Vibrational spectroscopy and solubility study of the mineral stringhamite CaCuSiO4•H2O

Stringhamite CaCuSiO4·H2O is a hydrated calcium copper silicate and is commonly known as a significant ‘healing’ mineral and is potentially a semi-precious jewel. Stringhamite is a neosilicate with Cu2+ in square planar coordination. Vibrational spectroscopy has been used to characterise the molecular structure of stringhamite. The intense sharp Raman band at 956 cm−1 is assigned to the ν1 (A1g) symmetric stretching vibration. Raman bands at 980, 997, 1061 cm−1 are assigned to the ν3 (A2u, B1g) antisymmetric stretching vibrations. Splitting of the ν3 vibrational mode supports the concept that the stringhamite SiO4 tetrahedron is strongly distorted. The intense bands at 505 and 519 cm−1 and at 570 cm−1 are assigned to the ν2 and ν4 vibrational modes. The question arises as to whether the mineral stringhamite can actually function as a healing mineral. An estimation of the solubility product at pH < 5 shows that the cupric ion can be released. The copper ion is a very powerful antibiological agent and thus the mineral stringhamite may well function as a healing mineral.

Investigation to enhance high speed rail accessibility

High Speed Rail (HSR) is rapidly gaining popularity worldwide as a safe and efficient transport option for long-distance travel. Designed to win market shares from air transport, HSR systems optimise their productivity between increasing speeds and station spacing to offer high quality service and gain ridership. Recent studies have investigated the effects that the deployment of HSR infrastructure has on spatial distribution and the economic development of cities and regions. Findings appear mostly positive at higher geographical scales, where HSR links connect major urban centres several hundred kilometres apart and already well positioned within a national or international context. Also, at the urban level, studies have shown regeneration and concentration effects around HSR station areas with positive returns on city’s image and economy. However, doubts persist on the effects of HSR at an intermediate scale, where the accessibility trade off on station spacing limits access to many small and medium agglomerations. Thereby, their ability to participate in the development opportunities facilitated by HSR infrastructure is significantly reduced. The locational advantages deriving from transport improvements appear contrasting especially in regions that tend to have a polycentric structure, where cities may present greater accessibility disparities between those served by HSR and those left behind. This thesis fits in this context where intermediate and regional cities do not directly enjoy the presence of an HSR station while having an existing or planned proximate HSR corridor. With the aim of understanding whether there might be a solution to this apparent incongruity, the research investigates strategies to integrate HSR accessibility at the regional level. While current literature recommends to commit with ancillary investments to the uplift of station areas and the renewal of feeder systems, I hypothesised the interoperability between the HSR and the conventional networks to explore the possibilities offered by mixed traffic and infrastructure sharing. Thus, I developed a methodology to quantify the exchange of benefits deriving from this synergistic interaction. In this way, it was possible to understand which level of service quality offered by alternative transit strategies best facilitates the distribution of accessibility benefits for areas far from actual HSR stations. Therefore, strategies were selected for their type of service capable of regional extensions and urban penetrations, while incorporating a combination of specific advantages (e.g. speed, sub-urbanity, capacity, frequency and automation) in order to emulate HSR quality with increasingly efficient services. The North-eastern Italian macro region was selected as case study to ground the research offering concurrently a peripheral polycentric metropolitan form, the presence of a planned HSR corridor with some portions of HSR infrastructure implementation, and the project to develop a suburban rail service extended regionally. Results show significant distributive potential, in terms of network effects produced in relation with HSR, in increasing proportions for all the strategies considered: a regional metro rail strategy (abbreviated RMR), a regional high speed rail strategy (abbreviated RHSR), a regional light rail transit (abbreviated LRT) strategy, and a non-stopping continuous railway system (abbreviated CRS) strategy. The provision of additional tools to value HSR infrastructure against its accessibility benefits and their regional distribution through alternative strategies beyond the actual HSR stations, would have great implications, both politically and technically, in moving towards new dimensions of HSR evaluation and development.

The market structure and characteristics of electronic games

A multi-billion dollar industry, electronic games have been experiencing strong and rapid growth in recent times. The world of games is not only exciting due to the magnificent growth of the industry however, but due to a host of other factors. This chapter explores electronic games, providing an analysis of the industry, key motivators for game play, the game medium and academic research concerning the effects of play. It also reviews the emerging relationship games share with sport, recognizing that they can replicate sports, facilitate sports participation and be played as a sport. These are complex relationships that have not yet been comprehensively studied. The current chapter serves to draw academic attention to the area and presents ideas for future research.

Fabrication of macro-mesoporous zirconia-alumina materials with a 1D hierarchical structure

A series of one dimensional (1D) zirconia/alumina nanocomposites were prepared by the deposition of zirconium species onto the 3D framework of boehmite nanofibres formed by dispersing boehmite nanofibres into butanol solution. The materials were calcined at 773K and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), N2 adsorption/desorption, infrared emission spectroscopy (IES). The results demonstrated that when the molar percentage X=100*Zr/(Al+Zr) was > 30 %, extremely long ZrO2/Al2O3 composite nanorods with evenly distributed ZrO2 nanocrystals on the surface were formed. The stacking of such nanorods gave rise to a new kind of macroporous material without the use of any organic space filler\template or other specific technologies. The mechanism for the formation of long ZrO2/Al2O3 composite nanorods was proposed in this work.

Fast detection of exact clones in business process model repositories

As organizations reach higher levels of business process management maturity, they often find themselves maintaining very large process model repositories, representing valuable knowledge about their operations. A common practice within these repositories is to create new process models, or extend existing ones, by copying and merging fragments from other models. We contend that if these duplicate fragments, a.k.a. ex- act clones, can be identified and factored out as shared subprocesses, the repository’s maintainability can be greatly improved. With this purpose in mind, we propose an indexing structure to support fast detection of clones in process model repositories. Moreover, we show how this index can be used to efficiently query a process model repository for fragments. This index, called RPSDAG, is based on a novel combination of a method for process model decomposition (namely the Refined Process Structure Tree), with established graph canonization and string matching techniques. We evaluated the RPSDAG with large process model repositories from industrial practice. The experiments show that a significant number of non-trivial clones can be efficiently found in such repositories, and that fragment queries can be handled efficiently.

Geostatistical analysis of adult Rhyzopertha dominica (F.) (Coleoptera: Bostrichidae) in wheat stored at constant temperatures

Insect monitoring and sampling programmes are used in the stored grains industry for the detection and estimation of insect pests. At the low pest densities dictated by economic and commercial requirements, the accuracy of both detection and abundance estimates can be influenced by variations in the spatial structure of pest populations over short distances. Geostatistical analysis of Rhyzopertha dominica populations in 2 dimensions showed that, in both the horizontal and vertical directions and at all temperatures examined, insect numbers were positively correlated over short (0-5cm) distances, and negatively correlated over longer (≥10cm) distances. Analysis in 3 dimensions showed a similar pattern, with positive correlations over short distances and negative correlations at longer distances. At 35°C, insects were located significantly further from the grain surface than at 25 and 30°C. Dispersion metrics showed statistically significant aggregation in all cases. This is the first research using small sample units, high sampling intensities, and a range of temperatures, to show spatial structuring of R. dominica populations over short distances. This research will have significant implications for sampling in the stored grains industry.

The relation between work motivation and project management success : an empirical investigation

The content and context of work significantly influences an employees’ satisfaction. While managers see work motivation as a tool to engage the employees so that they perform better, academicians value work motivation for its contribution to human behaviour. Though the relationship between employee motivation and project success has been extensively covered in the literature, more research focusing on the nature of job design on project success may have been wanting. We address this gap through this study. The present study contributes to the extant literature by suggesting an operational framework of work motivation for project—based organizations. We are also advancing the conceptual understanding of this variable by understanding how the different facets of work motivation have a differing impact of the various parameters of project performance. A survey instrument using standardized scales of work motivation and project success was used. 199 project workers from various industries completed the survey. We first ‘operationalized’ the definition of work motivation for the purpose of our study through a principal component analysis of work motivation items. We obtained a five factor structure that had items pertaining to employee development, work climate, goal clarity, and job security. We then performed a Pearson’s correlation analysis which revealed moderate to significant relationship between project outcomes ad work climate; project outcomes & employee development. In order to establish a causality between work motivation and project management success, we employed linear regression analysis. The results show that work climate is a significant predictor of client satisfaction, while it moderately influences the project quality. Further, bringing in objectivity to project work is important for a successful implementation.

Three-dimensional geological modelling and multivariate statistical analysis of water chemistry data to analyse and visualise aquifer structure and groundwater composition in the Wairau Plain, Marlborough District, New Zealand

Concerns regarding groundwater contamination with nitrate and the long-term sustainability of groundwater resources have prompted the development of a multi-layered three dimensional (3D) geological model to characterise the aquifer geometry of the Wairau Plain, Marlborough District, New Zealand. The 3D geological model which consists of eight litho-stratigraphic units has been subsequently used to synthesise hydrogeological and hydrogeochemical data for different aquifers in an approach that aims to demonstrate how integration of water chemistry data within the physical framework of a 3D geological model can help to better understand and conceptualise groundwater systems in complex geological settings. Multivariate statistical techniques(e.g. Principal Component Analysis and Hierarchical Cluster Analysis) were applied to groundwater chemistry data to identify hydrochemical facies which are characteristic of distinct evolutionary pathways and a common hydrologic history of groundwaters. Principal Component Analysis on hydrochemical data demonstrated that natural water-rock interactions, redox potential and human agricultural impact are the key controls of groundwater quality in the Wairau Plain. Hierarchical Cluster Analysis revealed distinct hydrochemical water quality groups in the Wairau Plain groundwater system. Visualisation of the results of the multivariate statistical analyses and distribution of groundwater nitrate concentrations in the context of aquifer lithology highlighted the link between groundwater chemistry and the lithology of host aquifers. The methodology followed in this study can be applied in a variety of hydrogeological settings to synthesise geological, hydrogeological and hydrochemical data and present them in a format readily understood by a wide range of stakeholders. This enables a more efficient communication of the results of scientific studies to the wider community.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vibrational spectroscopic study of the minerals nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O : implications for the molecular structure

Nekoite Ca3Si6O15•7H2O and okenite Ca10Si18O46•18H2O are both hydrated calcium silicates found respectively in contact metamorphosed limestone and in association with zeolites from the alteration of basalts. The minerals form two-Dimensional infinite sheets with other than six-membered rings with 3-, 4-, or 5-membered rings and 8-membered rings. The two minerals have been characterised by Raman, near-infrared and infrared spectroscopy. The Raman spectrum of nekoite is characterised by two sharp peaks at 1061 and 1092 cm-1 with bands of lesser intensity at 974, 994, 1023 and 1132 cm-1. The Raman spectrum of okenite shows an intense single Raman band at 1090 cm-1 with a shoulder band at 1075 cm-1.These bands are assigned to the SiO stretching vibrations of Si2O5 units. Raman water stretching bands of nekoite are observed at 3071, 3380, 3502 and 3567 cm-1. Raman spectrum of okenite shows water stretching bands at 3029, 3284, 3417, 3531 and 3607 cm-1. NIR spectra of the two minerals are subtly different inferring water with different hydrogen bond strengths. By using a Libowitzky empirical formula, hydrogen bond distances based upon these OH stretching vibrations. Two types of hydrogen bonds are distinguished: strong hydrogen bonds associated with structural water and weaker hydrogen bonds assigned to space filling water molecules.

Creativity in policing: building the necessary skills to solve complex and protracted investigations

Despite an increased focus on proactive policing in recent years, criminal investigation is still perhaps the most important task of any law enforcement agency. As a result, the skills required to carry out a successful investigation or to be an ‘effective detective’ have been subjected to much attention and debate (Smith and Flanagan, 2000; Dean, 2000; Fahsing and Gottschalk, 2008:652). Stelfox (2008:303) states that “The service’s capacity to carry out investigations comprises almost entirely the expertise of investigators.” In this respect, Dean (2000) highlighted the need to profile criminal investigators in order to promote further understanding of the cognitive approaches they take to the process of criminal investigation. As a result of his research, Dean (2000) produced a theoretical framework of criminal investigation, which included four disparate cognitive or ‘thinking styles’. These styles were the ‘Method’, ‘Challenge’, ‘Skill’ and ‘Risk’. While the Method and Challenge styles deal with adherence to Standard Operating Procedures (SOPs) and the internal ‘drive’ that keeps an investigator going, the Skill and Risk styles both tap on the concept of creativity in policing. It is these two latter styles that provide the focus for this paper. This paper presents a brief discussion on Dean’s (2000) Skill and Risk styles before giving an overview of the broader literature on creativity in policing. The potential benefits of a creative approach as well as some hurdles which need to be overcome when proposing the integration of creativity within the policing sector are then discussed. Finally, the paper concludes by proposing further research into Dean’s (2000) skill and risk styles and also by stressing the need for significant changes to the structure and approach of the traditional policing organisation before creativity in policing is given the status it deserves.

Towards an effective IT governance structure for organizations in developing economies

The pervasive use of IT is prominent amongst organizations in developing economies. However, there is growing evidence that these economies fail to capitalize on their IT investment to transform their organizations to be competitive both locally and globally. IT-related benefits are possible with appropriate governance of the IT-related resources, and we need to broaden our understanding on the IT governance mechanics suitable for organizations in the developing economies. In this study, we adopted an initial interpretive design to obtain a deeper understanding of the IT governance (ITG) environment and conceptions of the stakeholders on effective IT governance structures for the developing economies. We found that the presence of an IT Strategic Planning Committee, Multiple level of authority, and a Forum for informal discussions as the crucial components of an ITG structure in developing economies.

Regulation of proteasome structure and function

Proteasomes are cylindrical particles made up of a stack of four heptameric rings. In animal cells the outer rings are made up of 7 different types of alpha subunits and the inner rings are composed of 7 out of 10 possible different beta subunits. Regulatory complexes can bind to the ends of the cylinder.We have investigated aspects of the assembly, activity and subunit composition of core proteasome particles and 26S proteasomes, the localization of proteasome subpopulations, and the possible role of phosphorylation in determining proteasome localization, activities and association with regulatory components.

Updating and verification for multi-scale finite element model of structure behavior

The method on concurrent multi-scale model of structural behavior (CMSM-of-SB) for the purpose of structural health monitoring including model updating and validating has been studied. The detailed process of model updating and validating is discussed in terms of reduced scale specimen of the steel box girder in longitudinal stiffening truss of a long span bridge. Firstly, some influence factors affecting the accuracy of the CMSM-of-SB including the boundary restraint regidity, the geometry and material parameters on the toe of the weld and its neighbor are analyzed using sensitivity method. Then, sensitivity-based model updating technology is adopted to update the developed CMSM-of-SB and model verification is carried out through calculating and comparing stresses on different locations under various loading from dynamic characteristic and static response. It can be concluded that the CMSM-of-SB based on the substructure method is valid.