Real and imaginary parts of the vibrational relaxation of acetonitrile in its electrolyte solutions:new results for the dynamics of solvent molecules

Isotropic scattering Raman spectra of liquid acetonitrile (AN) solutions of LiBF4 and NaI at various temperatures and concentrations have been investigated. For the first time imaginary as well as real parts of the solvent vibrational correlation functions have been extracted from the spectra. Such imaginary parts are currently an important component of modern theories of vibrational relaxation in liquids. This investigation thus provides the first experimental data on imaginary parts of a correlation function in AN solutions. Using the fitting algorithm we recently developed, statistically confident models for the Raman spectra were deduced. The parameters of the band shapes, with an additional correction, of the ν2 AN vibration (CN stretching), together with their confidence intervals are also reported for the first time. It is shown that three distinct species, with lifetimes greater than ∼10−13 s, of the AN molecules can be detected in solutions containing Li+ and Na+. These species are attributed to AN molecules directly solvating cations; the single oriented and polarised molecules interleaving the cation and anion of a Solvent Shared Ion Pair (SShIP); and molecules solvating anions. These last are considered to be equivalent to the next layer of solvent molecules, because the CN end of the molecule is distant from the anion and thus less affected by the ionic charge compared with the anion situation. Calculations showed that at the concentrations employed, 1 and 0.3 M, there were essentially no other solvent molecules remaining that could be considered as bulk solvent. Calculations also showed that the internuclear distance in these solutions supported the proposal that the ionic entity dominating in solution was the SShIP, and other evidence was adduced that confirmed the absence of Contact Ion Pairs at these concentrations. The parameters of the shape of the vibrational correlation functions of all three species are reported. The parameters of intramolecular anharmonic coupling between the potential surfaces in AN and the dynamics of the intermolecular environment fluctuations and intermolecular energy transfer are presented. These results will assist investigations made at higher and lower concentrations, when additional species and interactions with AN molecules will be present.

The structure of the rare-earth phosphate glass(Sm2O3)0.205(P2O5)0.795 studied by anomalous dispersion neutron diffraction

The role of the Sm3+ ions in the structure of vitreous Sm2O3•4P2O5 has been investigated using the neutron diffraction anomalous dispersion technique, which employs the wavelength dependence of the real and imaginary parts of the neutron scattering length close to an absorption resonance. The data described here represent the first successful complete neutron anomalous dispersion study on an amorphous material. This experimental methodology permits one to determine exclusively the closest Sm• •• Sm separation. Knowledge of the R•••R (R = rare-earth) pairwise correlation is key to understanding the optical and magnetic properties of rare-earth phosphate glasses. The anomalous difference correlation function, ΔT''(r), shows a dominant feature pertaining to a Sm•••Sm separation, centred at 4.8 Å. The substantial width and marked asymmetry of this peak indicates that the minimum approach of Sm3+ ions could be as close as 4 Å. Information on other pairwise correlations is also revealed via analysis of T (r) and ΔT (r) correlation functions: Sm3+ ions display an average co-ordination number, n Sm(O), of 7, with a mean Sm–O bond length of 2.375(5) Å whilst the PO4 tetrahedra have a mean P–O bond length of 1.538(2) Å. Second- and third-neighbour correlations are also identified. These results corroborate previous findings. Such consistency lends support to the application of the anomalous dispersion technique to determine separations.

Cortical oscillatory activity associated with the perception of illusory and real visual contours

We used magnetoencephalography (MEG) to examine the nature of oscillatory brain rhythms when passively viewing both illusory and real visual contours. Three stimuli were employed: a Kanizsa triangle; a Kanizsa triangle with a real triangular contour superimposed; and a control figure in which the corner elements used to form the Kanizsa triangle were rotated to negate the formation of illusory contours. The MEG data were analysed using synthetic aperture magnetometry (SAM) to enable the spatial localisation of task-related oscillatory power changes within specific frequency bands, and the time-course of activity within given locations-of-interest was determined by calculating time-frequency plots using a Morlet wavelet transform. In contrast to earlier studies, we did not find increases in gamma activity (> 30 Hz) to illusory shapes, but instead a decrease in 10–30 Hz activity approximately 200 ms after stimulus presentation. The reduction in oscillatory activity was primarily evident within extrastriate areas, including the lateral occipital complex (LOC). Importantly, this same pattern of results was evident for each stimulus type. Our results further highlight the importance of the LOC and a network of posterior brain regions in processing visual contours, be they illusory or real in nature. The similarity of the results for both real and illusory contours, however, leads us to conclude that the broadband (< 30 Hz) decrease in power we observed is more likely to reflect general changes in visual attention than neural computations specific to processing visual contours.

An investigation of the prevalence and measurement of teams in organisations:the development and validation of the real team scale

This thesis begins with a review of the literature on team-based working in organisations, highlighting the variations in research findings, and the need for greater precision in our measurement of teams. It continues with an illustration of the nature and prevalence of real and pseudo team-based working, by presenting results from a large sample of secondary data from the UK National Health Service. Results demonstrate that ‘real teams’ have an important and significant impact on the reduction of many work-related safety outcomes. Based on both theoretical and methodological limitations of existing approaches, the thesis moves on to provide a clarification and extension of the ‘real team’ construct, demarcating this from other (pseudo-like) team typologies on a sliding scale, rather than a simple dichotomy. A conceptual model for defining real teams is presented, providing a theoretical basis for the development of a scale on which teams can be measured for varying extents of ‘realness’. A new twelve-item scale is developed and tested with three samples of data comprising 53 undergraduate teams, 52 postgraduate teams, and 63 public sector teams from a large UK organisation. Evidence for the content, construct and criterion-related validity of the real team scale is examined over seven separate validation studies. Theoretical, methodological and practical implications of the real team scale are then discussed.

Accuracy and applications of group MEG studies using cortical source locations estimated from participants' scalp surfaces

We contend that powerful group studies can be conducted using magnetoencephalography (MEG), which can provide useful insights into the approximate distribution of the neural activity detected with MEG without requiring magnetic resonance imaging (MRI) for each participant. Instead, a participant's MRI is approximated with one chosen as a best match on the basis of the scalp surface from a database of available MRIs. Because large inter-individual variability in sulcal and gyral patterns is an inherent source of blurring in studies using grouped functional activity, the additional error introduced by this approximation procedure has little effect on the group results, and offers a sufficiently close approximation to that of the participants to yield a good indication of the true distribution of the grouped neural activity. T1-weighted MRIs of 28 adults were acquired in a variety of MR systems. An artificial functional image was prepared for each person in which eight 5 × 5 × 5 mm regions of brain activation were simulated. Spatial normalisation was applied to each image using transformations calculated using SPM99 with (1) the participant's actual MRI, and (2) the best matched MRI substituted from those of the other 27 participants. The distribution of distances between the locations of points using real and substituted MRIs had a modal value of 6 mm with 90% of cases falling below 12.5 mm. The effects of this -approach on real grouped SAM source imaging of MEG data in a verbal fluency task are also shown. The distribution of MEG activity in the estimated average response is very similar to that produced when using the real MRIs. © 2003 Wiley-Liss, Inc.

The complexity of leadership and organisations

The thesis contributes to the evolving process of moving the study of Complexity from the arena of metaphor to something real and operational. Acknowledging this phenomenon ultimately changes the underlying assumptions made about working environments and leadership; organisations are dynamic and so should their leaders be. Dynamic leaders are behaviourally complex. Behavioural Complexity is a product of behavioural repertoire - range of behaviours; and behavioural differentiation - where effective leaders apply appropriate behaviour to the demands of the situation. Behavioural Complexity was operationalised using the Competing Values Framework (CVF). The CVF is a measure that captures the extent to which leaders demonstrate four behaviours on four quadrants: Control, Compete, Collaborate and Create, which are argued to be critical to all types of organisational leadership. The results provide evidence to suggest Behavioural Complexity is an enabler of leadership effectiveness; Organisational Complexity (captured using a new measure developed in the thesis) moderates Behavioural Complexity and leadership effectiveness; and leadership training supports Behavioural Complexity in contributing to leadership effectiveness. Most definitions of leadership come down to changing people’s behaviour. Such definitions have contributed to a popularity of focus in leadership research intent on exploring how to elicit change in others when maybe some of the popularity of attention should have been on eliciting change in the leader them self. It is hoped that this research will provoke interest into the factors that cause behavioural change in leaders that in turn enable leadership effectiveness and in doing so contribute to a better understanding of leadership in organisations.

Building up resilience of construction sector SMEs and their supply chains to extreme weather events

Wider scientific community now accept that the threat of climate change as real and thus acknowledge the importance of implementing adaptation measures in a global context. In the UK , the physical effects of climate change are likely to be directly felt in the form of extreme weather events, which are predicted to escalate in number and severity in future under the changing climatic conditions. Construction industry; which consists of supply chains running across various other industries, economies and regions, will also be affected due to these events. Thus, it is important that the construction organisations are well prepared to withstand the effects of extreme weather events not only directly affecting their organisations but also affecting their supply chains which in turn might affect the organisation concerned. Given the fact that more than 99% of construction sector businesses are SMEs, the area can benefit significantly from policy making to improve SME resilience and coping capacity. This paper presents the literature review and synthesis of a doctoral research study undertaken to address the issue of extreme weather resilience of construction sector SMEs and their supply chains. The main contribution of the paper to both academia and practitioners is a synthesis model that conceptualises the factors that enhances resilience of SMEs and their supply chains against extreme weather events. This synthesis model forms the basis of a decision making framework that will enable SMEs to both reduce their vulnerability and enhance their coping capacity against extreme weather. The value of this paper is further extended by the overall research design that is set forth as the way forward.

Transglutaminases as tanning agents for the leather industry

This study was aimed at determining whether the protein crosslinking enzymes, transglutaminases, had the potential to be used as tanning agents, using native bovine hide and purified soluble rat tail collagen as real and model substrates, respectively. We demonstrate that transglutaminases (TGs) were capable of covalently crosslinking collagen molecules together such that on average every collagen molecule contained at least one epsilon(gamma-glutamyl)lysine crosslink. However, transglutaminase-mediated crosslinking did not affect the denaturation temperature of either native bovine hide or soluble rat tail collagens when used in isolation or together with other proteins and bifunctional diamines as crosslinking facilitators. In an initial study into the effect of TG-mediated crosslinking on the tensile strength of chrome-tanned bovine hide, such crosslinking led to a 30 per cent decrease in tensile strength. Despite a change in the gel melting point mediated by epsilon(gamma-glutamyl)lysine crosslinking, the use of transglutaminases as alternative tanning agents seems unlikely given the present data.

A novel entropy measure for analysis of the electrocardiogram

There has been much recent research into extracting useful diagnostic features from the electrocardiogram with numerous studies claiming impressive results. However, the robustness and consistency of the methods employed in these studies is rarely, if ever, mentioned. Hence, we propose two new methods; a biologically motivated time series derived from consecutive P-wave durations, and a mathematically motivated regularity measure. We investigate the robustness of these two methods when compared with current corresponding methods. We find that the new time series performs admirably as a compliment to the current method and the new regularity measure consistently outperforms the current measure in numerous tests on real and synthetic data.

Ultrasonic inspection of austenitic stainless steel weldments

Ultrasonic waves interact in a complex manner with the metallurgical structure of austenitic weldments resulting in ambiguity when interpreting reflections and at times in misinterpretation of defect positions. In this work, current knowledge of the structure of austenitic welds is outlined, and the influence of this structure on the propagation of ultrasonic waves is reviewed. Using an established and highly accurate technique, data on velocity variations as a function of the angle between the direction of soundwave propagation and the axes of preferred grain orientation existing in such welds, are experimentally obtained. These results and existing theory are used to provide quantitative evidence of (i) anisotropy factors in austenitic welds, (ii) beam skewing effects for different wave modes and polarizations, and (iii) the extent of acoustic impedance mismatch between parent and weld metals. The existence of "false" indications is demonstrated, and suggestions are made into their nature. The effectiveness of conventional transverse wave techniques for inspecting artificial and real defects existing in austenitic weldments is experimentally investigated, the limitations are demonstrated, and possible solutions are proposed. The possibilities offered by the use of longitudinal angle probes for ultrasonic inspection of real and artificial defects existing in austenitic weldments are experimentally investigated, and parameters such as probe angle, frequency and scanning position are evaluated. Detailed work has been carried out on the interaction of ultrasound with fatigue and corrosion-fatigue cracks in the weld metal and the heat affected zones (HAZs) of 316 and 347 types of austenitic weldments, together with the influence of elastic compressive stresses, defect topography and defect geometry. Practical applications of all results are discussed, and more effective means of ultrasonic inspection of austenitic weldments are suggested.

The future of the public library:reimagining the moral economy of the 'people's university'

New media technologies, the digitisation of information, learning archives and heritage resources are changing the nature of the public library and museums services across the globe, and, in so doing, changing the way present and future users of these services interact with these institutions in real and virtual spaces. New digital technologies are rewriting the nature of participation, learning and engagement with the public library, and fashioning a new paradigm where virtual and physical spaces and educative and temporal environments operate symbiotically. It is with such a creatively disruptive paradigm that the £193 million Library of Birmingham project in the United Kingdom is being developed. New and old media forms and platforms are helping to fashion new public places and spaces that reaffirm the importance of public libraries as conceived in the nineteenth century. As people’s universities, the public library service offers a web of connective learning opportunities and affordances. This article considers the importance of community libraries as sites of intercultural understanding and practical social democracy. Their significance is reaffirmed through the initial findings in the first of a series of community interventions forming part of a long-term project, ‘Connecting Spaces and Places’, funded by the Royal Society of Arts.

The Library of Birmingham project:lifelong learning for the digital age

The Library of Birmingham (LoB) is a £193million project designed to provide a new space for lifelong learning and knowledge growth, a physical and virtual portal for Birmingham's citizens to the wider world. In cooperation with a range of private, public, and third-sector bodies, as well as individual citizens, the library, due to open in June 2013, will articulate a continuing process of organic growth and emergence. Key delivery themes focus on: arts and creativity, citizenship and community, enterprise and innovation, learning and skills and the new media ecology. A landmark design in the heart of the cultural district of the city, the LoB aims to stimulate sustainable economic growth, urban regeneration and social inclusion by offering a wide range of new digital learning services, real and virtual community spaces, and new opportunities for interpreting and exploiting internationally significant collections of documentary archives, photography, moving image, and rare printed books. Additionally, the LoB will offer physical space for creative, cultural, enterprise, and knowledge development. This paper outlines the cultural and educational thinking that informs the project and the challenges experienced in developing innovative service redesign.

Performing in a night-time leisure venue: a visual analysis of erotic dance

This article analyses a range of different meanings attached to images of erotic dance, with a particular focus on the 'impression management' (Goffman 1959) enacted by dancers. It presents a visual analysis of the work of a female erotic performer in a lesbian erotic dance venue in the UK. Still photographs, along with observational data and interviews, convey the complexity and skill of an erotic dancer's diverse gendered and sexualised performances. The visual data highlights the extensive 'aesthetic labour' (Nickson et al. 2001) and 'emotional labour' (Hochschild 1983) the dancer must put in to constructing her work 'self'. However, a more ambitious use of the visual is identified: the dancer's own use of images of her work. This use of the visual by dancers themselves highlights a more complex 'impression management' strategy undertaken by a dancer and brings into question the separation of 'real' and 'work' 'selves' in erotic dance. © Sociological Research Online, 1996-2012.

Polynomial function intervals for floating-point software verification

The focus of our work is the verification of tight functional properties of numerical programs, such as showing that a floating-point implementation of Riemann integration computes a close approximation of the exact integral. Programmers and engineers writing such programs will benefit from verification tools that support an expressive specification language and that are highly automated. Our work provides a new method for verification of numerical software, supporting a substantially more expressive language for specifications than other publicly available automated tools. The additional expressivity in the specification language is provided by two constructs. First, the specification can feature inclusions between interval arithmetic expressions. Second, the integral operator from classical analysis can be used in the specifications, where the integration bounds can be arbitrary expressions over real variables. To support our claim of expressivity, we outline the verification of four example programs, including the integration example mentioned earlier. A key component of our method is an algorithm for proving numerical theorems. This algorithm is based on automatic polynomial approximation of non-linear real and real-interval functions defined by expressions. The PolyPaver tool is our implementation of the algorithm and its source code is publicly available. In this paper we report on experiments using PolyPaver that indicate that the additional expressivity does not come at a performance cost when comparing with other publicly available state-of-the-art provers. We also include a scalability study that explores the limits of PolyPaver in proving tight functional specifications of progressively larger randomly generated programs. © 2014 Springer International Publishing Switzerland.

An introduction to forensic linguistics:language in evidence

From the accusation of plagiarism in The Da Vinci Code, to the infamous hoaxer in the Yorkshire Ripper case, the use of linguistic evidence in court and the number of linguists called to act as expert witnesses in court trials has increased rapidly in the past fifteen years. An Introduction to Forensic Linguistics: Language in Evidence provides a timely and accessible introduction to this rapidly expanding subject. Using knowledge and experience gained in legal settings – Malcolm Coulthard in his work as an expert witness and Alison Johnson in her work as a West Midlands police officer – the two authors combine an array of perspectives into a distinctly unified textbook, focusing throughout on evidence from real and often high profile cases including serial killer Harold Shipman, the Bridgewater Four and the Birmingham Six. Divided into two sections, 'The Language of the Legal Process' and 'Language as Evidence', the book covers the key topics of the field. The first section looks at legal language, the structures of legal genres and the collection and testing of evidence from the initial police interview through to examination and cross-examination in the courtroom. The second section focuses on the role of the forensic linguist, the forensic phonetician and the document examiner, as well as examining in detail the linguistic investigation of authorship and plagiarism. With research tasks, suggested reading and website references provided at the end of each chapter, An Introduction to Forensic Linguistics: Language in Evidence is the essential textbook for courses in forensic linguistics and language of the law.