Synthesis of 4-substituted-3(2H)-furanones with novel luminescence properties

The objective of this project was to prepare a range of 4-substituted 3-(2H)-furanones, and to investigate the relationship between their molecular structures and photoluminescence properties. The effects of substituents and conjugated linker unit were also investigated. After generation of the key 3(2H)-furanone heterocycle, extension of the conjugated framework at the C-4 position was achieved through Pd(0)-catalysed coupling reactions. Chapter one of the thesis comprises a review of the relavent literature and is split into three sections. These include information about the prevalence of 3-(2H)-furanones as natural products and synthetic routes to 3-(2H)-furanones in general. The synthetic routes are divided according to the synthetic precursor employed. The final section of chapter one outlines the fundamental principles and application of photoluminescence to organic compounds in general. Chapter two contains the results of the research achieved in the course of this work and a discussion of the findings. Two routes were successfully employed to generate 4-unsubstituted 3-(2H)-furanone moieties: (i) base induced cyclisation of hydroxyenones and (ii) isoxazole chemistry. A number of methods which proved ineffective in the production of furanones with the desired substitution pattern are also detailed. The majority of this study was focused on the introduction of substituents at the C-4 position of the 3-(2H)-furanone ring. This was achieved through the use of Sonogashira and Suzuki cross coupling protocols for Pd(0) catalysed C-C bond formation. The further functionalisation of some compounds was performed using transfer hydrogenation and “click chemistry” methodologies. Finally, the photophysical properties of 3-(2H)-furanones prepared in this project are discussed and the effect of substitution patterns in a complementary “push push” and “push pull” manner have also been investigated. All the experimental data and details of the synthetic methods employed, for the compounds prepared during the course of this research is contained in chapter three together with the spectroscopic and analytical properties of the compounds prepared.

Religion, the study of religion and other products of transnational and colonial imaginings

The category of ‘religion’ as contemporary scholarship has demonstrated is a fairly recent innovation, dating back only a few hundred years in Western thought, and ‘world religions’ as we think of it and as we teach it is an even more recent category, emerging out of European colonialism. Thus the academic study of religion is both the product and, at times, the agent of colonial modes of knowledge. And yet, it is perhaps because ‘religion’ continues to be invented and reinvented through connections across cultures that investigating the work of religious ideas and practices offers such fruitful possibilities for understanding the work of culture and power. This article investigates religion and the study of religion as a mode of anti-colonial practice, seeking to understand how each have the potential to cross boundaries, build bridges and produce critical insights into assumptions and worldviews too often taken for granted.

An investigation into reactivity and selectivity in cycloadditions of 1,3-dipoles with formamidines

The objective of this research was to investigate the synthesis of nitrile oxides and to study their reactivity in 1,3-dipolar cycloadditions with formamidines. Chapter one looks at the literature surrounding the 1,3-dipolar cycloaddition reaction. It explores the generation of 1,3-dipoles (mainly nitrile oxides) and dipolarophiles (predominantly amidines). It discusses the potential synthetic uses of the 1,3-dipolar cycloadducts. It examines both and inter- and intra-molecular cycloaddition reactions. It recognises the use of the 1,3-dipolar cycloadditions as a successful method in building natural products and oxadiazolines. The decomposition of oxadiazolines as a route to nitriles is also outlined in this chapter. Chapter two discusses the results of this research candidate. The preparation of nitrile oxide precursors - hydroximoyl halides - is outlined at first. The generation of nitrile oxides is then demonstrated, followed by the preparation of furoxans. Methods for preparing the reference materials (nitriles and ureas), which result from decomposition of oxadiazolines, then follow. The preparation of series of Δ2-1,2,4- oxadiazolines via the 1,3-dipolar cycloaddition reaction is illustrated in this chapter. The selectivity of the addition of nitrile oxides to dipolarophiles was tested by competition reactions, which are also described in this chapter. NMR techniques were used in the study of the kinetics of the 1,3-dipolar cycloadditions used for the preparation of a series of Δ2-1,2,4-oxadiazolines, which is addressed in this chapter. Chapter three charts the experimental procedures followed to gain results which are discussed in chapter two. It also outlines all analytical data produced during the course of this research.

Salted fish products from the Coptic monastery at Bawit, Egypt: evidence from the bones and texts

Fish bone assemblages are described that were recently discovered in the storage area of two rooms, dated to the 7th century AD, from the monastery of Bawit, Egypt. The species composition, the reconstructed sizes of the fish and the find contexts show that this material represents pickled fish (salsamenta). This product was made in one case of medium-sized Clarias catfish, whereas another assemblage, found inside an amphora, consisted of small-sized fish, mainly cyprinids and alestiids. The latter product was stored in a Late Roman Amphora 5/6 of Palestinian origin, traditionally considered as a container for wine. The amphora was clearly re-used since the fish found in it are Nilotic species which excludes that the salsamenta came from outside Egypt. A few additional finds of fish inside amphorae were available, but due to the low number of bones it was unclear if salted fish products were stored in them. Textual information provided by ostraca and papyri from the same site shows that the monks exerted fishing activities themselves and also suggests that the production of pickled fish took place locally. One of the two Nilotic fish taxa (Labeo) that is specifically mentioned by written evidence is the most common ingredient found in the amphora with abundant fish remains. The paper ends with a brief summary of other faunal evidence for salted fish products from monastic and other historic sites in Egypt.

Assessing variability and long-term trends in burned area by merging multiple satellite fire products

Long term, high quality estimates of burned area are needed for improving both prognostic and diagnostic fire emissions models and for assessing feedbacks between fire and the climate system. We developed global, monthly burned area estimates aggregated to 0.5° spatial resolution for the time period July 1996 through mid-2009 using four satellite data sets. From 2001ĝ€ "2009, our primary data source was 500-m burned area maps produced using Moderate Resolution Imaging Spectroradiometer (MODIS) surface reflectance imagery; more than 90% of the global area burned during this time period was mapped in this fashion. During times when the 500-m MODIS data were not available, we used a combination of local regression and regional regression trees developed over periods when burned area and Terra MODIS active fire data were available to indirectly estimate burned area. Cross-calibration with fire observations from the Tropical Rainfall Measuring Mission (TRMM) Visible and Infrared Scanner (VIRS) and the Along-Track Scanning Radiometer (ATSR) allowed the data set to be extended prior to the MODIS era. With our data set we estimated that the global annual area burned for the years 1997ĝ€ "2008 varied between 330 and 431 Mha, with the maximum occurring in 1998. We compared our data set to the recent GFED2, L3JRC, GLOBCARBON, and MODIS MCD45A1 global burned area products and found substantial differences in many regions. Lastly, we assessed the interannual variability and long-term trends in global burned area over the past 13 years. This burned area time series serves as the basis for the third version of the Global Fire Emissions Database (GFED3) estimates of trace gas and aerosol emissions.

Using fractal downscaling of satellite precipitation products for hydrometeorological applications

The objective of spatial downscaling strategies is to increase the information content of coarse datasets at smaller scales. In the case of quantitative precipitation estimation (QPE) for hydrological applications, the goal is to close the scale gap between the spatial resolution of coarse datasets (e.g., gridded satellite precipitation products at resolution L × L) and the high resolution (l × l; L»l) necessary to capture the spatial features that determine spatial variability of water flows and water stores in the landscape. In essence, the downscaling process consists of weaving subgrid-scale heterogeneity over a desired range of wavelengths in the original field. The defining question is, which properties, statistical and otherwise, of the target field (the known observable at the desired spatial resolution) should be matched, with the caveat that downscaling methods be as a general as possible and therefore ideally without case-specific constraints and/or calibration requirements? Here, the attention is focused on two simple fractal downscaling methods using iterated functions systems (IFS) and fractal Brownian surfaces (FBS) that meet this requirement. The two methods were applied to disaggregate spatially 27 summertime convective storms in the central United States during 2007 at three consecutive times (1800, 2100, and 0000 UTC, thus 81 fields overall) from the Tropical Rainfall Measuring Mission (TRMM) version 6 (V6) 3B42 precipitation product (~25-km grid spacing) to the same resolution as the NCEP stage IV products (~4-km grid spacing). Results from bilinear interpolation are used as the control. A fundamental distinction between IFS and FBS is that the latter implies a distribution of downscaled fields and thus an ensemble solution, whereas the former provides a single solution. The downscaling effectiveness is assessed using fractal measures (the spectral exponent β, fractal dimension D, Hurst coefficient H, and roughness amplitude R) and traditional operational scores statistics scores [false alarm rate (FR), probability of detection (PD), threat score (TS), and Heidke skill score (HSS)], as well as bias and the root-mean-square error (RMSE). The results show that both IFS and FBS fractal interpolation perform well with regard to operational skill scores, and they meet the additional requirement of generating structurally consistent fields. Furthermore, confidence intervals can be directly generated from the FBS ensemble. The results were used to diagnose errors relevant for hydrometeorological applications, in particular a spatial displacement with characteristic length of at least 50 km (2500 km2) in the location of peak rainfall intensities for the cases studied. © 2010 American Meteorological Society.

Rare variants create synthetic genome-wide associations.

Genome-wide association studies (GWAS) have now identified at least 2,000 common variants that appear associated with common diseases or related traits (http://www.genome.gov/gwastudies), hundreds of which have been convincingly replicated. It is generally thought that the associated markers reflect the effect of a nearby common (minor allele frequency >0.05) causal site, which is associated with the marker, leading to extensive resequencing efforts to find causal sites. We propose as an alternative explanation that variants much less common than the associated one may create "synthetic associations" by occurring, stochastically, more often in association with one of the alleles at the common site versus the other allele. Although synthetic associations are an obvious theoretical possibility, they have never been systematically explored as a possible explanation for GWAS findings. Here, we use simple computer simulations to show the conditions under which such synthetic associations will arise and how they may be recognized. We show that they are not only possible, but inevitable, and that under simple but reasonable genetic models, they are likely to account for or contribute to many of the recently identified signals reported in genome-wide association studies. We also illustrate the behavior of synthetic associations in real datasets by showing that rare causal mutations responsible for both hearing loss and sickle cell anemia create genome-wide significant synthetic associations, in the latter case extending over a 2.5-Mb interval encompassing scores of "blocks" of associated variants. In conclusion, uncommon or rare genetic variants can easily create synthetic associations that are credited to common variants, and this possibility requires careful consideration in the interpretation and follow up of GWAS signals.

Fate of products of degradation processes: consequences for climatic change.

The end products of atmospheric degradation are not only CO2 and H2O but also sulfate and nitrate depending on the chemical composition of the substances which are subject to degradation processes. Atmospheric degradation has thus a direct influence on the radiative balance of the earth not only due to formation of greenhouse gases but also of aerosols. Aerosols of a diameter of 0.1 to 2 micrometer, reflect short wave sunlight very efficiently leading to a radiative forcing which is estimated to be about -0.8 watt per m2 by IPCC. Aerosols also influence the radiative balance by way of cloud formation. If more aerosols are present, clouds are formed with more and smaller droplets and these clouds have a higher albedo and are more stable compared to clouds with larger droplets. Not only sulfate, but also nitrate and polar organic compounds, formed as intermediates in degradation processes, contribute to this direct and indirect aerosol effect. Estimates for the Netherlands indicate a direct effect of -4 watt m-2 and an indirect effect of as large as -5 watt m-2. About one third is caused by sulfates, one third by nitrates and last third by polar organic compounds. This large radiative forcing is obviously non-uniform and depends on local conditions.

Prevalence of MRSA and Antimicrobial Resistance of Staphylococcus aureus in Maryland Ground Meat Products

Gemstone Team Antibiotic Resistance

Peptide interfacial biomaterials improve endothelial cell adhesion and spreading on synthetic polyglycolic acid materials.

Resorbable scaffolds such as polyglycolic acid (PGA) are employed in a number of clinical and tissue engineering applications owing to their desirable property of allowing remodeling to form native tissue over time. However, native PGA does not promote endothelial cell adhesion. Here we describe a novel treatment with hetero-bifunctional peptide linkers, termed "interfacial biomaterials" (IFBMs), which are used to alter the surface of PGA to provide appropriate biological cues. IFBMs couple an affinity peptide for the material with a biologically active peptide that promotes desired cellular responses. One such PGA affinity peptide was coupled to the integrin binding domain, Arg-Gly-Asp (RGD), to build a chemically synthesized bimodular 27 amino acid peptide that mediated interactions between PGA and integrin receptors on endothelial cells. Quartz crystal microbalance with dissipation monitoring (QCMD) was used to determine the association constant (K (A) 1 x 10(7) M(-1)) and surface thickness (~3.5 nm). Cell binding studies indicated that IFBM efficiently mediated adhesion, spreading, and cytoskeletal organization of endothelial cells on PGA in an integrin-dependent manner. We show that the IFBM peptide promotes a 200% increase in endothelial cell binding to PGA as well as 70-120% increase in cell spreading from 30 to 60 minutes after plating.

Convenient synthetic routes to bidentate and monodentate 2-, 3- and 4-pyridyl phosphines: potentially useful ligands for water-soluble complex catalysts

The monodentate and bidentate pyridyl phosphines, PR3 and R2P(CH2)2PR2, where R=3- or 4-pyridyl can be prepared in high yields by treatment of butyllithium/TMEDA/3- or 4-bromopyridine with PCl3 or Cl2P(CH2)2PCl2 at low temperature. 1,2-Bis(di-2-pyridylphosphino)ethane is conveniently synthesised by an alternative route involving reaction of 1,2-dibromoethane with lithium di-2-pyridylphosphide.

Flo/Stress: an integrated software module to predict stress in electronic products

Software technology that predicts stress in electronic systems and packages, developed as part of TCS Programme, is described. The software is closely integrated within a thermal design tool providing the ability to simulate the coupled effects of airflow, temperature and stress on product performance. This integrated approach to analysis will help decrease the number of design cycles.

A case based model to assist in the design process in the manufacture of furniture products

This paper describes progress on a project to utilise case based reasoning methods in the design and manufacture of furniture products. The novel feature of this research is that cases are represented as structures in a relational database of products, components and materials. The paper proposes a method for extending the usual "weighted sum" over attribute similarities for a ·single table to encompass relational structures over several tables. The capabilities of the system are discussed, particularly with respect to differing user objectives, such as cost estimation, CAD, cutting scheme re-use, and initial design. It is shown that specification of a target case as a relational structure combined with suitable weights can fulfil several user functions. However, it is also shown that some user functions cannot satisfactorily be specified via a single target case. For these functions it is proposed to allow the specification of a set of target cases. A derived similarity measure between individuals and sets of cases is proposed.

Response Surface Modeling and Optimisation for Reliable Electronic Products

The aim of integrating computational mechanics (FEA and CFD) and optimization tools is to speed up dramatically the design process in different application areas concerning reliability in electronic packaging. Design engineers in the electronics manufacturing sector may use these tools to predict key design parameters and configurations (i.e. material properties, product dimensions, design at PCB level. etc) that will guarantee the required product performance. In this paper a modeling strategy coupling computational mechanics techniques with numerical optimization is presented and demonstrated with two problems. The integrated modeling framework is obtained by coupling the multi-physics analysis tool PHYSICA - with the numerical optimization package - Visua/DOC into a fuJly automated design tool for applications in electronic packaging. Thermo-mechanical simulations of solder creep deformations are presented to predict flip-chip reliability and life-time under thermal cycling. Also a thermal management design based on multi-physics analysis with coupled thermal-flow-stress modeling is discussed. The Response Surface Modeling Approach in conjunction with Design of Experiments statistical tools is demonstrated and used subsequently by the numerical optimization techniques as a part of this modeling framework. Predictions for reliable electronic assemblies are achieved in an efficient and systematic manner.

Decision support systems for eco-friendly electronic products

This paper discusses an optimisation based decision support system and methodology for electronic packaging and product design and development which is capable of addressing in efficient manner specified environmental, reliability and cost requirements. A study which focuses on the design of a flip-chip package is presented. Different alternatives for the design of the flip-chip package are considered based on existing options for the applied underfill and volume of solder material used to form the interconnects. Variations in these design input parameters have simultaneous effect on package aspects such as cost, environmental impact and reliability. A decision system for the design of the flip-chip that uses numerical optimisation approach is used to identify the package optimal specification which satisfies the imposed requirements. The reliability aspect of interest is the fatigue of solder joints under thermal cycling. Transient nonlinear finite element analysis (FEA) is used to simulate the thermal fatigue damage in solder joints subject to thermal cycling. Simulation results are manipulated within design of experiments and response surface modelling framework to provide numerical model for reliability which can be used to quantify the package reliability. Assessment of the environmental impact of the package materials is performed by using so called Toxic Index (TI). In this paper we demonstrate the evaluation of the environmental impact only for underfill and lead-free solder materials. This evaluation is based on the amount of material per flip-chip package. Cost is the dominant factor in contemporary flip-chip packaging industry. In the optimisation based decision support system for the design of the flip-chip package, cost of materials which varies as a result of variations in the design parameters is considered.