Evaluation of a sol-gel derived carbon composite electrode as an amperometric detector for capillary electrophoresis

In this paper, we report the construction and application of a sol-gel derived carbon composite electrode (CCE) as an amperometric detector for capillary electrophoresis. The electrochemical properties were characterized and compared with those of conventional carbon fiber and carbon paste electrode (CPE). Experimental results show that peak-to-peak noise of CCE was about 20% of CPE and electrode capacitance was comparatively low. When applied to the detection of dopamine and epinephrine, the optimal detection potential for CCE was 0.1 V lower than CPE under the same separation conditions; CCE with diameter of 75 and 100 mum could achieve a low detection limit of 3.10(-8) and 6.10(-8) M for the detection of epinephrine, which approaching that of the 33-mum diameter carbon fiber electrode. Also, the linearity for epinephrine at CCE was more than two orders of magnitude, which was slightly wider than that of carbon fiber electrode. Applications to real sample analysis were tested by the determination of betahistine dihydrochloride in tablets and human urine. Using CCE with diameter less than or equal to100 mum as an amperometric detector after capillary electrophoresis separation, a low detection limit and a wide linear range combined with excellent reproducibility were obtained. This CCE possesses of many advantages, namely, convenience, ease of fabrication, low cost and high stability.

CRYSTAL-STRUCTURE AND THERMODYNAMIC PARAMETERS OF NYLON-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density rho(c), amorphous density rho(a), equilibrium heat of fusion DELTAH(m)degrees and equilibrium melting temperature T(m)degrees. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity, rho(c) and rho(a) were estimated to be 1.098 and 1.003 g/cm3 respectively. The rho(c) obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 angstrom, b = 5.4 angstrom, c = 27.8 angstrom, alpha = 49-degrees, beta = 77-degrees, gamma = 63.5-degrees. The unit cell contained one monomeric unit, the space group was P1BAR, and the correct value of rho(c) was 1.135 g/cm3. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. DELTAH(m)degrees was estimated to be 244.0 J/g by extrapolation of DELTAH(m)degrees in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V(sp)c = 1/rho(c)). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T(m)-T(c) method failed in determining T(m)degrees and a Kamide double extrapolation method was adopted. The T(m)degrees value so obtained was 487 K.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Qualitative evaluation of KA24 (Knowledge Access 24)

Durbin, J. & Urquhart, C. (2003). Qualitative evaluation of KA24 (Knowledge Access 24). Aberystwyth: Department of Information Studies, University of Wales Aberystwyth. Sponsorship: Knowledge Access 24 (NHS)

Revisão bibliográfica

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Medicina Dentária

Mermera: Non-Coherent Distributed Shared Memory for Parallel Computing

The proliferation of inexpensive workstations and networks has prompted several researchers to use such distributed systems for parallel computing. Attempts have been made to offer a shared-memory programming model on such distributed memory computers. Most systems provide a shared-memory that is coherent in that all processes that use it agree on the order of all memory events. This dissertation explores the possibility of a significant improvement in the performance of some applications when they use non-coherent memory. First, a new formal model to describe existing non-coherent memories is developed. I use this model to prove that certain problems can be solved using asynchronous iterative algorithms on shared-memory in which the coherence constraints are substantially relaxed. In the course of the development of the model I discovered a new type of non-coherent behavior called Local Consistency. Second, a programming model, Mermera, is proposed. It provides programmers with a choice of hierarchically related non-coherent behaviors along with one coherent behavior. Thus, one can trade-off the ease of programming with coherent memory for improved performance with non-coherent memory. As an example, I present a program to solve a linear system of equations using an asynchronous iterative algorithm. This program uses all the behaviors offered by Mermera. Third, I describe the implementation of Mermera on a BBN Butterfly TC2000 and on a network of workstations. The performance of a version of the equation solving program that uses all the behaviors of Mermera is compared with that of a version that uses coherent behavior only. For a system of 1000 equations the former exhibits at least a 5-fold improvement in convergence time over the latter. The version using coherent behavior only does not benefit from employing more than one workstation to solve the problem while the program using non-coherent behavior continues to achieve improved performance as the number of workstations is increased from 1 to 6. This measurement corroborates our belief that non-coherent shared memory can be a performance boon for some applications.

The Viking age glass beads of Ireland and their North Atlantic context

Hitherto, the majority of studies which have included the discussion of Viking glass beads have mainly focused on the assemblages from individual sites, with limited use of known parallels. Exceptions to this include recent publications regarding the Icelandic material and Callmer’s 1977 catalogue of the finds from mainland Scandinavia, now over thirty years old. Analysis of these finds from Ireland was, for the most part, non-existent. The aim of this research is to address this lack of analysis within Ireland, while incorporating the wider context of the beads within the Viking North Atlantic. The research thus examines the use of glass beads of diagnostically Scandinavian manufacture and import found in Ireland, particularly in relation to their context and distribution. The history of research from Ireland as well as from across the Viking world is considered and explored throughout the thesis, with critique of methods and discussions used. Focussed analysis of both published and unpublished material detailing artefacts from Scandinavia (especially Vestfold), Britain, Iceland, the Faroe Islands and L’Anse aux Meadows is presented within the thesis in order to provide the greater picture for the core section of the thesis, the glass beads found in Ireland. Three appendices are included within Volume 2, databases of the glass beads under discussion from Ireland, the Vestfold region graves in Norway and the topsoil finds from the Kaupang trading place, also located within Vestfold. These appendices therefore represent the first-hand analysis of glass beads by the author. In total, this research represents the most up-to-date analysis of Viking glass beads from Ireland and presents a new look at the patterns of use, trade and interpersonal contact that affected the everyday lives of individuals living within Viking Age Ireland.

Development of a general internet attitude scale and internet self-efficacy scale

The measurement of users’ attitudes towards and confidence with using the Internet is an important yet poorly researched topic. Previous research has encountered issues that serve to obfuscate rather than clarify. Such issues include a lack of distinction between the terms ‘attitude’ and ‘self-efficacy’, the absence of a theoretical framework to measure each concept, and failure to follow well-established techniques for the measurement of both attitude and self-efficacy. Thus, the primary aim of this research was to develop two statistically reliable scales which independently measure attitudes towards the Internet and Internet self-efficacy. This research addressed the outlined issues by applying appropriate theoretical frameworks to each of the constructs under investigation. First, the well-known three component (affect, behaviour, cognition) model of attitudes was applied to previous Internet attitude statements. The scale was distributed to four large samples of participants. Exploratory factor analyses revealed four underlying factors in the scale: Internet Affect, Internet Exhilaration, Social Benefit of the Internet and Internet Detriment. The final scale contains 21 items, demonstrates excellent reliability and achieved excellent model fit in the confirmatory factor analysis. Second, Bandura’s (1997) model of self-efficacy was followed to develop a reliable measure of Internet self-efficacy. Data collected as part of this research suggests that there are ten main activities which individuals can carry out on the Internet. Preliminary analyses suggested that self-efficacy is confounded with previous experience; thus, individuals were invited to indicate how frequently they performed the listed Internet tasks in addition to rating their feelings of self-efficacy for each task. The scale was distributed to a sample of 841 participants. Results from the analyses suggest that the more frequently an individual performs an activity on the Internet, the higher their self-efficacy score for that activity. This suggests that frequency of use ought to be taken into account in individual’s self-efficacy scores to obtain a ‘true’ self-efficacy score for the individual. Thus, a formula was devised to incorporate participants’ previous experience of Internet tasks in their Internet self-efficacy scores. This formula was then used to obtain an overall Internet self-efficacy score for participants. Following the development of both scales, gender and age differences were explored in Internet attitudes and Internet self-efficacy scores. The analyses indicated that there were no gender differences between groups for Internet attitude or Internet self-efficacy scores. However, age group differences were identified for both attitudes and self-efficacy. Individuals aged 25-34 years achieved the highest scores on both the Internet attitude and Internet self-efficacy measures. Internet attitude and self-efficacy scores tended to decrease with age with older participants achieving lower scores on both measures than younger participants. It was also found that the more exposure individuals had to the Internet, the higher their Internet attitude and Internet self-efficacy scores. Examination of the relationship between attitude and self-efficacy found a significantly positive relationship between the two measures suggesting that the two constructs are related. Implication of such findings and directions for future research are outlined in detail in the Discussion section of this thesis.

Beyond simple imaging with energetic beams – nanopatterning, correlative microscopy and statistical analysis of inclusions

Electron microscopy (EM) has advanced in an exponential way since the first transmission electron microscope (TEM) was built in the 1930’s. The urge to ‘see’ things is an essential part of human nature (talk of ‘seeing is believing’) and apart from scanning tunnel microscopes which give information about the surface, EM is the only imaging technology capable of really visualising atomic structures in depth down to single atoms. With the development of nanotechnology the demand to image and analyse small things has become even greater and electron microscopes have found their way from highly delicate and sophisticated research grade instruments to key-turn and even bench-top instruments for everyday use in every materials research lab on the planet. The semiconductor industry is as dependent on the use of EM as life sciences and pharmaceutical industry. With this generalisation of use for imaging, the need to deploy advanced uses of EM has become more and more apparent. The combination of several coinciding beams (electron, ion and even light) to create DualBeam or TripleBeam instruments for instance enhances the usefulness from pure imaging to manipulating on the nanoscale. And when it comes to the analytic power of EM with the many ways the highly energetic electrons and ions interact with the matter in the specimen there is a plethora of niches which evolved during the last two decades, specialising in every kind of analysis that can be thought of and combined with EM. In the course of this study the emphasis was placed on the application of these advanced analytical EM techniques in the context of multiscale and multimodal microscopy – multiscale meaning across length scales from micrometres or larger to nanometres, multimodal meaning numerous techniques applied to the same sample volume in a correlative manner. In order to demonstrate the breadth and potential of the multiscale and multimodal concept an integration of it was attempted in two areas: I) Biocompatible materials using polycrystalline stainless steel and II) Semiconductors using thin multiferroic films. I) The motivation to use stainless steel (316L medical grade) comes from the potential modulation of endothelial cell growth which can have a big impact on the improvement of cardio-vascular stents – which are mainly made of 316L – through nano-texturing of the stent surface by focused ion beam (FIB) lithography. Patterning with FIB has never been reported before in connection with stents and cell growth and in order to gain a better understanding of the beam-substrate interaction during patterning a correlative microscopy approach was used to illuminate the patterning process from many possible angles. Electron backscattering diffraction (EBSD) was used to analyse the crystallographic structure, FIB was used for the patterning and simultaneously visualising the crystal structure as part of the monitoring process, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to analyse the topography and the final step being 3D visualisation through serial FIB/SEM sectioning. II) The motivation for the use of thin multiferroic films stems from the ever-growing demand for increased data storage at lesser and lesser energy consumption. The Aurivillius phase material used in this study has a high potential in this area. Yet it is necessary to show clearly that the film is really multiferroic and no second phase inclusions are present even at very low concentrations – ~0.1vol% could already be problematic. Thus, in this study a technique was developed to analyse ultra-low density inclusions in thin multiferroic films down to concentrations of 0.01%. The goal achieved was a complete structural and compositional analysis of the films which required identification of second phase inclusions (through elemental analysis EDX(Energy Dispersive X-ray)), localise them (employing 72 hour EDX mapping in the SEM), isolate them for the TEM (using FIB) and give an upper confidence limit of 99.5% to the influence of the inclusions on the magnetic behaviour of the main phase (statistical analysis).

Towards policy-based self-configuration of embedded systems

This paper describes work towards the deployment of flexible self-management into real-time embedded systems. A challenging project which focuses specifically on the development of a dynamic, adaptive automotive middleware is described, and the specific self-management requirements of this project are discussed. These requirements have been identified through the refinement of a wide-ranging set of use cases requiring context-sensitive behaviours. A sample of these use-cases is presented to illustrate the extent of the demands for self-management. The strategy that has been adopted to achieve self-management, based on the use of policies is presented. The embedded and real-time nature of the target system brings the constraints that dynamic adaptation capabilities must not require changes to the run-time code (except during hot update of complete binary modules), adaptation decisions must have low latency, and because the target platforms are resource-constrained the self-management mechanism have low resource requirements (especially in terms of processing and memory). Policy-based computing is thus and ideal candidate for achieving the self-management because the policy itself is loaded at run-time and can be replaced or changed in the future in the same way that a data file is loaded. Policies represent a relatively low complexity and low risk means of achieving self-management, with low run-time costs. Policies can be stored internally in ROM (such as default policies) as well as externally to the system. The architecture of a designed-for-purpose powerful yet lightweight policy library is described. A suitable evaluation platform, supporting the whole life-cycle of feasibility analysis, concept evaluation, development, rigorous testing and behavioural validation has been devised and is described.

A case study of the effectiveness of the electronic survey as a research tool for measuring students' experience of e-learning

This paper uses a case study approach to consider the effectiveness of the electronic survey as a research tool to measure the learner voice about experiences of e-learning in a particular institutional case. Two large scale electronic surveys were carried out for the Student Experience of e-Learning (SEEL) project at the University of Greenwich in 2007 and 2008, funded by the UK Higher Education Academy (HEA). The paper considers this case to argue that, although the electronic web-based survey is a convenient method of quantitative and qualitative data collection, enabling higher education institutions swiftly to capture multiple views of large numbers of students regarding experiences of e-learning, for more robust analysis, electronic survey research is best combined with other methods of in-depth qualitative data collection. The advantages and disadvantages of the electronic survey as a research method to capture student experiences of e-learning are the focus of analysis in this short paper, which reports an overview of large-scale data collection (1,000+ responses) from two electronic surveys administered to students using surveymonkey as a web-based survey tool as part of the SEEL research project. Advantages of web-based electronic survey design include flexibility, ease of design, high degree of designer control, convenience, low costs, data security, ease of access and guarantee of confidentiality combined with researcher ability to identify users through email addresses. Disadvantages of electronic survey design include the self-selecting nature of web-enabled respondent participation, which tends to skew data collection towards students who respond effectively to email invitations. The relative inadequacy of electronic surveys to capture in-depth qualitative views of students is discussed with regard to prior recommendations from the JISC-funded Learners' Experiences of e-Learning (LEX) project, in consideration of the results from SEEL in-depth interviews with students. The paper considers the literature on web-based and email electronic survey design, summing up the relative advantages and disadvantages of electronic surveys as a tool for student experience of e-learning research. The paper concludes with a range of recommendations for designing future electronic surveys to capture the learner voice on e-learning, contributing to evidence-based learning technology research development in higher education.

Characterisation of freeze-dried wafers and solvent evaporated films as potential drug delivery systems to mucosal surfaces

Freeze-dried (lyophilised) wafers and solvent cast films from sodium alginate (ALG) and sodium carboxymethylcellulose (CMC) have been developed as potential drug delivery systems for mucosal surfaces including wounds. The wafers (ALG, CMC) and films (CMC) were prepared by freeze-drying and drying in air (solvent evaporation) respectively, aqueous gels of the polymers containing paracetamol as a model drug. Microscopic architecture was examined using scanning electron microscopy, hydration characteristics with confocal laser scanning microscopy and dynamic vapour sorption. Texture analysis was employed to investigate mechanical characteristics of the wafers during compression. Differential scanning calorimetry was used to investigate polymorphic changes of paracetamol occurring during formulation of the wafers and films. The porous freeze-dried wafers exhibited higher drug loading and water absorption capacity than the corresponding solvent evaporated films. Moisture absorption, ease of hydration and mechanical behaviour were affected by the polymer and drug concentration. Two polymorphs of paracetamol were observed in the wafers and films, due to partial conversion of the original monoclinic to the orthorhombic polymorph during the formulation process. The results showed the potential of employing the freeze-dried wafers and solvent evaporated films in diverse mucosal applications due to their ease of hydration and based on different physical mechanical properties exhibited by both type of formulations.

Assessment of the potential impacts of coasteering on rocky intertidal habitats in Wales

The relatively new recreational pursuit of coasteering, which has developed in the St David's area of Pembrokeshire, appears to be expanding rapidly. The majority of local commercial recreation providers (outdoor pursuit centers etc.) now appear to offer this pursuit. The majority of the rocky coastlines where it takes place lie within Pembrokeshire Marine Special Area of Conservation (SAC), and are also Sites of Special Scientific Interest (SSSI). No assessment has yet been undertaken of coasteering's potential impact on the intertidal habitats. Therefore the Countryside Council for Wales (CCW) commissioned the Marine Life Information Network (MarLIN) to undertake a desk study of the likely environmental effects of coasteering on rocky intertidal habitats within the Pembrokeshire marine SAC. The desk study was based on a review of the available literature, and in particular the effects of trampling on rocky intertidal communities. Communities (as biotopes) within the Pembrokeshire marine SAC likely to be exposed to coasteering activities were identified from Phase I biotope data for the area, provided by CCW. Where possible, existing research by MarLIN into the intolerance, recoverability and sensitivity of the biotopes identified, was used to identify their potential vulnerability to trampling. The literature review revealed that: - foliose canopy forming algae (e.g. fucoids) were particularly intolerant and sensitive to trampling impacts; - trampling damaged erect coralline turfs, barnacles, and resulted in an increase in bare space; in some cases paths across the shore were visible; - on brown algae dominated shores, understorey algae could suffer due to increased desiccation but algal turf species, opportunists and gastropod grazers (e.g. limpets) could increase in abundance as an indirect effect of trampling, and that - trampling impacts resulted from physical contact and wear and were dependant on the intensity, duration, and frequency of trampling, and even the type of footwear used. A total of 19 intolerant rocky intertidal biotopes were identified as potentially vulnerable to trampling and hence coasteering within the Pembrokeshire marine SAC, of which six are of Welsh importance and eight are nationally rare or scarce. Trampling is a highly localized impact and it was not possible to identify biotopes, and hence communities, actually impacted by coasteering activities in the Pembrokeshire marine SAC. In addition, the majority of the literature addresses the impacts of trampling on wave sheltered or moderately exposed brown algal dominated shores, while coasteering occurs on more wave exposed, steeply inclined shores. Therefore, direct survey of the routes used by coasteering groups within the Pembrokeshire marine SAC is required to identify the intensity, duration and frequency of trampling impact, together with the communities impacted. Given the paucity of data concerning trampling effects in the rocky intertidal in the UK, a survey of the impacts of coasteering would provide an opportunity to examine the effects of trampling and visitor use in steep rocky, wave exposed shores. The report recognizes the potential to engage coasteerers in contributing to the development of strategies for minimizing adverse impacts, recording impacts and collecting information of use in identifying climate change and the occurrence of non-native species.

Acquisition of continuous plankton recorder data

The Continuous Plankton Recorder has been deployed on a seasonal basis in the north Pacific since 2000, accumulating a database of abundance measurements for over 290 planktonic taxa in over 3,500 processed samples. There is an additional archive of over 10,000 samples available for further analyses. Exxon Valdez Oil Spill Trustee Council financial support has contributed to about half of this tally, through four projects funded since 2002. Time series of zooplankton variables for sub-regions of the survey area are presented together with abstracts of eight papers published using data from these projects. The time series covers a period when the dominant climate signal in the north Pacific, the Pacific Decadal Oscillation (PDO), switched with unusual frequency between warm/positive states (pre-1999 and 2003-2006) and cool/negative states (1999-2002 and 2007). The CPR data suggest that cool negative years show higher biomass on the shelf and lower biomass in the open ocean, while the reverse is true in warm (PDO positive) years with lower shelf biomass (except 2005) and higher oceanic biomass. In addition, there was a delay in plankton increase on the Alaskan shelf in the colder spring of 2007, compared to the warmer springs of the preceding years. In warm years, smaller species of copepods which lack lipid reserves are also more common. Availability of the zooplankton prey to higher trophic levels (including those that society values highly) is therefore dependent on the timing of increase and peak abundance, ease of capture and nutritional value. Previously published studies using these data highlight the wide-ranging applicability of CPR data and include collaborative studies on; phenology in the key copepod species Neocalanus plumchrus, descriptions of distributions of decapod larvae and euphausiid species, the effects of hydrographic features such as mesoscale eddies and the North Pacific Current on plankton populations and a molecularbased investigation of macro-scale population structure in N. cristatus. The future funding situation is uncertain but the value of the data and studies so far accumulated is considerable and sets a strong foundation for further studies on plankton dynamics and interactions with higher trophic levels in the northern Gulf of Alaska.

Monitoring changes in phytoplankton abundance and composition in the Northwest Atlantic: a comparison of results obtained by Continuous Plankton Recorder sampling and colour satellite imagery

Phytoplankton abundance in the NW Atlantic was measured by continuous plankton recorder (CPR) sampling along tracks between Iceland and the western Scotian Shelf from 1998 to 2006, when sea-surface chlorophyll (SSChl) measurements were also being made by ocean colour satellite imagery using the SeaWiFS sensor. Seasonal and inter-annual changes in phytoplankton abundance were examined using data collected by both techniques, averaged over each of four shelf regions and four deep ocean regions. CPR sampling had gaps (missing months) in all regions and in the four deep ocean regions satellite observations were too sparse between November and February to be of use. Average seasonal cycles of SSChl were similar to those of total diatom abundance in seven regions, to those of the phytoplankton colour index in six regions, but were not similar to those of total dinoflagellate abundance anywhere. Large inter-annual changes in spring bloom dynamics were captured by both samplers in shelf regions. Changes in annual (or 8 months) averages of SSChl did not generally follow those of the CPR indices within regions and multi-year averages of SSChl, and the three CPR indices were generally higher in shelf than in deep ocean regions. Remote sensing and CPR sampling provide complementary ways of monitoring phytoplankton in the ocean: the former has superior temporal and spatial coverage and temporal resolution, and the latter provides better taxonomic information.