Stability of large flexible damped spacecraft modeled as elastic continua

Vibrational stability of a large flexible, structurally damped spacecraft subject to large rigid body rotations is analysed modelling the system as an elastic continuum. Using solution of rigid body attitude motion under torque free conditions and modal analysis, the vibrational equations are reduced to ordinary differential equations with time-varying coefficients. Stability analysis is carried out using Floquet theory and Sonin-Polya theorem. The cases of spinning and non-spinning spacecraft idealized as a flexible beam plate undergoing simple structural vibration are analysed in detail. The critical damping required for stabilization is shown to be a function of the spacecraft's inertia ratio and the level of disturbance.

Small State Cultures of Consensus : State Traditions and Consensus-Seeking in the Neo-Corporatist and Neutrality Policies in Post-1945 Austria and Finland

Austria and Finland are persistently referred to as the “success stories” of post-1945 European history. Notwithstanding their different points of departure, in the course of the Cold War both countries portrayed themselves as small and neutral border-states in the world dictated by superpower politics. By the 1970s, both countries frequently ranked at the top end in various international classifications regarding economic development and well-being in society. This trend continues today. The study takes under scrutiny the concept of consensus which figures centrally in the two national narratives of post-1945 success. Given that the two domestic contexts as such only share few direct links with one another and are more obviously different than similar in terms of their geographical location, historical experiences and politico-cultural traditions, the analogies and variations in the anatomies of the post-1945 “cultures of consensus” provide an interesting topic for a historical comparative and cross-national examination. The main research question concerns the identification and analysis of the conceptual and procedural convergence points of the concepts of the state and consensus. The thesis is divided into six main chapters. After the introduction, the second chapter presents the theoretical framework in more detail by focusing on the key concepts of the study – the state and consensus. Chapter two also introduces the comparative historical and cross-national research angles. Chapter three grounds the key concepts of the state and consensus in the historical contexts of Austria and Finland by discussing the state, the nation and democracy in a longer term comparative perspective. The fourth and fifth chapter present case studies on the two policy fields, the “pillars”, upon which the post-1945 Austrian and Finnish cultures of consensus are argued to have rested. Chapter four deals with neo-corporatist features in the economic policy making and chapter five discusses the building up of domestic consensus regarding the key concepts of neutrality policies in the 1950s and 1960s. The study concludes that it was not consensus as such but the strikingly intense preoccupation with the theme of domestic consensus that cross-cut, in a curiously analogous manner, the policy-making processes studied. The main challenge for the post-1945 architects of Austrian and Finnish cultures of consensus was to find strategies and concepts for consensus-building which would be compatible with the principles of democracy. Discussed at the level of procedures, the most important finding of the study concerns the triangular mechanism of coordination, consultation and cooperation that set into motion and facilitated a new type of search for consensus in both post-war societies. In this triangle, the agency of the state was central, though in varying ways. The new conceptions concerning a small state’s position in the Cold War world also prompted cross-nationally perceivable willingness to reconsider inherited concepts and procedures of the state and the nation. At the same time, the ways of understanding the role of the state and its relation to society remained profoundly different in Austria and Finland and this basic difference was in many ways reflected in the concepts and procedures deployed in the search for consensus and management of domestic conflicts. For more detailed information, please consult the author.

Accuracy of absorbed dose in external photon beam radiotherapy : what level is sufficient and how to approach it?

Radiation therapy (RT) plays currently significant role in curative treatments of several cancers. External beam RT is carried out mostly by using megavoltage beams of linear accelerators. Tumor eradication and normal tissue complications correlate to dose absorbed in tissues. Normally this dependence is steep and it is crucial that actual dose within patient accurately correspond to the planned dose. All factors in a RT procedure contain uncertainties requiring strict quality assurance. From hospital physicist´s point of a view, technical quality control (QC), dose calculations and methods for verification of correct treatment location are the most important subjects. Most important factor in technical QC is the verification that radiation production of an accelerator, called output, is within narrow acceptable limits. The output measurements are carried out according to a locally chosen dosimetric QC program defining measurement time interval and action levels. Dose calculation algorithms need to be configured for the accelerators by using measured beam data. The uncertainty of such data sets limits for best achievable calculation accuracy. All these dosimetric measurements require good experience, are workful, take up resources needed for treatments and are prone to several random and systematic sources of errors. Appropriate verification of treatment location is more important in intensity modulated radiation therapy (IMRT) than in conventional RT. This is due to steep dose gradients produced within or close to healthy tissues locating only a few millimetres from the targeted volume. The thesis was concentrated in investigation of the quality of dosimetric measurements, the efficacy of dosimetric QC programs, the verification of measured beam data and the effect of positional errors on the dose received by the major salivary glands in head and neck IMRT. A method was developed for the estimation of the effect of the use of different dosimetric QC programs on the overall uncertainty of dose. Data were provided to facilitate the choice of a sufficient QC program. The method takes into account local output stability and reproducibility of the dosimetric QC measurements. A method based on the model fitting of the results of the QC measurements was proposed for the estimation of both of these factors. The reduction of random measurement errors and optimization of QC procedure were also investigated. A method and suggestions were presented for these purposes. The accuracy of beam data was evaluated in Finnish RT centres. Sufficient accuracy level was estimated for the beam data. A method based on the use of reference beam data was developed for the QC of beam data. Dosimetric and geometric accuracy requirements were evaluated for head and neck IMRT when function of the major salivary glands is intended to be spared. These criteria are based on the dose response obtained for the glands. Random measurement errors could be reduced enabling lowering of action levels and prolongation of measurement time interval from 1 month to even 6 months simultaneously maintaining dose accuracy. The combined effect of the proposed methods, suggestions and criteria was found to facilitate the avoidance of maximal dose errors of up to even about 8 %. In addition, their use may make the strictest recommended overall dose accuracy level of 3 % (1SD) achievable.

Hybrid Modelling of Titan's Interaction with the Magnetosphere of Saturn

In this dissertation we study the interaction between Saturn's moon Titan and the magnetospheric plasma and magnetic field. The method of research is a three-dimensional computer simulation model, that is used to simulate this interaction. The simulation model used is a hybrid model. Hybrid models enable individual tracking or tracing of ions and also take into account the particle motion in the propagation of the electromagnetic fields. The hybrid model has been developed at the Finnish Meteorological Institute. This thesis gives a general description of the effects that the solar wind has on Earth and other planets of our solar system. Planetary satellites can also have similar interactions with the solar wind but also with the plasma flows of planetary magnetospheres. Titan is clearly the largest among the satellites of Saturn and also the only known satellite with a dense atmosphere. It is the atmosphere that makes Titan's plasma interaction with the magnetosphere of Saturn so unique. Nevertheless, comparisons with the plasma interactions of other solar system bodies are valuable. Detecting charged plasma particles requires in situ measurements obtainable through scientific spacecraft. The Cassini mission has been one of the most remarkable international efforts in space science. Since 2004 the measurements and images obtained from instruments onboard the Cassini spacecraft have increased the scientific knowledge of Saturn as well as its satellites and magnetosphere in a way no one was probably able to predict. The current level of science on Titan is practically unthinkable without the Cassini mission. Many of the observations by Cassini instrument teams have influenced this research both the direct measurements of Titan as well as observations of its plasma environment. The theoretical principles of the hybrid modelling approach are presented in connection to the broader context of plasma simulations. The developed hybrid model is described in detail: e.g. the way the equations of the hybrid model are solved is shown explicitly. Several simulation techniques, such as the grid structure and various boundary conditions, are discussed in detail as well. The testing and monitoring of simulation runs is presented as an essential routine when running sophisticated and complex models. Several significant improvements of the model, that are in preparation, are also discussed. A main part of this dissertation are four scientific articles based on the results of the Titan model. The Titan model developed during the course of the Ph.D. research has been shown to be an important tool to understand Titan's plasma interaction. One reason for this is that the structures of the magnetic field around Titan are very much three-dimensional. The simulation results give a general picture of the magnetic fields in the vicinity of Titan. The magnetic fine structure of Titan's wake as seen in the simulations seems connected to Alfvén waves an important wave mode in space plasmas. The particle escape from Titan is also a major part of these studies. Our simulations show a bending or turning of Titan's ionotail that we have shown to be a direct result of the basic principles in plasma physics. Furthermore, the ion flux from the magnetosphere of Saturn into Titan's upper atmosphere has been studied. The modelled ion flux has asymmetries that would likely have a large impact in the heating in different parts of Titan's upper atmosphere.

Five-level inverter scheme for an open-end winding induction machine with less number of switches

Higher level of inversion is achieved with a less number of switches in the proposed scheme. The scheme proposes a five-level inverter for an open-end winding induction motor which uses only two DC-link rectifiers of voltage rating of Vdc/4, a neutral-point clamped (NPC) three-level inverter and a two-level inverter. Even though the two-level inverter is connected to the high-voltage side, it is always in square-wave operation. Since the two-level inverter is not switching in a pulse width modulated fashion and the magnitude of switching transient is only half compared to the convention three-level NPC inverter, the switching losses and electromagnetic interference is not so high. The scheme is experimentally verified on a 2.5 kW induction machine.

Baculovirus mediated high-level expression of luciferase in silkworm cells and larvae

Bombyx mori nuclear polyhedrosis virus (BmNPV)-based baculovirus expression system exploits silkworm larvae as an economical alternative to large-scale cell cultures for production of biomolecules. To generate recombinant BmNPV at high efficiency, we have achieved high efficiency transfection of B. mori cells, BmN, through lipofection. Optimal conditions for lipofection were standardized by quantification of the transient expression level of firefly luciferase (luc) reporter gene under control of an immediate early gene promoter of BmNPV Lipofection was 50-fold and 100-fold more efficient than the calcium phosphate method for transfecting BmN and Sf9 cells, respectively. Lipofection enabled us to generate a recombinant BmNPV (vBmluc), harboring luc under control of the strong polyhedrin promoter On infection with vBmluc, luciferase was expressed at very high levels, 170 mu g/10(6) BmN cells or 13 mg/larva. Expression of luciferase in vBmluc-infected larvae was visualized by luminescence emission instantaneously following luciferin injection generating ''glowing silkworms''.

Reconstructing Solid Model from 2D Scanned Images of Biological Organs for Finite Element Simulation

This work presents a methodology to reconstruct 3D biological organs from image sequences or other scan data using readily available free softwares with the final goal of using the organs (3D solids) for finite element analysis. The methodology deals with issues such as segmentation, conversion to polygonal surface meshes, and finally conversion of these meshes to 3D solids. The user is able to control the detail or the level of complexity of the solid constructed. The methodology is illustrated using 3D reconstruction of a porcine liver as an example. Finally, the reconstructed liver is imported into the commercial software ANSYS, and together with a cyst inside the liver, a nonlinear analysis performed. The results confirm that the methodology can be used for obtaining 3D geometry of biological organs. The results also demonstrate that the geometry obtained by following this methodology can be used for the nonlinear finite element analysis of organs. The methodology (or the procedure) would be of use in surgery planning and surgery simulation since both of these extensively use finite elements for numerical simulations and it is better if these simulations are carried out on patient specific organ geometries. Instead of following the present methodology, it would cost a lot to buy a commercial software which can reconstruct 3D biological organs from scanned image sequences.

Metabolites of PPI-2458, a selective, irreversible inhibitor of methionine aminopeptidase-2: structure determination and In vivo activity

The natural product fumagillin exhibits potent antiproliferative and antiangiogenic properties. The semisynthetic analog PPI-2458, (3R,4S,5S,6R)-5-methoxy-4-(2R,3R)-2-methyl-3-(3-methylbut-2-enyl) oxiran-2-yl]-1-oxaspiro2.5]octan-6-yl] N-(2R)-1-amino-3-methyl-1-oxobutan-2-yl]carbamate, demonstrates rapid inactivation of its molecular target, methionine aminopeptidase-2 (MetAP2), and good efficacy in several rodent models of cancer and inflammation with oral dosing despite low apparent oral bioavailability. To probe the basis of its in vivo efficacy, the metabolism of PPI-2458 was studied in detail. Reaction phenotyping identified CYP3A4/5 as the major source of metabolism in humans. Six metabolites were isolated from liver microsomes and characterized by mass spectrometry and nuclear resonance spectroscopy, and their structures were confirmed by chemical synthesis. The synthetic metabolites showed correlated inhibition of MetAP2 enzymatic activity and vascular endothelial cell growth. In an ex vivo experiment, MetAP2 inhibition in white blood cells, thymus, and lymph nodes in rats after single dosing with PPI-2458 and the isolated metabolites was found to correlate with the in vitro activity of the individual species. In a phase 1 clinical study, PPI-2458 was administered to patients with non-Hodgkin lymphoma. At 15 mg administered orally every other day, MetAP2 in whole blood was 80% inactivated for up to 48 hours, although the exposure of the parent compound was only similar to 10% that of the summed cytochrome P450 metabolites. Taken together, the data confirm the participation of active metabolites in the in vivo efficacy of PPI-2458. The structures define a metabolic pathway for PPI-2458 that is distinct from that of TNP-470 ((3R, 4S, 5S, 6R)-5-methoxy-4-(2R, 3R)-2-methyl-3-(3-methylbut-2-enyl)oxiran-2-yl]-1-oxaspiro2.5]octan-6 -yl] N-(2-chloroacetyl)carbamate). The high level of MetAP2 inhibition achieved in vivo supports the value of fumagillin-derived therapeutics for angiogenic diseases.

A fluorescent molecularly-imprinted polymer gate with temperature and pH as inputs for detection of alpha-fetoprotein

In this work, we have reported a new approach on the use of stimuli-responsive molecularly imprinted polymer (MIP) for trace level sensing of alpha-fetoprotein (AFP), which is a well know cancer biomarker. The stimuli-responsive MIP is composed of three components, a thermo-responsive monomer, a pH responsive component (tyrosine derivative) and a highly fluorescent vinyl silane modified carbon dot. The synthesized AFP-imprinted polymer possesses excellent selectivity towards their template molecule and dual-stimuli responsive behavior. Along with this, the imprinted polymer was also explored as `OR' logic gate with two stimuli (pH and temperature) as inputs. However, the non-imprinted polymers did not have such `OR' gate property, which confirms the role of template binding. The imprinted polymer was also used for estimation of AFP in the concentration range of 3.96-80.0 ng mL(-1), with limit of detection (LOD) 0.42 ng mL(-1). The role of proposed sensor was successfully exploited for analysis of AFP in real human blood plasma, serum and urine sample. (C) 2015 Elsevier B.V. All rights reserved.

Mechanism Analysis of Landslide of a Layered Slope Induced by Drawdown of Water Level

The frequent drawdown of water level of Yangtze River will greatly influence the stability of the widely existing slopes in the Three Gorges reservoir zone, especially those layered ones. Apart from the fluctuating speed of water level, the different geological materials will also play important roles in the failure of slopes. Thus, it must be first to study the mechanism of such a landslide caused by drawdown of water level.A new experimental setup is designed to study the performance of a layered slope under the drawdown of water level. The pattern of landslide of a layered slope induced by drawdown of water level has been explored by means of simulating experiments. The influence of fluctuating speed of water level on the stability of the layered slope is probed,especially the whole process of deformation and development of landslide of the slope versus time. The experimental results show that the slope is stable during the water level rising, and the sliding body occurs in the upper layer of the slope under a certain drawdown speed of water level. In the process of slope failure, some new small sliding body will develop on the main sliding body, and the result is that they speed up the disassembly of the whole slope.Based on the simulating experiment on landslide of a layered slope induced by drawdown of water level, the stress and displacement field of the slope are calculated.The seepage velocity, the pore water pressure, and the gradient of pore water head are also calculated for the whole process of drawdown of water level. The computing results are in good agreement with the experimental results. Accordingly, the mechanism of deformation and landslide of the layered slope induced by drawdown of water level is analyzed. It may provide basis for treating this kind of layered slopes in practical engineering.

Influence of low-gravity level on crystal-growth in floating-zone

The influence of low gravity level on crystal growth in the floating zone, which involves thermocapillary convection, phase change convection, thermal and solutal diffusion, is investigated numerically by a finite element method for the silicon crystal growth process. The velocity, temperature, concentration fields and phase change interfaces depending on heating temperature and growth rates are analyzed. The influence of low gravity level on the concentration is studied especially. The results show that the non-uniformities of concentration are about 10(-3) for growth rate nu(p) = 5.12 x 10(-8) m/s, 10(-2) for nu(p) = 5.12 x 10(-7) m/s and relatively larger for larger growth rate in the gravity level g = 0-9.8 m/s2. The thermocapillary effect is strong in comparison with the Bridgman system, and the level of low gravity is relatively insensitive for lower growth rates.

High-speed streams from coronal holes and the accelerating mechanism of the solar-wind

In this paper, the general Mach number equation is derived, and the influence of typical energy forms in the solar wind is analysed in detail. It shows that the accelerating process of the solar wind is influenced critically by the form of heating in the corona, and that the transonic mechanism is mainly the result of the adjustment of the variation of the crosssection of flowing tubes and the heat source term.The accelerating mechanism for both the high-speed stream from the coronal hole and the normal solar wind is similar. But, the temperature is low in the lower level of the coronal hole and more heat energy supply in the outside is required, hence the high speed of the solar wind; while the case with the ordinary coronal region is just the opposite, and the velocity of the solar wind is therefore lower. The accelerating process for various typical parameters is calculated, and it is found that the high-speed stream may reach 800 km/sec.

An examination of fluctuations in the “concentration index” of purse seiners and baitboats in the fishery for tropical tunas in the Eastern Pacific, 1951-1961

ENGLISH: In the eastern Pacific Ocean nearly all of the commercial catches of yellowfin tuna (Thunnus albacares) and skipjack (Katsuwonus pelamis) are taken by two types of vessels, baitboats, which use pole and line in conjunction with live-bait, and purse-seiners. From its inception until very recently (1959), this fishery was dominated by baitboats. This method of fishing has been described by Godsil (1938) and Shimada and Schaefer (1956). From 1951 through 1958 baitboats caught between 66.4 and 90.8 per cent of the yellowfin and between 87.2 and 95.3 per cent of the skipjack landed by the California-based fleet. These vessels fished for tuna throughout the year and covered virtually all of the area from southern California to northern Chile. The purse-seine fishery for tunas developed out of the round-haul net fisheries for California sardines and other species. Scofield (1951) gives a detailed description of the development of gear and fishing methods. Prior to 1959 many of the seiners engaged in other fisheries during the fall and early winter months and consequently most of the fishing effort for tuna occurred in the period February-August. The vessels were quite small, averaging approximately 120 tons carrying capacity (Broadhead and Marshall, 1960), in comparison to the baitboats, of which the most numerous size-class was 201-300 tons. The seiners were naturally more restricted in range than the baitboats and most of their effort was restricted to the northern grounds. During the period 1959-61 most of the large baitboats were converted for purse-seining and the existing seiner fleet was modernized. These developments increased the range of the seiner fleet and resulted in a wider and more nearly even spatial and temporal distribution of effort. By the early part of 1961, the purse-seine fleet approximated the level of the preconversion baitboat fleet in amount of effort applied and area covered. The changes in the purse-seine fishery and the fishing methods employed in the modernized fleet are described by Orange and Broadhead (1959), Broadhead and Marshall (1960), McNeely (1961) and Broadhead (1962). The change in the relative importance of the two gears is illustrated by the decline in the proportion of the total logged tonnage landed by California-based baitboats, in comparison to the proportion landed by seiners. In 1959 baitboats landed 49.5 per cent of the yellowfin and 87.8 per cent of the skipjack. In 1960 these percentages were 22.9 and 74.7 respectively and in 1961 the decline continued to 12.6 per cent of the yellowfin and 30.0 per cent of the skipjack (Schaefer, 1962). In previous Bulletins of this Commission (Griffiths, 1960; Calkins, 1961) the baitboat catch and effort statistics were used to compute two indices of population density and an index of concentration of fishing effort and the fluctuations of these indices were analyzed in some detail. Due to the change in the relative importance of the two gears it is appropriate to extend this investigation to include the purse-seine data. The objectives of this paper are to compute two indices of population density and an index of concentration of fishing effort and to examine the fluctuations in these indices before and after the changes in the fishery. A further objective is to compare the purse-seine indices with those of the baitboats for the same time periods. SPANISH: En el Océano Pacífico Oriental casi todas las capturas comerciales del atún aleta amarilla (Thunnus albacares) y del barrilete (Katsuwonus pelamis) son efectuadas por dos tipos de barcos, los barcos de carnada que emplean la caña y el anzuelo en conjunto con la carnada viva, y los barcos rederos. Desde su comienzo hasta hace poco tiempo (1959), esta pesquería estaba dominada por los barcos de carnada. El método de pesca usado por estos barcos ha sido descrito por Godsil (1938) y por Shimada y Schaefer (1956). De 1951 a 1958, los barcos de carnada pescaron entre el 66.4 y el 90.8 por ciento del atún aleta amarilla y entre el 87.2 y el 95.3 por ciento del barrilete descargados por la flota que tiene su base en California. Estos barcos pescaron atún durante todo el año y cubrieron virtualmente toda el área de California meridional hasta la parte norte de Chile. La pesquería del atún con redes de cerco se originó en las pesquerías de las sardinas de California y otras especies, con redes que se remolcaban circularmente. Scofield (1951) dá una descripción detallada del desarrollo de los métodos y del equipo de pesca. Antes de 1959 muchos de los rederos se dedicaban a otras pesquerías durante los meses del otoño y a principios del invierno y consecuentemente, la mayor parte del esfuerzo depesca para la producción del atún ocurría en el período febrero-agosto. Las embarcaciones eran bastante pequeñas, con un promedio de aproximadamente 120 toneladas de capacidad para el transporte (Broadhead y Marshall, 1960) en comparación con los barcos de carnada, de los cuales la clase de tamaño más numerosa era de 201 a 300 toneladas. Los rederos estaban naturalmente más restringidos en su radio de acción que los barcos de carnada y la mayor parte de su esfuerzo se limitaba a las localidades del norte. Durante el período 1959-61, la mayoría de los grandes barcos de carnada fueron convertidos al sistema de pesca con redes de cerco, y se modernizó la flota existente de los rederos. Estos cambios aumentaron el alcance de la flota de los barcos rederos dando como resultado una distribución más amplia y casi más uniforme del esfuerzo espaciado y temporal. En la primera parte del año 1961, la flota de rederos se aproximó al nivel de la preconversión de la flota de clipers, en la cantidad de esfuerzo aplicado y al área comprendida. Los cambios en la pesquería con red y los métodos de pesca empleados en la flota modernizada, han sido descritos por Orange y Broadhead (1959), Broadl1ead y Marshall (1960), McNeely (1961) y Broadhead (1962). El cambio en la importancia relativa de los dos sistemas de pesca está ilustrado por la declinación en la proporción del tonelaje total registrado, como descargado por los barcos de carnada que tienen su base en California, comparado con la proporción desembarcada por los barcos rederos. En 1959 los clipers descargaron el 49.5 por ciento del atún aleta amarilla y el 87.8 por ciento del barrilete. En 1960 estos porcentajes fueron del 22.9 y 74.7 respectivamente, y en 1961 continuó la reducción hasta el 12.6 por ciento del atún aleta amarilla y el 30.0 por ciento del barrilete (Schaefer, 1962). En Boletines anteriores de la Comisión (Griffiths, 1960; Calkins, 1961) las estadísticas de la pesca y el esfuerzo de los clipers se utilizaron para computar dos índices de la densidad de población y un índice de la concentración del esfuerzo de pesca, y se analizaron algo detalladamente las fluctuaciones de estos índices. Debido al cambio en la importancia relativa de los dos sistemas de pesca, es conveniente extender esta investigación para incluir los datos correspondientes a los barcos rederos. Los objetivos del presente estudio son de computar dos índices de la densidad de población y un índice de la concentración del esfuerzo de pesca, y examinar las fluctuaciones en estos índices, antes y después de los cambios en la pesquería. Otro objetivo es de comparar los índices de los barcos rederos, con aquellos de los clipers en los mismos períodos de tiempo.

Assessing the accessibility of everyday products

If a product is being designed to be genuinely inclusive, then the designers need to be able to assess the level of exclusion of the product that they are working on and to identify possible areas of improvement. To be of practical use, the assessments need to be quick, consistent and repeatable. The aim of this workshop is to invite attendees to participate in the evaluation of a number of everyday objects using an assessment technique being considered by the workshop organisers. The objectives of the workshop include evaluating the effectiveness of the assessment method, evaluating the accessibility of the products being assessed and to suggest revisions to the assessment scales being used. The assessment technique is to be based on the ONS capability measures [1]. This source recognises fourteen capability scales of which seven are particularly pertinent to product evaluation, namely: motion, dexterity, reach and stretch, vision, hearing, communication, and intellectual functioning. Each of these scales ranges from 0 (fully able) through 1 (minimal impairment) to 10 (severe impairment). The attendees will be asked to rate the products on these scales. Clearly the assessed accessibility of the product depends on the assumptions made about the context of use. The attendees will be asked to clearly note the assumptions that they are making about the context in which the product is being assessed. For instance, with a hot water bottle, assumptions have to be made about the availability of hot water and these can affect the overall accessibility rating. The workshop organisers will not specify the context of use as the aim is to identify how assessors would use the assessment method in the real world. The objects being assessed will include items such as remote controls, pill bottles, food packaging, hot water bottles and mobile telephones. the attendees will be encouraged to assess two or more products in detail. Helpers will be on hand to assist and observe the assessments. The assessments will be collated and compared and feedback about the assessment method sought from the attendees. Drawing on a preliminary review of the assessment results, initial conclusions will be presented at the end of the workshop. More detailed analyses will be made available in subsequent proceedings. It is intended that the workshop will provide workshop attendees with an opportunity to perform hands-on assessment of a number everyday products and identify features which are inclusive and those that are not. It is also intended to encourage an appreciation of the capabilities to be considered when evaluating accessibility.

Development of Metalloenzyme Dioxygen Reduction Cathodes

The prime thrust of this dissertation is to advance the development of fuel cell dioxygen reduction cathodes that employ some variant of multicopper oxidase enzymes as the catalyst. The low earth-abundance of platinum metal and its correspondingly high market cost has prompted a general search amongst chemists and materials scientists for reasonable alternatives to this metal for facilitating catalytic dioxygen reduction chemistry. The multicopper oxidases (MCOs), which constitute a class of enzyme that naturally catalyze the reaction O₂ + 4H⁺ + 4e^- → 2H₂O, provide a promising set of biochemical contenders for fuel cell cathode catalysts. In MCOs, a substrate reduces a copper atom at the type 1 site, where charge is then transferred to a trinuclear copper cluster consisting of a mononuclear type 2 or “normal copper” site and a binuclear type 3 copper site. Following the reduction of all four copper atoms in the enzyme, dioxygen is then reduced to water in two two-electron steps, upon binding to the trinuclear copper cluster. We identified an MCO, a laccase from the hyperthermophilic bacterium Thermus thermophilus strain HB27, as a promising candidate for cathodic fuel cell catalysis. This protein demonstrates resilience at high temperatures, exhibiting no denaturing transition at temperatures high as 95°C, conditions relevant to typical polymer electrolyte fuel cell operation.

In Chapter I of this thesis, we discuss initial efforts to physically characterize the enzyme when operating as a heterogeneous cathode catalyst. Following this, in Chapter II we then outline the development of a model capable of describing the observed electrochemical behavior of this enzyme when operating on porous carbon electrodes. Developing a rigorous mathematical framework with which to describe this system had the potential to improve our understanding of MCO electrokinetics, while also providing a level of predictive power that might guide any future efforts to fabricate MCO cathodes with optimized electrochemical performance. In Chapter III we detail efforts to reduce electrode overpotentials through site-directed mutagenesis of the inner and outer-sphere ligands of the Cu sites in laccase, using electrochemical methods and electronic spectroscopy to try and understand the resultant behavior of our mutant constructs. Finally, in Chapter IV, we examine future work concerning the fabrication of enhanced MCO cathodes, exploring the possibility of new cathode materials and advanced enzyme deposition techniques.