The Synthesis and properties of functionalised polymers

The aim of this project was to synthesise fluorinated polymers that might act as hot material in a guest-host system for use in non-linear optical applications. These polymers would be expected to have the advantage over materials such as poly(vinylidene fluoride) which is known to be incompatible with many nlo active materials. A series of bicyclic fluorinated monomers was prepared by the reaction of fluorinated dienophiles with cyclopentadiene in a series of Diels-Alder reactions. The monomers were purified and then used in ring opening metathesis polymerisation. The materials were then characterised by gel permeation chromatography and nuclear magnetic resonance spectroscopy and cast as films for determination of their activities as nlo materials using a Nd/YAG laser system. The second harmonic intensity of each was measured relative to quartz. However no materials of significant activity were produced. In an attempt to produce polymers that might subsequently be functionalised the polymerisation of 1,2-methylenedioxybenzene and 1,4-benzodioxane was investigated.

Liquid-phase adsorption of n-paraffins on type 5A molecular sieves

As a basis for the commercial separation of normal paraffins a detailed study has been made of factors affecting the adsorption of binary liquid mixtures of high molecular weight normal paraffins (C12, C16, and C20) from isooctane on type 5A molecular sieves. The literature relating to molecular sieve properties and applications, and to liquid-phase adsorption of high molecular weight normal paraffin compounds by zeolites, was reviewed. Equilibrium isotherms were determined experimentally for the normal paraffins under investigation at temperatures of 303oK, 323oK and 343oK and showed a non-linear, favourable- type of isotherm. A higher equilibrium amount was adsorbed with lower molecular weight normal paraffins. An increase in adsorption temperature resulted in a decrease in the adsorption value. Kinetics of adsorption were investigated for the three normal paraffins at different temperatures. The effective diffusivity and the rate of adsorption of each normal paraffin increased with an increase in temperature in the range 303 to 343oK. The value of activation energy was between 2 and 4 kcal/mole. The dynamic properties of the three systems were investigated over a range of operating conditions (i.e. temperature, flow rate, feed concentration, and molecular sieve size in the range 0.032 x 10-3 to 2 x 10-3m) with a packed column. The heights of adsorption zones calculated by two independent equations (one based on a constant width, constant velocity and adsorption zone and the second on a solute material balance within the adsorption zone) agreed within 3% which confirmed the validity of using the mass transfer zone concept to provide a simple design procedure for the systems under study. The dynamic capacity of type 5A sieves for n-eicosane was lower than for n-hexadecane and n-dodecane corresponding to a lower equilibrium loading capacity and lower overall mass transfer coefficient. The values of individual external, internal, theoretical and experimental overall mass transfer coefficient were determined. The internal resistance was in all cases rate-controlling. A mathematical model for the prediction of dynamic breakthrough curves was developed analytically and solved from the equilibrium isotherm and the mass transfer rate equation. The experimental breakthrough curves were tested against both the proposed model and a graphical method developed by Treybal. The model produced the best fit with mean relative percent deviations of 26, 22, and 13% for the n-dodecane, n-hexadecane, and n-eicosane systems respectively.

Formulation of topical non-steroidal anti-inflammatory agents

Reversed-pahse high-performance liquid chromatographic (HPLC) methods were developed for the assay of indomethacin, its decomposition products, ibuprofen and its (tetrahydro-2-furanyl)methyl-, (tetrahydro-2-(2H)pyranyl)methyl- and cyclohexylmethyl esters. The development and application of these HPLC systems were studied. A number of physico-chemical parameters that affect percutaneous absorption were investigated. The pKa values of indomethacin and ibuprofen were determined using the solubility method. Potentiometric titration and the Taft equation were also used for ibuprofen. The incorporation of ethanol or propylene glycol in the solvent resulted in an improvement in the aqueous solubility of these compounds. The partition coefficients were evaluated in order to establish the affinity of these drugs towards the stratum corneum. The stability of indomethacin and of ibuprofen esters were investigated and the effect of temperature and pH on the decomposition rates were studied. The effect of cetyltrimethylammonium bromide on the alkaline degradation of indomethacin was also followed. In the presence of alcohol, indomethacin alcoholysis was observed and the kinetics of decomposition were subjected to non-linear regression analysis and the rate constants for the various pathways were quantified. The non-isothermal, sufactant non-isoconcentration and non-isopH degradation of indomethacin were investigated. The analysis of the data was undertaken using NONISO, a BASIC computer program. The degradation profiles obtained from both non-iso and iso-kinetic studies show that there is close concordance in the results. The metabolic biotransformation of ibuprofen esters was followed using esterases from hog liver and rat skin homogenates. The results showed that the esters were very labile under these conditions. The presence of propylene glycol affected the rates of enzymic hydrolysis of the ester. The hydrolysis is modelled using an equation involving the dielectric constant of the medium. The percutaneous absorption of indomethacin and of ibuprofen and its esters was followed from solutions using an in vitro excised human skin model. The absorption profiles followed first order kinetics. The diffusion process was related to their solubility and to the human skin/solvent partition coefficient. The percutaneous absorption of two ibuprofen esters from suspensions in 20% propylene glycol-water were also followed through rat skin with only ibuprofen being detected in the receiver phase. The sensitivity of ibuprofen esters to enzymic hydrolysis compared to the chemical hydrolysis may prove valuable in the formulation of topical delivery systems.

SAS/OWA:ordered weighted averaging in SAS optimization

This paper explores the use of the optimization procedures in SAS/OR software with application to the ordered weight averaging (OWA) operators of decision-making units (DMUs). OWA was originally introduced by Yager (IEEE Trans Syst Man Cybern 18(1):183-190, 1988) has gained much interest among researchers, hence many applications such as in the areas of decision making, expert systems, data mining, approximate reasoning, fuzzy system and control have been proposed. On the other hand, the SAS is powerful software and it is capable of running various optimization tools such as linear and non-linear programming with all type of constraints. To facilitate the use of OWA operator by SAS users, a code was implemented. The SAS macro developed in this paper selects the criteria and alternatives from a SAS dataset and calculates a set of OWA weights. An example is given to illustrate the features of SAS/OWA software. © Springer-Verlag 2009.

Self-calibrated, multi-spectral photometric stereo for 3D face capture

This paper addresses the problem of obtaining 3d detailed reconstructions of human faces in real-time and with inexpensive hardware. We present an algorithm based on a monocular multi-spectral photometric-stereo setup. This system is known to capture high-detailed deforming 3d surfaces at high frame rates and without having to use any expensive hardware or synchronized light stage. However, the main challenge of such a setup is the calibration stage, which depends on the lights setup and how they interact with the specific material being captured, in this case, human faces. For this purpose we develop a self-calibration technique where the person being captured is asked to perform a rigid motion in front of the camera, maintaining a neutral expression. Rigidity constrains are then used to compute the head's motion with a structure-from-motion algorithm. Once the motion is obtained, a multi-view stereo algorithm reconstructs a coarse 3d model of the face. This coarse model is then used to estimate the lighting parameters with a stratified approach: In the first step we use a RANSAC search to identify purely diffuse points on the face and to simultaneously estimate this diffuse reflectance model. In the second step we apply non-linear optimization to fit a non-Lambertian reflectance model to the outliers of the previous step. The calibration procedure is validated with synthetic and real data.

Compensation of nonlinear fibre impairments in coherent systems employing spectrally efficient modulation formats

We investigate electronic mitigation of linear and non-linear fibre impairments and compare various digital signal processing techniques, including electronic dispersion compensation (EDC), single-channel back-propagation (SC-BP) and back-propagation with multiple channel processing (MC-BP) in a nine-channel 112 Gb/s PM-mQAM (m=4,16) WDM system, for reaches up to 6,320 km. We show that, for a sufficiently high local dispersion, SC-BP is sufficient to provide a significant performance enhancement when compared to EDC, and is adequate to achieve BER below FEC threshold. For these conditions we report that a sampling rate of two samples per symbol is sufficient for practical SC-BP, without significant penalties.

Reconstruction of an unsteady flow from incomplete boundary data:Part I. Theory

Purpose – To propose and investigate a stable numerical procedure for the reconstruction of the velocity of a viscous incompressible fluid flow in linear hydrodynamics from knowledge of the velocity and fluid stress force given on a part of the boundary of a bounded domain. Design/methodology/approach – Earlier works have involved the similar problem but for stationary case (time-independent fluid flow). Extending these ideas a procedure is proposed and investigated also for the time-dependent case. Findings – The paper finds a novel variation method for the Cauchy problem. It proves convergence and also proposes a new boundary element method. Research limitations/implications – The fluid flow domain is limited to annular domains; this restriction can be removed undertaking analyses in appropriate weighted spaces to incorporate singularities that can occur on general bounded domains. Future work involves numerical investigations and also to consider Oseen type flow. A challenging problem is to consider non-linear Navier-Stokes equation. Practical implications – Fluid flow problems where data are known only on a part of the boundary occur in a range of engineering situations such as colloidal suspension and swimming of microorganisms. For example, the solution domain can be the region between to spheres where only the outer sphere is accessible for measurements. Originality/value – A novel variational method for the Cauchy problem is proposed which preserves the unsteady Stokes operator, convergence is proved and using recent for the fundamental solution for unsteady Stokes system, a new boundary element method for this system is also proposed.

Characteristics of motor resonance predict the pattern of flash-lag effects for biological motion

Background - When a moving stimulus and a briefly flashed static stimulus are physically aligned in space the static stimulus is perceived as lagging behind the moving stimulus. This vastly replicated phenomenon is known as the Flash-Lag Effect (FLE). For the first time we employed biological motion as the moving stimulus, which is important for two reasons. Firstly, biological motion is processed by visual as well as somatosensory brain areas, which makes it a prime candidate for elucidating the interplay between the two systems with respect to the FLE. Secondly, discussions about the mechanisms of the FLE tend to recur to evolutionary arguments, while most studies employ highly artificial stimuli with constant velocities. Methodology/Principal Finding - Since biological motion is ecologically valid it follows complex patterns with changing velocity. We therefore compared biological to symbolic motion with the same acceleration profile. Our results with 16 observers revealed a qualitatively different pattern for biological compared to symbolic motion and this pattern was predicted by the characteristics of motor resonance: The amount of anticipatory processing of perceived actions based on the induced perspective and agency modulated the FLE. Conclusions/Significance - Our study provides first evidence for an FLE with non-linear motion in general and with biological motion in particular. Our results suggest that predictive coding within the sensorimotor system alone cannot explain the FLE. Our findings are compatible with visual prediction (Nijhawan, 2008) which assumes that extrapolated motion representations within the visual system generate the FLE. These representations are modulated by sudden visual input (e.g. offset signals) or by input from other systems (e.g. sensorimotor) that can boost or attenuate overshooting representations in accordance with biased neural competition (Desimone & Duncan, 1995).

Evolution of timing jitter in nonlinearly-guided, dispersion managed transmission systems

Timing jitter is a major factor limiting the performance of any high-speed, long-haul data transmission system. It arises from a number of reasons, such as interaction with accumulated spontaneous emission, inter-symbol interference (ISI), electrostriction etc. Some effects causing timing jitter can be reduced by means of non-linear filtering, using, for example, a nonlinear optical loop mirror (NOLM) [1]. The NOLM has been shown to reduce the timing jitter by suppressing the ASE and by stabilising the pulse duration [2, 3]. In this paper, we investigate the dynamics of timing jitter in a 2R regenerated system, nonlinearly guided by NOLMs at bit rates of 10, 20, 40, and 80- Gbit/s. Transmission performance of an equivalent non-regenerated (generic) system is taken as a reference.

Antecedents, mechanisms and processes of deinstitutionalization and institutional change:a case study approach to understanding enterprise under duress

Adopting a grounded theory methodology, the study describes how an event and pressure impact upon a process of deinstitutionalization and institutional change. Three case studies were theoretically sampled in relation to each other. They yielded mainly qualitative data from methods that included interviews, observations, participant observations, and document reviews. Each case consisted of a boundaried cluster of small enterprises that were not industry specific and were geographically dispersed. Overall findings describe how an event, i.e. a stimulus, causes disruption, which in turn may cause pressure. Pressure is then translated as a tension within the institutional environment, which is characterized by opposing forces that encourage institutional breakdown and institutional maintenance. Several contributions are made: Deinstitutionalization as a process is inextricable from the formation of institutions – both are needed to make sense of institutional change on a conceptual level but are also inseparable experientially in the field; stimuli are conceptually different to pressures; the historical basis of a stimulus may impact on whether pressure and institutional change occurs; pressure exists in a more dynamic capacity rather than only as a catalyst; institutional breakdown is a non-linear irregular process; ethical and survival pressures as new types were identified; institutional current, as an underpinning mechanism, influences how the tension between institutional breakdown and maintenance plays out.