Some aspects of the interaction of humic substances with metal ions

Humic substances are the major organic constituents of soils and sediments. They are heterogeneous, polyfunctional, polydisperse, macromolecular and have no accurately known chemical structure. Their interactions with radionuclides are particularly important since they provide leaching mechanisms from disposal sites. The central theme to this research is the interaction of heavy metal actinide analogues with humic materials. Studies described focus on selected aspects of the characteristics and properties of humic substances. Some novel approaches to experiments and data analysis are pursued. Several humic substances are studied; all but one are humic acids, and those used most extensively were obtained commercially. Some routine characterisation techniques are applied to samples in the first instance. Humic substances are coloured, but their ultra-violet and visible absorption spectra are featureless. Yet, they fluoresce over a wide range of wavelengths. Enhanced fluorescence in the presence of luminescent europium(III) ions is explained by energy transfer from irradiated humic acid to the metal ion in a photophysical model. Nuclear magnetic resonance spectroscopy is applied to the study of humic acids and their complexes with heavy metals. Proton and carbon-13 NMR provides some structural and functionality information; Paramagnetic lanthanide ions affect these spectra. Some heavy metals are studied as NMR nuclei, but measurements are restricted by their sensitivity. A humic acid is fractionated yielding a broad molecular weight distribution. Electrophoretic mobilities and particle radii determined by Laser Doppler Electrophoretic Light Scattering are sensitive to the conditions of the supporting media, and the concentration and particle size distribution of humic substances. In potentiometric titrations of humate dispersions, the organic matter responds slowly and the mineral acid addition is buffered. Proton concentration data is modelled and a mechanism is proposed involving two key stages, both resulting in proton release after some conformational changes.

Interaction of metal salts with polyethers

The dielectric properties of pure low to medium molecular weight poly(ethylene glycol) and poly(propylene glycol) and a variety of their salt complexes have been studied through the measurement of the dielectric permittivity and dielectric loss over a range of frequency and temperature. The major proportion of this study has been concerned with the examination of the nature of the interaction between mercuric chloride and poly(propylene glycol) (PPG). Other salt-poly-ether combinations have also been considered such as cobalt chloride-PPG cadmium chloride-PPG zinc chloride-PPG and ferric chloride-PEG (polyethylene glycol). Some of this work was also supported by chemical shift and spin-lattice Nuclear Magnetic Resonance (N.M.R.) spectroscopy. The dielectric permittivity data were analysed using the Onsager relation to calculate the mean dipole moment per dipolar unit. This approach was employed in the discussion of various models proposed for the structure of salt-polyether complexes. The effect of mercuric chloride on the statistical conformations of poly(propylene-glycol) was studied in a quantitative manner using the relationships of marchal-Benoit. The dielectric relaxation activation energy and mean energy difference between gauche and trans conformations of poly(propylene glycol) in the presence of mercuric chloride, both showed a distinct minimum when the concentration of mercuric chloride was close to 5 mole %. Opposite behaviour was observed for the Cole-Cole parameter. It was concluded that the majority of the dielectric data could be rationalised in terms of a 5-membered cyclic complex formed between mercuric chloride and PPG in which the complexed segment of the polyether-(OMeCH2CH2O)- adopted either gauche or cis conformations.

Support vector machines to detect physiological patterns for EEG and EMG-based human-computer interaction:a review

Support Vector Machines (SVMs) are widely used classifiers for detecting physiological patterns in Human-Computer Interaction (HCI). Their success is due to their versatility, robustness and large availability of free dedicated toolboxes. Frequently in the literature, insufficient details about the SVM implementation and/or parameters selection are reported, making it impossible to reproduce study analysis and results. In order to perform an optimized classification and report a proper description of the results, it is necessary to have a comprehensive critical overview of the application of SVM. The aim of this paper is to provide a review of the usage of SVM in the determination of brain and muscle patterns for HCI, by focusing on electroencephalography (EEG) and electromyography (EMG) techniques. In particular, an overview of the basic principles of SVM theory is outlined, together with a description of several relevant literature implementations. Furthermore, details concerning reviewed papers are listed in tables, and statistics of SVM use in the literature are presented. Suitability of SVM for HCI is discussed and critical comparisons with other classifiers are reported.

Broader or deeper? Exploring the most effective intervention profile for public small business support

Most advanced economies offer publicly financed advice services to start-up firms and SMEs. In England, local or regional Business Links organisations have provided these services, and divided their support into nonintensive one-off contacts providing information or advice and more intensive support involving a diagnostic process and repeated interaction with firms. A key choice for Business Link managers is how to shape their intervention strategies, balancing resources between intensive and nonintensive support. Drawing on resource dependency theory, we develop a typology of intervention strategies for Business Links in England which reflects differences in the breadth and depth of the support provided. We then test the impacts of these alternative intervention models on client companies using both subjective assessments by firms and econometric treatment models that allow for selection bias. Our key empirical result is that Business Links’ choice of intervention strategy has a significant effect both on actual and on perceived business outcomes, with our results emphasising the value of depth over breadth. The implication is that where additional resources are available for business support these should be used to deepen the assistance provided rather than extend assistance to a wider group of firms.

Domain and nucleotide dependence of the interaction between Saccharomyces cerevisiae translation elongation factors 3 and 1A

Eukaryotic translation elongation factor 3 (eEF3) is a fungal-specific ATPase proposed to catalyze the release of deacylated-tRNA from the ribosomal E-site. In addition, it has been shown to interact with the aminoacyl-tRNA binding GTPase elongation factor 1A (eEF1A), perhaps linking the E and A sites. Domain mapping demonstrates that amino acids 775-980 contain the eEF1A binding sites. Domain III of eEF1A, which is also involved in actin-related functions, is the site of eEF3 binding. The binding of eEF3 to eEF1A is enhanced by ADP, indicating the interaction is favored post-ATP hydrolysis but is not dependent on the eEF1A-bound nucleotide. A temperature-sensitive P915L mutant in the eEF1A binding site of eEF3 has reduced ATPase activity and affinity for eEF1A. These results support the model that upon ATP hydrolysis, eEF3 interacts with eEF1A to help catalyze the delivery of aminoacyl-tRNA at the A-site of the ribosome. The dynamics of when eEF3 interacts with eEF1A may be part of the signal for transition of the post to pre-translocational ribosomal state in yeast.

Transformational-transactional leadership and upward influence:the role of Relative Leader-Member Exchanges (RLMX) and Perceived Organizational Support (POS)

By utilizing the resource theory of social exchange (Foa & Foa, 1974), we attempted to cast light on the dynamics of the relationship between transformational-transactional leadership and employees' upward influence tactics. Using data collected in two time points (N=200, 1. year apart), we found perceptions of transformational leadership (Time 1) to be positively related to the use of soft and rational upward influence tactics (Time 2) whereas transactional leadership (Time 1) was positively related to the use of soft and hard upward influence tactics (Time 2). We also found support for a 3-way interaction between transformational-transactional leadership, relative Leader Member Exchanges (RLMX) and Perceived Organizational Support (POS) on employees' upward influence tactics. Specifically, in resource-constrained conditions (low RLMX and low POS), employees were likely to use soft tactics to influence a manager they perceived as transformational to a greater extent than in resource-munificent conditions. They were also likely to employ higher levels of soft and hard tactics to influence a transactional manager in resource-constrained rather than in resource-munificent conditions. © 2012 Elsevier Inc.

Designing a safety management support system using open architecture databases: the requirements of information representation in the support of managers' risk-related decision-making

This research was conducted at the Space Research and Technology Centre o the European Space Agency at Noordvijk in the Netherlands. ESA is an international organisation that brings together a range of scientists, engineers and managers from 14 European member states. The motivation for the work was to enable decision-makers, in a culturally and technologically diverse organisation, to share information for the purpose of making decisions that are well informed about the risk-related aspects of the situations they seek to address. The research examined the use of decision support system DSS) technology to facilitate decision-making of this type. This involved identifying the technology available and its application to risk management. Decision-making is a complex activity that does not lend itself to exact measurement or precise understanding at a detailed level. In view of this, a prototype DSS was developed through which to understand the practical issues to be accommodated and to evaluate alternative approaches to supporting decision-making of this type. The problem of measuring the effect upon the quality of decisions has been approached through expert evaluation of the software developed. The practical orientation of this work was informed by a review of the relevant literature in decision-making, risk management, decision support and information technology. Communication and information technology unite the major the,es of this work. This allows correlation of the interests of the research with European public policy. The principles of communication were also considered in the topic of information visualisation - this emerging technology exploits flexible modes of human computer interaction (HCI) to improve the cognition of complex data. Risk management is itself an area characterised by complexity and risk visualisation is advocated for application in this field of endeavour. The thesis provides recommendations for future work in the fields of decision=making, DSS technology and risk management.

Business cycles, long waves, and company langevity in Birmingham area metal industries 1780-1980

This doctoral thesis originates from an observational incongruence between the perennial aims and aspirations of economic endeavour and actually recorded outcomes, which frequently seem contrary to those intended and of a recurrent, cyclical type. The research hypothesizes parallel movement between unstable business environments through time, as expressed by periodically fluctuating levels of economic activity, and the precipitation rates of industrial production companies. A major problem arose from the need to provide theoretical and empirical cohesion from the conflicting, partial and fragmented interpretations of several hundred historians and economists, without which the research question would remain unanswerable. An attempt to discover a master cycle, or superimposition theorem, failed, but was replaced by minute analysis of both the concept of cycles and their underlying data-bases. A novel technique of congregational analysis emerged, resulting in an integrated matrix of numerical history. Two centuries of industrial revolution history in England and Wales was then explored and recomposed for the first time in a single account of change, thereby providing a factual basis for the matrix. The accompanying history of the Birmingham area provided the context of research into the failure rates and longevities of firms in the city's staple metal industries. Sample specific results are obtained for company longevities in the Birmingham area. Some novel presentational forms are deployed for results of a postal questionnaire to surviving firms. Practical demonstration of the new index of national economic activity (INEA) in relation to company insolvencies leads to conclusions and suggestions for further applications of research into the tempo of change, substantial Appendices support the thesis and provide a compendium of information covering immediately contiguous domains.

Reduced metal transferrin binding in neurological diseases

By employing G75 gel-filtration chromotography, it has been demonstrated that human plasma gallium speciation (and by implication, Al speciation) is bimodal. Normally, gallium was predominantly bound to a high molecular weight fraction which was presumably transferrin. Literature reviews and experimental work throughout this thesis provided evidence to support this idea. An aluminium-transferrin species was assumed to be relatively non-toxic and a protective function for this complex has been suggested. A second, low molecular weight species of gallium was observed and its identity has been suggested to be citrate. The results of this thesis support the concept citrate was a gallium binding ligand present in the plasma, but there was another species (tentatively identified as phosphate) which bound gallium to a much greater degree than did citrate in the majority of samples studied. The consequence of a low molecular weight species of aluminium is the possibility that this leads to a more rapid, uncontrolled deposition of the metal in the brain compared to a transferrin mediated mechanism. Plasma speciation studies in Alzheimer's disease, Parkinson's disease, Down's syndrome, and neonates has revealed an altered ratio of the two gallium species found in control subjects. In all groups there was an increase in the potentially more neurotoxic low molecular weight species. These observations have led to a suggested mechanism of accumulation of metals in the brain, which is known to occur in the first three groups. Possible pathogenic mechanisms are described. The results can also offer an explanation to the reported increased sensitivity to the toxic effects of aluminium in the neonate. Speciation studies on normal plasma has shown the balance between high and low molecular weight species of gallium to be influenced by many physiological factors. There appears to be a fine equilibrium between both species which can be altered without any great difficulty. Therefore, in the diseased groups studied, it is possible that there are subtle biochemical changes within the circulatory system to affect the equilibrium which results in an increased low molecular weight species of aluminium. Furthermore, it has been demonstrated that there is a group of normal controls with no clinical signs of Alzheimer's or Parkinson's disease which have reduced transferrin binding. This indicates there is a population of healthy people who are at risk to the development of either disease.

Modeling naturalistic argumentation in research literatures:representation and interaction design issues

This article characterizes key weaknesses in the ability of current digital libraries to support scholarly inquiry, and as a way to address these, proposes computational services grounded in semiformal models of the naturalistic argumentation commonly found in research literatures. It is argued that a design priority is to balance formal expressiveness with usability, making it critical to coevolve the modeling scheme with appropriate user interfaces for argument construction and analysis. We specify the requirements for an argument modeling scheme for use by untrained researchers and describe the resulting ontology, contrasting it with other domain modeling and semantic web approaches, before discussing passive and intelligent user interfaces designed to support analysts in the construction, navigation, and analysis of scholarly argument structures in a Web-based environment. © 2007 Wiley Periodicals, Inc. Int J Int Syst 22: 17–47, 2007.

Transition metal ion co-ordination in hydrophilic polymer membrane

This thesis is concerned with the investigation of transition metal (TM) ion complexation with hydrophilic membranes composed of copolymers of 4-vinyl pyridine & 4-methyl-4'vinyl- 2,2'-bipyridine with 2-hydroxyethyl methacrylate. The Cu(II), CoCII) & Fe(II) complexes with these coordinating membranes were characterised by a variety of techniques, in order to assess the effect of the polymer on the properties of the complex, and vice versa. A detailed programme of work was instigated into the kinetics of formation for the polymer-bound tris(bipyridyl) iron(II) complex; the rate and extent of complex formation was found to be anion-dependent. This is explained in terms of the influence of the anion on the transport properties and water content of the membrane, the controlling factor in the development of the tris-complex being the equilibrium concentration of Fe(II) in the gel matrix. A series of transport studies were performed with a view to the potential application of complexing hydrogel membranes for aqueous TM ion separations. A number of salts were studied individually and shown to possess a range of permeabilities; the degree of interaction between particular metal-ion:ligand combinations is given by the lag-time observed before steady-state permeation is achieved. However, when two TM salts that individually display different transport properties were studied in combination, they showed similar lag-times & permeabilities, characteristic of the more strongly coordinating metal ion. This 'anti-selective' nature thus renders the membrane systems unsuitable for TM ion separations. Finally, attempts were made to synthesise and immobilise a series of N ,0-donor macrocyclic ligands into hydrogel membranes. Although the functionalisation reactions failed, limited transport data was obtained from membranes in which the ligands were physically entrapped within the polymer matrix.

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.

Carbon nanotube-supported metal catalysts for NOx reduction using hydrocarbon reductants. Part 1:catalyst preparation, characterization and NOx reduction characteristics

A dual catalyst system for the Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR), including distinct low and high temperature formulations, is proposed as a means to abate NOx emissions from diesel engines. Given that satisfactory high temperature HC-SCR catalysts are already available, this work focuses on the development of an improved low temperature formulation. Pt supported on multiwalled carbon nantubes (MWCNTs) was found to exhibit superior NOx reduction activity in comparison with Pt/Al2O3, while the MWCNT support displayed a higher resistance to oxidation than activated carbon. Refluxing the MWCNT support in a 1:1 mixture of H2SO4 and HNO3 prior to the metal deposition step proved to be beneficial for the metal dispersion and the NOx reduction performance of the resulting catalysts. This support effect is ascribed to the increased Brønsted acidity of the acid-treated MWCNTs, which in turn enhances the partial oxidation of the hydrocarbon reductant. Further improvements in the HC-SCR performance of MWCNT-based formulations were achieved using a 3:1 Pt–Rh alloy as the supported phase.

In-situ XPS study on the reducibility of Pd-promoted Cu/CeO2 catalysts for the oxygen-assisted water-gas-shift reaction

Cu/CeO2, Pd/CeO2, and CuPd/CeO2 catalysts were prepared and their reduction followed by in-situ XPS in order to explore promoter and support interactions in a bimetallic CuPd/CeO2 catalyst effective for the oxygen-assisted water-gas-shift (OWGS) reaction. Mutual interactions between Cu, Pd, and CeO2 components all affect the reduction process. Addition of only 1 wt% Pd to 30 wt% Cu/CeO2 greatly enhances the reducibility of both dispersed CuO and ceria support. In-vacuo reduction (inside XPS chamber) up to 400 °C results in a continuous growth of metallic copper and Ce3+ surface species, although higher temperatures results in support reoxidation. Supported copper in turn destabilizes metallic palladium metal with respect to PdO, this mutual perturbation indicating a strong intimate interaction between the Cu–Pd components. Despite its lower intrinsic reactivity towards OWGS, palladium addition at only 1 wt% loading significantly improved CO conversion in OWGS reaction over a monometallic 30 wt% Cu/CeO2 catalysts, possibly by helping to maintain Cu in a reduced state during reaction.