The Mechanism of the Benzilic Acid Rearrangement: A Study of the Benzilic Acid Rearrangement by Isotopic Tracer Techniques

Abstract Not Provided

USE OF DRINKING WATER TREATMENT RESIDUALS AS A SOIL AMENDMENT FOR STORMWATER NUTRIENT TREATMENT

Stormwater runoff has been implicated as a major source of excess nutrients to surface waters, contributing to the development of eutrophic conditions. Bioretention, a promising technology for urban stormwater pollution treatment, was investigated to determine if an aluminum-based water treatment residual (WTR) amended bioretention soil media (BSM) could adsorb phosphorus to produce discharge concentrations below 25 μg/L. Batch, small column, and vegetated column studies were employed to determine both the optimal BSM mixture and media performance. Media tests demonstrated P adsorption proportional to WTR addition. Final selected experimental media consisted of 75% sand, 10% silt, 5.8% clay, 5.2% WTR, and 3.4% bark mulch (air dry mass basis).This media showed excellent P removal relative to a non-WTR-amended media. Whereas the control media leached P (71.1% increase in mass), the experimental media adsorbed 85.7% of the P mass applied, displaying a cumulative effluent EMC of 16.1 μg/L, below the 25 μg/L goal

A Quality Framework for Software Development (QFSD)

INTRODUCTION. This research delivers a new complete and prescriptive software development framework, known as the Quality Framework for Software Development (QFSD) for immediate use by software development practitioners. Whilst there are a number of existing methodologies available, and many software development standards they fail to address the complete development lifecycle. A review of current literature supports this assertion. AIMS AND OBJECTIVES. The overall aim of the research is to create a new software development framework, applying it to a substantial number of real-world software projects in two different industrial software development environments and thereby demonstrating its effectiveness. METHODS. Based on a review of the available research approaches and strategies, the researcher selected 'pragmatism' as the most suitable for this research. This selection was driven by two contributory factors. The first was that in order to conduct the research the researcher would have active participation in the majority of the research activities. The second was that the deliverables from the research should be immediately useable for the benefit of software practitioners and hence not be regarded as a theoretical framework. The approach was further refined by adopting Action Research and Case Study strategies. The research was divided in to stages each of which was executed within separate companies. The companies were very different in terms of their business areas, culture and views on quality and specifically quality of software deliverables. RESULTS. The research findings provided a strong indication that a holistic software development framework does provide an improvement in software project deliverables quality and repeatability in terms of schedules and quality. In the case of Fisher–Rosemount it enabled them to attain ISO 9000/Ticket accreditation. In addition, by providing all processes and tools in a single web based environment the adoption by software developers, project managers and senior management was very high

Economics of Cattle Production Systems Post CAP Reform.

End of Project ReportThe radical reform of the Common Agricultural Policy (CAP) in the early 1990’s impacted directly and indirectly on most of the farm enterprises in Ireland. The direct focus of the reform was largely confined to the cereal and beef enterprises. The reforms consisted of: • A phased reduction in the institutional support prices for cereals and beef of the order of 30 per cent • A phased switch to a direct payment system of farm income support to compensate for the product price reductions. Most farms in Ireland have a cattle enterprise, either alone or in combination with other land using enterprises. Therefore, the reforms of the CAP affected almost all the farms in the country either directly or indirectly. For cattle farmers, the potential consequencee of these changes could be far reaching in terms of their magnitude and their permeation into the details of the husbandry practices of the production system(s) themselves. These changes clearly impact on the economic efficiency of beef systems without necessarily affecting technical efficiency of the systems. The economic optimum cattle production systems would thus be achieved by using the best mix of feed resource costs, carcass values and direct payments. The purpose of the study was to: • determine the economic impact on the cattle enterprise of the switch to: • lower EU prices for beef • lower EU prices for cereals and as a consequence a lower price for concentrate feeds • the direct payment system of income support • identify the economic optimum cattle production system(s) that would arise from these changes • quantify the sensitivity of the economic optimum system to key policy, economic and technical production variables

A Monte Carlo Model for LET Spectra of 200 MeV Protons Used for Microelectronic Testing

The direct ionization Linear Energy Transfer (LET) for 200 MeV protons in silicon is much smaller than that for higher charged particles since LET increases as the square of the ion charge. However, occasionally the proton interacts with the silicon nuclei and produces a shower of fragments and a recoiling nucleus. When this happens, the LET produced is much greater than the direct ionization LET. Testing the single event effect susceptibility of components using energetic (200 MeV) protons is often the only viable option for system level testing commercial-off-the-shelf (COTS) avionics that have not been designed for space environments. However, the question of how a system tested with protons will perform in a heavy ion environment arises. Here the concern is not only with prediction of on-orbit upset rate, but also about possibility of on-orbit failures that were not observed during proton testing

New and Novel Cyclisation Reactions of Imidoylketenes

The effect of scale on the conversion to products in flash vacuum pyrolysis experiments was studied using four model reactions. Overall, conversion was dependent on rection scale up to 0.5 g, but above 0.5 g, the effect was minimal and within experimental error. This effect was shown to be due to variations in contact time of the molecules in the furnace tube. Altering the furnace tube diameter had the effect of increasing the conversion to product. The pyrolysis of ortho-anilinomethylene Meldrum’s acid derivatives was investigated. Typically the 8-substituted quinolin-4-one was obtained as the major product, with a few exceptions. Certain substituents (such as nitro) were found to react with the ketene produced in the reaction to give alternative products, while others (such as chloro- and N-unsubstituted amides) gave the 3-substituted quinolin-4- ones via ipso-cyclisation and migration of the substituent. The regioselectivity of the pyrolysis of meta-anilinomethylene Meldrum’s acid derivatives, to give 5- and 7-substituted quinolin-4-ones, was studied. In general a 3:1 – 4:1 ratio of regioisomers was obtained, in favour of the 7-substituted quinolin-4-one. Substituents capable of hydrogen bonding, such as hydroxy-, were shown to give the 5-substituted quinolin-4-one exclusively and DFT calculations were employed to show that, in these examples, the 5-substituted product was favoured energetically. The pyrolysis of the methylene Meldrum’s acid derivative of 3-aminophenol gave 8-hydroxyquinolizinone as the sole product at low temperatures, with 5- hydroxyquinolinone as the major product formed at higher temperatures. The mechanism involves a regioselective electrocyclisation, followed by a hydrogen transfer and generation of a new ketene. Cyclisation of this ketene gives the quinolizinone. The scope of this reaction was explored, with a number of derivatives synthesised, and substitution on the aminophenol and the ketene generator was tolerated. The reactivity of the quinolizinones was also explored. The hydroxygroup was found to be phenol-like and underwent similar reactions, such as alkylations and acetylations. The compound was found to be highly reactive towards electrophiles, reacting in the 1- and 3- positions of the ring system, often in both positions. The pyrolysis of the aminomethylene Meldrum’s acid derivatives of certain pyridazinones was shown to give pyridopyrazidinediones. In some examples, a 4 second product based on a pyrrolopyridazine ring system was observed and DFT calculations show that the mechanism involves probably an electrocyclisation, followed by a decarboxylation reaction. Pyrolysis of amino acid ester derivatives of methylene Meldrum’s acid were shown to give N-unsubstituted 3-hydroxypyrroles and 1H-pyrrol-3(2H)-ones. Different amino acids were tolerated in the reaction, as were different electronwithdrawing groups in place of the amino acid ester. DFT calculations were employed to explore the mechanism of the reaction. 3-Hydroxypyrrole was also synthesised from the pyrolysis of Meldrum’s acid derivative of glycine tert-butyl ester, and the reactivity of the compound explored for the first time. The compound was found to be reactive towards electrophiles, such as diazonium salts, and could be O-acetylated under appropriate conditions

Conservative Management of Paediatric Clavicle Fractures

Paediatric clavicle fractures have traditionally been treated nonoperatively. Recent studies have recommended operative management for displaced midshaft fractures. We conducted a retrospective review of all clavicle fractures in children aged one to sixteen over a two-year period. We classified fractures and evaluated followup and clinical outcome. We identified 190 fractures. There were 135 boys and 55 girls. 65% of fractures were displaced and 35% undisplaced. Mean radiographic and clinical followup was 35 days and 44 days, respectively. Clavicle fractures in children heal with nonoperative management. Radiographs of clavicle fractures in children are unnecessary in the absence of clinical symptoms

Investigation of pulse shape characteristics on the laser ablation dynamics of TiN coatings in the ns regime

n this work, the ablation dynamics of TiN coating with a ns-pulsed fibre laser in a wide range of pulse durations were studied. Critical time instances within the pulse duration were assessed by reflected pulse analysis. Digital holography was employed to investigate the shock wave expansion dynamics within and beyond the pulse duration. The results depict that the absorption behaviour changes as a function of the pulse rise time. Moreover, planar expansion of the shock wave is observed, which is generally linked to higher machining quality and absence of excessive plasma. The results of the study are interpreted to depict the required characteristics of optimized pulse shapes in the ns-region for improved micromachining performance

Laser micromachining of TiN coatings with variable pulse durations and shapes in ns regime

"The micro-structuring of thin surface coatings has become increasingly popular following the discovery of improved performance, especially in terms of the resulting tribological properties. The directwriting of microstructures via laser ablation offers flexibility, extending the applicability ofmicro-structuring to variousmaterials and machined geometries. However, the laser ablation of coatings requires better comprehension to provide sufficientmachining quality with improved productivity to render such processes more viable for industrial applications. This paper presents the processing conditions for the ablation of approximately 4-μm-thick coatings of TiN in the ns pulse regime, which is generally characterised by higher productivity with low machining quality. A range of pulse durations between 12 ns and 200 ns was employed. The effect of pulse duration on ablation threshold fluence and irradiance was investigated. The pulse shape was decomposed into peak and tail regions to investigate their respective effects on the ablation process. The opportune regulation of pulse properties allowed for themaintenance of high productivity and high-quality laser micromachining under delicate processing conditions, in the case of ceramic TiN surface coatings with limited thickness.

Toll-like receptors and NOD-like receptors in rheumatic diseases

The past 10 years have seen the description of families of receptors that drive proinflammatory cytokine production in infection and tissue injury. Two major classes have been examined in the context of inflammatory joint disease - the Toll-like receptors (TLRs) and NOD-like receptors (NLRs). TLRs such as TLR2 and TLR4 are being implicated in the pathology of rheumatoid arthritis, ankylosing spondylitis, lyme arthritis and osteoarthritis. Nalp3 has been identified as a key NLR for IL-1β production and has been shown to have a particular role in gout. These findings present new therapeutic opportunities, possibly allowing for the replacement of biologics with small molecule inhibitors