increase in the weir loading, as the flow regime changed from the spray to the mixed regime the point and the tray efficiencies increased from approximately 30 to 80%.Through the mixed flow regime the efficiencies were found to remain fairly constant, and as the operating conditions were changed to maintain an emulsified flow regime there was a decrease in the resulting efficiencies. The results of the estimated coefficient of mixing for the small and large hole diameter trays show that the extent of liquid mixing on an operating tray generally increased with increasing capacity factor, but decreased with increasing weir loads. This demonstrates that above certain weir loads, the effect of eddy diffusion mechanism on the process of liquid mixing on an operating tray to be negligible.

Studies on the generalisation of Gaussian processes and Bayesian neural networks

The assessment of the reliability of systems which learn from data is a key issue to investigate thoroughly before the actual application of information processing techniques to real-world problems. Over the recent years Gaussian processes and Bayesian neural networks have come to the fore and in this thesis their generalisation capabilities are analysed from theoretical and empirical perspectives. Upper and lower bounds on the learning curve of Gaussian processes are investigated in order to estimate the amount of data required to guarantee a certain level of generalisation performance. In this thesis we analyse the effects on the bounds and the learning curve induced by the smoothness of stochastic processes described by four different covariance functions. We also explain the early, linearly-decreasing behaviour of the curves and we investigate the asymptotic behaviour of the upper bounds. The effect of the noise and the characteristic lengthscale of the stochastic process on the tightness of the bounds are also discussed. The analysis is supported by several numerical simulations. The generalisation error of a Gaussian process is affected by the dimension of the input vector and may be decreased by input-variable reduction techniques. In conventional approaches to Gaussian process regression, the positive definite matrix estimating the distance between input points is often taken diagonal. In this thesis we show that a general distance matrix is able to estimate the effective dimensionality of the regression problem as well as to discover the linear transformation from the manifest variables to the hidden-feature space, with a significant reduction of the input dimension. Numerical simulations confirm the significant superiority of the general distance matrix with respect to the diagonal one.In the thesis we also present an empirical investigation of the generalisation errors of neural networks trained by two Bayesian algorithms, the Markov Chain Monte Carlo method and the evidence framework; the neural networks have been trained on the task of labelling segmented outdoor images.

Evolutionary neural networks : models and applications

The scaling problems which afflict attempts to optimise neural networks (NNs) with genetic algorithms (GAs) are disclosed. A novel GA-NN hybrid is introduced, based on the bumptree, a little-used connectionist model. As well as being computationally efficient, the bumptree is shown to be more amenable to genetic coding lthan other NN models. A hierarchical genetic coding scheme is developed for the bumptree and shown to have low redundancy, as well as being complete and closed with respect to the search space. When applied to optimising bumptree architectures for classification problems the GA discovers bumptrees which significantly out-perform those constructed using a standard algorithm. The fields of artificial life, control and robotics are identified as likely application areas for the evolutionary optimisation of NNs. An artificial life case-study is presented and discussed. Experiments are reported which show that the GA-bumptree is able to learn simulated pole balancing and car parking tasks using only limited environmental feedback. A simple modification of the fitness function allows the GA-bumptree to learn mappings which are multi-modal, such as robot arm inverse kinematics. The dynamics of the 'geographic speciation' selection model used by the GA-bumptree are investigated empirically and the convergence profile is introduced as an analytical tool. The relationships between the rate of genetic convergence and the phenomena of speciation, genetic drift and punctuated equilibrium arc discussed. The importance of genetic linkage to GA design is discussed and two new recombination operators arc introduced. The first, linkage mapped crossover (LMX) is shown to be a generalisation of existing crossover operators. LMX provides a new framework for incorporating prior knowledge into GAs.Its adaptive form, ALMX, is shown to be able to infer linkage relationships automatically during genetic search.

Study of the deposition, properties and applications of electroless deposits containing particles

The deposition efficiencies of a number of electroless nickel and cobalt plating solutions were studied and in the case of nickel compared with a commercial plating solution Nifoss 80. At the optimum plating conditions (92ºC and pH 4.5) Nifoss 80 produced nickel layers most efficiently, the alkaline cobalt solution operated most efficiently at 90ºC and pH 9. The methods of producing compostte layers containing 2-3 µm carbide particles and chromium powder is described. Nickel and cobalt layers containing approximately 27% carbide particles, or 40% (Ni) and 30% (Co) chromium particles by volume were obtained. This value is independent of the particle concentration in the plating solution within the range (20~200 g/l). Hardness of the nickel. as deposited was 515 Hv, this was increased to a maximum of 1155 Hv by heat treatment at 200ºC for 5 hours in vacuum. Incorporation. of .chromium carbide particles resulted in a maximum hardness of 1225 Hv after heating at 500ºC for 5 hours in vacuum and chromium particles resulted in a maximum hardness of 16S0 Hv after heat treatment at 400ºC for 2 hours in vacuum. Similarly the hardness of cobalt as deposited was 600 Hv, this was increased to a maximum of 1300 Hv after heat treatment at 400ºC for 1 hour. Incorporation of chromium carbide particles resulted jn a maximum hardness of 1405 Hv after heating at 400ºC for 5 hours in vacuum and chromium particles resulted in a maximum hardness of 1440 Hv after. heat treating for 2 hours at 400ºC in vacuum. The structure of the deposits was studied by optical and scanning electron microscopy. The wear rate and coefficient of friction was determined by a pin and disc method. Wear rate and coefficient of friction decreased with increase in hardness. The wear resistance of the materials was also determined using a simulated forging test. Dies made of standard die steel were coated and the wear rates of the layers as deposited and after heat treatment were compared with those of uncoated tools. The wear resistance generally increased with hardness, it was 50-75% more than the uncoated die steel. Acetic acid salt spray test and outdoor exposure for six months was used to study the corrosion behaviour of the deposits and potentiodynamic curves plotted to find their corrosion potential. Nickel deposit exhibited less staining than carbide composite deposits and nickel-chromium deposits had the most noble corrosion potential.

The impact of visual-verbal relationships on native-nonnative english speakers' reading processes and comprehension

The aim of this study was to comparatively investigate the impact of visual-verbal relationships that exist in expository texts on the reading process and comprehension of readers from different language background: native speakers of English (LI) and speakers of English as a foreign language (EFL). The study focussed, in this respect, on the visual elements (VEs) mainly graphs and tables that accompanied the selected texts. Two major experiments were undertaken. The first, was for the reading process using the post-reading questionnaire technique. Participants were 163 adult readers representing three groups: 77 (LI), 56 (EFL postgraduates); and 30 (EFL undergraduates). The second experiment was for the reading comprehension using cloze procedure. Participants were 123 representing the same above gorups: 50, 33 and 40 respectively. It was hypothesised that the LI readers would make use of VEs in the reading process in ways different from both EFL groups and that use would enhance each group's comprehension in different aspects and to different levels. In the analysis of the data of both experiments two statistical measurements were used. The chi-square was used to measure the differences between frequencies and the t-test was used to measure the differences between means. The results indicated a significant relationship between readers' language background and the impact of visual-verbal relationships on their reading processes and comprehension of such type of texts. The results also revealed considerable similarities between the two EFL groups in the reading process of texts accompanied by VEs. In the reading comprehension, however, the EFL undergraduates seemed to benefit from the visual-verbal relationships in their comprehension more than the postgraduates, suggesting a weak relationship of this impact for older EFL readers. Furthermore, the results showed considerable similarities between the reading process of texts accompanied by VEs and of whole prose texts. Finally an evaluation of this study was undertaken as well as practical implications for EFL readers and suggestions for future research.

UV-inscription, polarization-dependant loss characteristics and applications of 45° tilted fiber gratings

We have UV-inscribed and theoretically and experimentally analyzed fiber gratings with the structure tilted at 45° and implemented this type of devices as an in-fiber polarizer. A systematic investigation has been carried out on the characterization of 45° tilted fiber gratings (45° TFGs) in terms of the polarization-dependant loss (PDL) and thermal response. The detailed theoretical modeling has revealed a linear correlation between the grating length and the PDL, which has been proved by the experimental results. For the first time, we have examined the UV beam diffraction from a tilted phase mask and designed the UV-inscription system to suit the 45° TFG fabrication. Experimentally, a 24 mm long 45° TFG UV-inscribed in standard telecom single-mode fiber exhibited around 25 dB PDL at 1530 nm and an over ~300 nm bandwidth of PDL spectrum. By the concatenation method, a 44 mm long grating showed a PDL as high as 40 dB that is close to the high polarization extinction ratio of commercial products. Moreover, we have revealed that the PDL of 45° TFGs has low thermal influence, which is desirable for real application devices. Finally, we experimentally demonstrated an all-fiber twist sensor system based on a 45° and an 81° TFG.

Survey and applications of standardized energy metrics to mobile networks

The energy consumption and the energy efficiency have become very important issue in optimizing the current as well as in designing the future telecommunications networks. The energy and power metrics are being introduced in order to enable assessment and comparison of the energy consumption and power efficiency of the telecommunications networks and other transmission equipment. The standardization of the energy and power metrics is a significant ongoing activity aiming to define the baseline energy and power metrics for the telecommunications systems. This article provides an up-to-date overview of the energy and power metrics being proposed by the various standardization bodies and subsequently adopted worldwide by the equipment manufacturers and the network operators. © Institut Télécom and Springer-Verlag 2012.and Springer-Verlag 2012.