Developing a categorisation system for rapists' speech

Case linkage, the linking of crimes into series, is used in policing in the UK and other countries. Previous researchers have proposed using rapists' speech in this practice; however, researching this application requires the development of a reliable coding system for rapists' speech. A system was developed based on linguistic theories of pragmatics which allowed for the categorization of an utterance into a speech act type (e.g. directive). Following this classification, the qualitative properties of the utterances (e.g. the degree of threat it carried) could be captured through the use of rating scales. This system was tested against a previously developed system using 188 rapists' utterances taken from victims' descriptions of rape. The pragmatics-based system demonstrated higher inter-rater reliability whilst enabling the classification of a greater number of rapists' utterances. Inter-rater reliability for the subscales was also tested using a sub-sample of 50 rapists' utterances and inter-item correlations were calculated. Seventy-six per cent of the subscales had satisfactory to high inter-rater reliability. Based on these findings and the inter-item correlations, the classification system was revised. The potential use of this system for the practices of case linkage and offender profiling is discussed.

Synthetic molecular mimics of naturally occurring cyclopentenones exhibit antifungal activity towards pathogenic fungi

The naturally occurring reactive electrophilic species 12-oxo-phytodienoic acid (12-oxo-PDA) is a potent antifungal agent, whereas the plant growth regulator jasmonic acid, which is synthesized from 12-oxo-PDA, is ineffective. To address what structural features of the molecule endow it with antifungal activity, we synthesized a series of molecular mimics of 12-oxo-PDA varying in the length of the alkyl chain at its C-4 ring position. The octyl analogue (4-octyl cyclopentenone) was the most effective at suppressing spore germination and subsequent mycelial growth of a range of fungal pathogens and was particularly effective against Cladosporium herbarum and Botrytis cinerea, with minimum fungicidal concentrations in the range 100-200 µM. Introduction of a carboxyl group to the end of the chain, mimicking natural fatty acids, markedly reduced antifungal efficacy. Electrolyte leakage, indicative of membrane perturbation, was evident in both C. herbarum and B. cinerea exposed to 4-octyl cyclopentenone. Lipid composition analysis of the fungal spores revealed that those species with a high oil content, namely Fusarium oxysporum and Alternaria brassicicola, were less sensitive to 4-octyl cyclopentenone. The comparable hydrophobicity of 4-octyl cyclopentenone and 12-oxo-PDA accounts for the similar spore suppression activity of these two compounds. The relative ease of synthesis of 4-octyl cyclopentenone makes it an attractive compound for potential use as an antifungal agent. © 2011 SGM.

The visualisation of vitreous using surface modified poly(lactic-co-glycolic acid) microparticles

AIMS To demonstrate the potential use of in vitro poly(lactic-co-glycolic acid) (PLGA) microparticles in comparison with triamcinolone suspension to aid visualisation of vitreous during anterior and posterior vitrectomy. METHODS PLGA microparticles (diameter 10-60 microm) were fabricated using single and/or double emulsion technique(s) and used untreated or following the surface adsorption of a protein (transglutaminase). Particle size, shape, morphology and surface topography were assessed using scanning electron microscopy (SEM) and compared with a standard triamcinolone suspension. The efficacy of these microparticles to enhance visualisation of vitreous against the triamcinolone suspension was assessed using an in vitro set-up exploiting porcine vitreous. RESULTS Unmodified PLGA microparticles failed to adequately adhere to porcine vitreous and were readily washed out by irrigation. In contrast, modified transglutaminase-coated PLGA microparticles demonstrated a significant improvement in adhesiveness and were comparable to a triamcinolone suspension in their ability to enhance the visualisation of vitreous. This adhesive behaviour also demonstrated selectivity by not binding to the corneal endothelium. CONCLUSION The use of transglutaminase-modified biodegradable PLGA microparticles represents a novel method of visualising vitreous and aiding vitrectomy. This method may provide a distinct alternative for the visualisation of vitreous whilst eliminating the pharmacological effects of triamcinolone acetonide suspension.

Spatially clustered associations in health GIS

Overlaying maps using a desktop GIS is often the first step of a multivariate spatial analysis. The potential of this operation has increased considerably as data sources and Web services to manipulate them are becoming widely available via the Internet. Standards from the OGC enable such geospatial mashups to be seamless and user driven, involving discovery of thematic data. The user is naturally inclined to look for spatial clusters and correlation of outcomes. Using classical cluster detection scan methods to identify multivariate associations can be problematic in this context, because of a lack of control on or knowledge about background populations. For public health and epidemiological mapping, this limiting factor can be critical but often the focus is on spatial identification of risk factors associated with health or clinical status. Spatial entropy index HSu for the ScankOO analysis of the hypothetical dataset using a vicinity which is fixed by the number of points without distinction between their labels. (The size of the labels is proportional to the inverse of the index) In this article we point out that this association itself can ensure some control on underlying populations, and develop an exploratory scan statistic framework for multivariate associations. Inference using statistical map methodologies can be used to test the clustered associations. The approach is illustrated with a hypothetical data example and an epidemiological study on community MRSA. Scenarios of potential use for online mashups are introduced but full implementation is left for further research.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Spatially clustered associations in health related geospatial data

Overlaying maps using a desktop GIS is often the first step of a multivariate spatial analysis. The potential of this operation has increased considerably as data sources an dWeb services to manipulate them are becoming widely available via the Internet. Standards from the OGC enable such geospatial ‘mashups’ to be seamless and user driven, involving discovery of thematic data. The user is naturally inclined to look for spatial clusters and ‘correlation’ of outcomes. Using classical cluster detection scan methods to identify multivariate associations can be problematic in this context, because of a lack of control on or knowledge about background populations. For public health and epidemiological mapping, this limiting factor can be critical but often the focus is on spatial identification of risk factors associated with health or clinical status. In this article we point out that this association itself can ensure some control on underlying populations, and develop an exploratory scan statistic framework for multivariate associations. Inference using statistical map methodologies can be used to test the clustered associations. The approach is illustrated with a hypothetical data example and an epidemiological study on community MRSA. Scenarios of potential use for online mashups are introduced but full implementation is left for further research.

Simultaneous refractive index and temperature measurement using a cascaded long-period grating device

We present a compact scheme for simultaneous temperature and surrounding refractive index (SRI) measurement using two long period gratings (LPGs) of different periods inscribed side-by-side in a single piece of a double-cladding fibre. One of the LPGs is sensitive to both SRI and temperature changes whilst the second is SRI-insensitive but shows spectral shift with temperature changes. In addition, we show that a resonance peak of the SRI-insensitive LPG can be designed to appear in the EDFA wavelength region with potential use for gain flattening applications.

The effect of complexes on combustion

The twin goals of low and efficient fuel use and minimum emissions are increasingly being addressed by research in both the motor and the catalyst industries of the world. This study was designed to attempt to investigate these goals. For diesel engine vehicles, this can be achieved by improving the efficiency of the fuel combustion in the combustion chamber. By having a suitable oxidation catalyst in the fuel one would expect the efficiency of the fuel combustion to be increased and fewer partial oxidation products to be formed. Also by placing a catalyst converter in the exhaust system partial oxidation products may be converted to more desirable final products. Finally, in this research the net catalytic effect of using an additive treated fuel and a blank ceramic monolith to trap the metal in the exhaust gases for potential use as catalytic converter was investigated. Suitable metal additives must yield a stable solution in the fuel tank. That is, they should not react with the air, water and rust that are always present. The research was targeted on the synthesis of hydrocarbon-soluble complexes that might exhibit unusually slow rates of ligand substitution. For materials containing metal ions, these properties are best met by using multi-dentate ligands that form neutral complexes. Metal complexes have been synthesised using acetylacetone derivatives, schiff base ligands and macrocyclic polyamine ligands, as potential pro-oxidant additives. Their thermal stabilities were also investigated using a differential thermal analysis instrument. The complexes were then investigated as potential additives for use in diesel fuel. The tests were conducted under controlled conditions using a diesel combustion bomb simulating the combustion process in the D.I. diesel engine, a test bed engine, and a vehicle engine.

Synthetic analogues of protein-lipid complexes

Hypercoiling poly(styrene-alt-maleic anhydride) (PSMA) is known to undergo conformational transition in response to environmental stimuli. The association of PSMA with lipid 2-dilauryl-sn-glycero-3-phosphocholine (DLPC) produces polymer-lipid complex analogues to lipoprotein assemblies found in lung surfactant. These complexes represent a new bio-mimetic delivery vehicle with applications in the cosmetic and pharmaceutical industries. The primary aim of this study was to develop a better understanding of PSMA-DLPC association by using physical and spectroscopic techniques. Ternary phase diagrams were constructed to examine the effects of various factors, such as molecular weight, pH and temperature on PSMA-DLPC association. 31P-NMR spectroscopy was used to investigate the polymorphic changes of DLPC upon associating with PSMA. The Langmuir Trough technique and surface tension measurement were used to explore the association behaviour of PSMA both at the interface and in the bulk of solution, as well as its interaction with DLPC membranes. The ultimate aim of this study was to investigate the potential use of PSMA-DLPC complexes to improve the bioavailability and therapeutic efficacy of a range of drugs. Typical compounds of ophthalmic interest range from new drugs such as Pirenzepine, which has attracted clinical interest for the control of myopia progression, to the well-established family of non-steroid anti-inflammatory drugs. These drugs have widely differing structures, sizes, solubility profiles and pH-sensitivities. In order to understand the ways in which these characteristics influence incorporation and release behaviour, the marker molecules Rhodamine B and Oil Red O were chosen. PSMA-DLPC complexes, incorporated with marker molecules and Pirenzepine, were encapsulated in hydrogels of the types used for soft contact lenses. Release studies were conducted to examine if this smart drug delivery system can retain such compounds and deliver them at a slow rate over a prolonged period of time.

Unrepeatered transmission through ultra-long fiber laser cavities

We present a study on the potential use of ultra-longlasercavities for unrepeateredfiber communication, based on the theory of nonlinearity management. A comparison is offered between the performance of ultra-longlasers and standard bi-directional distributed amplification schemes in nonrepeated transmission. Links based on both traditional (SMF/DCF) and modern Ultrawave transmissionfibers are considered.

Cellular uptake and biological activity of synthetic hammerhead ribozymes

Glioblastoma Multiforme (GBM) is a highly malignant form of brain cancer for which there is no effective cure. The over-expression of a number of genes, including the epidermal growth factor receptor (EGFr), has been implicated as a causative factor of tumourigenesis. Ribozymes are a class of ribonucleic acid that possess enzymatic properties. They can inhibit gene-expression in a highly sequence specific manner by catalysing the trans-cleavage of target RNA. The potential use of synthetic hammerhead ribozymes as novel anti-brain tumour agents was investigated in this study. The successful use of synthetic, exogenously administered ribozymes for such applications will require chemical modifications that improve biological stability and a fundamental understanding of cellular uptake mechanisms. Chimeric 2'-O-methylated hammerhead ribozymes proved to be significantly more stable (>4000-fold) in serum than unmodified RNA ribozymes and exhibited high in vitro catalytic activity. The cellular association of an internally [32P]-labelled 2'-O-methylated chimeric ribozyme in U87-MG human glioma cells was temperature-, energy- and pH-dependent and involved an active process that could be competed with a variety of polyanions. Indications are that the predominant mechanism of uptake is by adsorptive and / or receptor mediated endocytosis. Twenty 2'-O-methylated chimeric ribozymes were designed to cleave various sites along the EGFr mRNA. In vitro, 18 ribozymes exhibited high activity in cleaving a complementary short substrate. Using LipofectAMINETM as a delivery agent, the efficacy of these ribozymes was evaluated in the A431 cell line, which expresses amplified levels of EGFr. Studies revealed that although the ribozymes were taken up by the cells and remained stable over a period of 4 days, no significant reduction in either EGFr expression or cell proliferation was evident. The presence of telomerase, a ribonucleoprotein responsible for telomere elongation, has been strongly associated with tumour progression. The biological activity of a 2'-O-methylated ribozyme targeted against the RNA component of telomerase was determined. The ribozyme exhibited specific dose-dependent inhibition of telomerase activity in U87-MG cell lysates with an IC50 of –4μM. When 4μM ribozyme was delivered to intact U87-MG cells, complexed to LipofectAMINETM, telomerase activity was significantly reduced to 74.5±4.17% of the untreated control. Free ribozyme showed no significant inhibitory effect demonstrating the importance of an appropriate delivery system for optimum delivery of exogenously administered ribozymes.

The controlled release of macromolecules from macroporous hydrophyllic polymer matrices

This work has used novel polymer design and fabrication technology to generate bead form polymer based systems, with variable, yet controlled release properties, specifically for the delivery of macromolecules, essentially peptides of therapeutic interest. The work involved investigation of the potential interaction between matrix ultrastructural morphology, in vitro release kinetics, bioactivity and immunoreactivity of selected macromolecules with limited hydrolytic stability, delivered from controlled release vehicles. The underlying principle involved photo-polymerisation of the monomer, hydroxyethyl methacrylate, around frozen ice crystals, leading to the production of a macroporous hydrophilic matrix. Bead form matrices were fabricated in controllable size ranges in the region of 100µm - 3mm in diameter. The initial stages of the project involved the study of how variables, delivery speed of the monomer and stirring speed of the non solvent, affectedthe formation of macroporous bead form matrices. From this an optimal bench system for bead production was developed. Careful selection of monomer, solvents, crosslinking agent and polymerisation conditions led to a variable but controllable distribution of pore sizes (0.5 - 4µm). Release of surrogate macromolecules, bovine serum albumin and FITC-linked dextrans, enabled factors relating to the size and solubility of the macromolecule on the rate of release to be studied. Incorporation of bioactive macromolecules allowed retained bioactivity to be determined (glucose oxidase and interleukin-2), whilst the release of insulin enabled determination of both bioactivity (using rat epididymal fat pad) and immunoreactivity (RIA). The work carried out has led to the generation of macroporous bead form matrices, fabricated from a tissue biocompatible hydrogel, capable of the sustained, controlled release of biologically active peptides, with potential use in the pharmaceutical and agrochemical industries.

The durability of cement bound minestone

The demand for road making materials continues to pressurise the supply of traditional good quality aggregates. Over the years, therefore, consideration has been given to alternative materials including industrial wastes. This thesis is concerned with potential use of Minestone, the by-product of coal mining, for the lower structural layers of pavement construction. Because of their clay like nature, Minestones do not merit consideration for such applications in an unbound state and, therefore, some form of stabilisation is necessary. Previous research has demonstrated that certain cement bound minestones, containing between 5 and 10 per cent cement, satisfy current Department of Transport requirements for use in pavement construction and, furthermore, they are not frost susceptible. However, doubts concerning the durability of cement bound minestones still remain. The thesis includes a review of both the cement and lime stabilisation techniques and also traces the origin and development of the methods used to assess the quality and durability of stabilised materials. An experimental study is described in which cement bound minestone specimens were subjected to a programme of tests which examined compressive strength, resistance to immersion, and resistance to freezing and thawing. The results of the tests were related to the properties of the raw materials. It was discovered that the response to cement stabilisation was governed mainly by the source of the minestone and, to a lesser degree, the cement content. It was also found that resistance in the durability tests was generally improved when the initial moisture content was raised above the optimum value. The result suggest that current methods for assessing cement stabilised materials are not appropriate to cement bound minestones. Alternative methods and criteria, based on volume change and retained strength following immersion and freeze-thaw tests, have been proposed. It is believed that these methods and criteria should also apply to other cement bound materials.

Properties of seawater bitterns with regard to liquid-desiccant cooling

This study concerns the properties of the concentrated bittern solutions occurring as by-product from solar salt works, in relation to their potential use as liquid desiccants in cooling systems. Solutions of compositions similar to those of bitterns have been made up in the laboratory, as have concentrated mixtures of MgCl2–MgSO4–H2O. Measurements of vapour pressure have been carried out using an isoteniscope and are reported together with measurements of density and viscosity. Several theoretical models representing these properties are reviewed and compared against the experimental results; the average agreement between theory and experiment is within 5% for vapour pressure and better for the preferred models of the other two properties. Based on these findings, an expression is provided for the equilibrium relative humidity of bitterns as a function of concentration relative to raw seawater. The vapour pressures of bittern solutions are found to be similar to those of solutions containing only magnesium chloride but having the same mass fraction of total salts. Therefore magnesium chloride solution is a reasonable model for bitterns for the purpose of developing the proposed cooling system.

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.