Caesium bis­(5-bromo­salicyl­aldehyde thio­semicarbazonato-κ3O,N,S)ferrate(III): supramolecular arrangement of low-spin FeIII complex anions mediated by Cs+ cations

The synthesis and crystal structure determination (at 293 K) of the title complex, Cs[Fe(C8H6BrN3OS)2], are reported. The compound is composed of two dianionic O,N,S-tridentate 5-bromo­salicyl­aldehyde thio­semicarbazonate(2-) ligands coord­inated to an FeIII cation, displaying a distorted octa­hedral geometry. The ligands are orientated in two perpendicular planes, with the O- and S-donor atoms in cis positions and the N-donor atoms in trans positions. The complex displays inter­molecular N-H...O and N-H...Br hydrogen bonds, creating R44(18) rings, which link the FeIII units in the a and b directions. The FeIII cation is in the low-spin state at 293 K.

Organic reactions in ionic liquids: oxidative dimerisation of thioamides with phenyliodine(III) diacetate

The room temperature ionic liquid, 1-n-butylpyridinium tetrafluoroborate (BPyBF4), is used as a “green“ recyclable solvent for the oxidative dimerisation of thioamides with phenyliodine(III) diacetate which provides a facile, efficient and environmentally benign method for the synthesis of 3,5-diaryl-1,2,4-thiadiazoles.

Policy into practice:a study of public policy implementation and the role of learning

Public policy becomes managerial practice through a process of implementation. There is an established literature within Implementation Studies which explains the variables and some of the processes involved in implementation, but less attention has been focused upon how public service managers convert new policy initiatives into practice. The research proposes that managers and their organisations have to go through a process of learning in order to achieve the implementation of public policy. Data was collected over a five year period from four case studies of capital investment appraisal in the British National Health Service. Further data was collected from taped interviews by key actors within the case studies. The findings suggest that managers do learn to implement policy and four factors are important in this learning process. These are; (i) the nature of bureaucratic responsibility; (ii) the motivation of actors towards learning; (iii) the passage of time which allows for the development of competence and (iv) the use of project team structures. The research has demonstrated that the conversion of policy into practice occurs through the operationalisation of solutions to policy problems via job tasks. As such it suggests that in understanding how policy is implemented, technical learning is more important than cultural learning, in this context. In conclusion, a "Model of Learned Implementation" is presented, together with a discussion of some of the implications of the research. These are the possible use of more pilot projects for new policy initiatives and the more systematic diffusion of knowledge about implementation solutions.

Optimization of PCB component placements for the collect-and-place machines

This paper presents two hybrid genetic algorithms (HGAs) to optimize the component placement operation for the collect-and-place machines in printed circuit board (PCB) assembly. The component placement problem is to optimize (i) the assignment of components to a movable revolver head or assembly tour, (ii) the sequence of component placements on a stationary PCB in each tour, and (iii) the arrangement of component types to stationary feeders simultaneously. The objective of the problem is to minimize the total traveling time spent by the revolver head for assembling all components on the PCB. The major difference between the HGAs is that the initial solutions are generated randomly in HGA1. The Clarke and Wright saving method, the nearest neighbor heuristic, and the neighborhood frequency heuristic are incorporated into HGA2 for the initialization procedure. A computational study is carried out to compare the algorithms with different population sizes. It is proved that the performance of HGA2 is superior to HGA1 in terms of the total assembly time.

The mechanics of the conform continuous extrusion process

The work describes the programme of activities relating to a mechanical study of the Conform extrusion process. The main objective was to provide a basic understanding of the mechanics of the Conform process with particular emphasis placed on modelling using experimental and theoretical considerations. The experimental equipment used includes a state of the art computer-aided data-logging system and high temperature loadcells (up to 260oC) manufactured from tungsten carbide. Full details of the experimental equipment is presented in sections 3 and 4. A theoretical model is given in Section 5. The model presented is based on the upper bound theorem using a variation of the existing extrusion theories combined with temperature changes in the feed metal across the deformation zone. In addition, constitutive equations used in the model have been generated from existing experimental data. Theoretical and experimental data are presented in tabular form in Section 6. The discussion of results includes a comprehensive graphical presentation of the experimental and theoretical data. The main findings are: (i) the establishment of stress/strain relationships and an energy balance in order to study the factors affecting redundant work, and hence a model suitable for design purposes; (ii) optimisation of the process, by determination of the extrusion pressure for the range of reduction and changes in the extrusion chamber geometry at lower wheel speeds; and (iii) an understanding of the control of the peak temperature reach during extrusion.

Environmental features which limit organization and industry viability:a study of the footwear industry

This thesis proposes a conceptual framework for the analysis of organizational environments. Three primary segments of the task environment - the transaction environment, the industrial environment and the ecotone are delineated. The interrelationships between the organization and these three environmental segments are examined. It is suggested that the task environment i) defines the nature of the task confronting the organization and the economic, political and social position of the organization within this network; ii) influences the way organizations and industries are organized; iii) prevents recognition of the need for adaptation and change; and iv) limits the alternatives available to the organization should changes in the environment render existing technology, behaviour and structures obsolete. The British Footwear Industry provides an example of how this framework might be used to investigate the problem of industry decline and organization viability. It is argued that the explanations usually put forth to explain organization failure and industrial decline have not taken into consideration the environmental factors which affect organization and industry viability. The shift from national markets to global markets has altered the composition of the task environment and has changed the nature of competition from firm versus firm to environment versus environment. Organizations do not compete in the market, their products do. These products are often produced by organizations embedded in environments which are significantly different from the one in which the focal organization and industry are embedded.

The metabolism of n-methyl compounds

The metabolism of compounds containing the N-methyl group is discussed with particular consideration being made to the possible role of the product of oxidative metabolism, the N-hydroxymethyl moiety, in the generation of potentially toxic, reactive electrophiles. Particular pathways which are considered are: (i), the production of formaldehyde; (ii), the generation of iminium ions or imines; and (iii), the formation of N-formyl compounds which might act as formylating agents. 4-Chloro-N-(hydroxymethyl)benzamide and 3-(4-chlorophenyl)-1-hydroxy-methyl-1-methylurea (the product of oxidative metabolism of 3-(4-chlorophenyl)-1,1-dimethylurea) are model carbinolamides which do not readily release formaldehyde. The electrophilic properties of these model carbinolamides were investigated: neither reacted with nucleophiles such as cyanide or glutathione under physiological conditions. In contrast, N-(acetoxymethyl)-4-chlorobenzamide yielded the cyanomethylamide with potassium cyanide and S-(4-chlorobenzamidomethyl)glutathione with glutathione. 4-Chloro-N-(hydroxymethyl)benzamide and 3-(4-chlorophenyl)-1,1-dimethylurea were not biotransformed to electrophilic moieties when incubated with mouse hepatic 9000 x g supernatant and Acetyl-CoA or PAPS-generating system. N-(Acetoxymethyl)-4-chlorobenzamide was non-mutagenic to Salmonella typhimurium in the short term bacterial assay; but toxicity to the bacteria was observed. 4-Chloro-N-(hydroxymethyl)benzamide and 3-(4-chlorophenyl)-1,1-dimethylurea showed no mutagenicity or toxicity in the mutagenicity assay including an Aroclor-induced rat hepatic 9000 x g supernatant. Addition of Acetyl-CoA or a PAPS-generating system did not produce a mutagenic response. 4-Chloro-N-formlbenzamide did not act as a formylating agent towards the weak nucleophile aniline. However, 4-chloro-N-formylbenzamide, N-formylbenzamide, 3-(4-chlorophenyl)-1-formyl-1-methylurea and 3-(4-chlorophenyl)-1-formylurea are all metabolised by mouse hepatic mirosomes and post-microsomal supernatant. The results demonstrate the potential for N-hydroxymethyl compounds to generate highly reactive species if these are substrates for conjugation with sulphate (or acetate). The model compounds employed here, apparently do not show any ability to be conjugated themselves, however, other N-hydroxymethyl compounds might be readily conjugated. The formation of N-formyl compounds does not appear to be toxicologically significant, as adjudged on limited experiments performed, but rather represent a detoxification pathway.

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 visual cortex in Alzheimer disease:laminar distribution of the pathological changes in visual areas V1 and V2

Alzheimer’s disease (AD) is an important neurodegenerative disorder causing visual problems in the elderly population. The pathology of AD includes the deposition in the brain of abnormal aggregates of ?-amyloid (A?) in the form of senile plaques (SP) and abnormally phosphorylated tau in the form of neurofibrillary tangles (NFT). A variety of visual problems have been reported in patients with AD including loss of visual acuity (VA), colour vision and visual fields; changes in pupillary responses to mydriatics, defects in fixation and in smooth and saccadic eye movements; changes in contrast sensitivity and in visual evoked potentials (VEP); and disturbances in complex visual tasks such as reading, visuospatial function, and in the naming and identification of objects. In addition, pathological changes have been observed to affect the eye, visual pathway, and visual cortex in AD. To better understand degeneration of the visual cortex in AD, the laminar distribution of the SP and NFT was studied in visual areas V1 and V2 in 18 cases of AD which varied in disease onset and duration. In area V1, the mean density of SP and NFT reached a maximum in lamina III and in laminae II and III respectively. In V2, mean SP density was maximal in laminae III and IV and NFT density in laminae II and III. The densities of SP in laminae I of V1 and NFT in lamina IV of V2 were negatively correlated with patient age. No significant correlations were observed in any cortical lamina between the density of NFT and disease onset or duration. However, in area V2, the densities of SP in lamina II and lamina V were negatively correlated with disease duration and disease onset respectively. In addition, there were several positive correlations between the densities of SP and NFT in V1 with those in area V2. The data suggest: (1) NFT pathology is greater in area V2 than V1, (2) laminae II/III of V1 and V2 are most affected by the pathology, (3) the formation of SP and NFT in V1 and V2 are interconnected, and (4) the pathology may spread between visual areas via the feed-forward short cortico-cortical connections.

An empirical examination of the strategic decision-making process:the relationship between context, process, and outcomes

Despite concerted academic interest in the strategic decision-making process (SDMP) since the 1980s, a coherent body of theory capable of guiding practice has not materialised. This is because many prior studies focus only on a single process characteristic, often rationality or comprehensiveness, and have paid insufficient attention to context. To further develop theory, research is required which examines: (i) the influence of context from multiple theoretical perspectives (e.g. upper echelons, environmental determinism); (ii) different process characteristics from both synoptic formal (e.g. rationality) and political incremental (e.g. politics) perspectives, and; (iii) the effects of context and process characteristics on a range of SDMP outcomes. Using data from 30 interviews and 357 questionnaires, this thesis addresses several opportunities for theory development by testing an integrative model which incorporates: (i) five SDMP characteristics representing both synoptic formal (procedural rationality, comprehensiveness, and behavioural integration) and political incremental (intuition, and political behaviour) perspectives; (ii) four SDMP outcome variables—strategic decision (SD) quality, implementation success, commitment, and SD speed, and; (iii) contextual variables from the four theoretical perspectives—upper echelons, SD-specific characteristics, environmental determinism, and firm characteristics. The present study makes several substantial and original contributions to knowledge. First, it provides empirical evidence of the contextual boundary conditions under which intuition and political behaviour positively influence SDMP outcomes. Second, it establishes the predominance of the upper echelons perspective; with TMT variables explaining significantly more variance in SDMP characteristics than SD specific characteristics, the external environment, and firm characteristics. A newly developed measure of top management team expertise also demonstrates highly significant direct and indirect effects on the SDMP. Finally, it is evident that SDMP characteristics and contextual variables influence a number of SDMP outcomes, not just overall SD quality, but also implementation success, commitment, and SD speed.

Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.

NOx storage-reduction characteristics of Ba-based lean NOx trap catalysts subjected to simulated road aging

In order to study the effect of washcoat composition on lean NOx trap (LNT) aging characteristics, fully formulated monolithic LNT catalysts containing varying amounts of La-stabilized CeO2 (5 wt% La2O3) or CeO2-ZrO2 (Ce:Zr = 70:30) were subjected to accelerated aging on a bench reactor. Subsequent catalyst evaluation revealed that aging resulted in deterioration of the NOx storage, NOx release and NOx reduction functions, whereas the observation of lean phase NO2 slip for all of the aged catalysts indicated that LNT performance was not limited by the kinetics of NO oxidation. After aging, all of the catalysts showed increased selectivity to NH3 in the temperature range 250–450 °C. TEM, H2 chemisorption, XPS and elemental analysis data revealed two main changes which can explain the degradation in LNT performance. First, residual sulfur in the catalysts, present as BaSO4, decreased catalyst NOx storage capacity. Second, sintering of the precious metals in the washcoat was observed, which can be expected to decrease the rate of NOx reduction. Additionally, sintering is hypothesized to result in segregation of the precious metal and Ba phases, resulting in less efficient NOx spillover from Pt to Ba during NOx adsorption, as well as decreased rates of reductant spillover from Pt to Ba and reverse NOx spillover during catalyst regeneration. Spectacular improvement in LNT durability was observed for catalysts containing CeO2 or CeO2-ZrO2 relative to their non-ceria containing analog. This was attributed to (i) the ability of ceria to participate in NOx storage/reduction as a supplement to the main Ba NOx storage component; (ii) the fact that Pt and CeO2(-ZrO2) are not subject to phase segregation; and (iii) the ability of ceria to trap sulfur, resulting in decreased sulfur accumulation on the Ba component.

The visual cortex in alzheimer's disease:laminar distribution of the pathological changes in visual areas V1 and V2

Alzheimer's disease (AD) is an important neurodegenerative disorder causing visual problems in the elderly population. The pathology of AD includes the deposition in the brain of abnormal aggregates of β-amyloid (Aβ) in the form of senile plaques (SP) and abnormally phosphorylated tau in the form of neurofibrillary tangles (NFT). A variety of visual problems have been reported in patients with AD including loss of visual acuity (VA), colour vision and visual fields; changes in pupillary responses to mydriatics, defects in fixation and in smooth and saccadic eye movements; changes in contrast sensitivity and in visual evoked potentials (VEP); and disturbances in complex visual tasks such as reading, visuospatial function, and in the naming and identification of objects. In addition, pathological changes have been observed to affect the eye, visual pathway, and visual cortex in AD. To better understand degeneration of the visual cortex in AD, the laminar distribution of the SP and NFT was studied in visual areas V1 and V2 in 18 cases of AD which varied in disease onset and duration. In area V1, the mean density of SP and NFT reached a maximum in lamina III and in laminae II and III respectively. In V2, mean SP density was maximal in laminae III and IV and NFT density in laminae II and III. The densities of SP in laminae I of V1 and NFT in lamina IV of V2 were negatively correlated with patient age. No significant correlations were observed in any cortical lamina between the density of NFT and disease onset or duration. However, in area V2, the densities of SP in lamina II and lamina V were negatively correlated with disease duration and disease onset respectively. In addition, there were several positive correlations between the densities of SP and NFT in V1 with those in area V2. The data suggest: (1) NFT pathology is greater in area V2 than V1, (2) laminae II/III of V1 and V2 are most affected by the pathology, (3) the formation of SP and NFT in V1 and V2 are interconnected, and (4) the pathology may spread between visual areas via the feed-forward short cortico-cortical connections. © 2012 by Nova Science Publishers, Inc. All rights reserved.