Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Role of copper in reducing hospital environment contamination

The environment may act as a reservoir for pathogens that cause healthcare-associated infections (HCAIs). Approaches to reducing environmental microbial contamination in addition to cleaning are thus worthy of consideration. Copper is well recognised as having antimicrobial activity but this property has not been applied to the clinical setting. We explored its use in a novel cross-over study on an acute medical ward. A toilet seat, set of tap handles and a ward entrance door push plate each containing copper were sampled for the presence of micro-organisms and compared to equivalent standard, non-copper-containing items on the same ward. Items were sampled once weekly for 10 weeks at 07:00 and 17:00. After five weeks, the copper-containing and non-copper-containing items were interchanged. The total aerobic microbial counts per cm2 including the presence of ‘indicator micro-organisms’ were determined. Median numbers of microorganisms harboured by the copper-containing items were between 90% and 100% lower than their control equivalents at both 07:00 and 17:00. This reached statistical significance for each item with one exception. Based on the median total aerobic cfu counts from the study period, five out of ten control sample points and zero out of ten copper points failed proposed benchmark values of a total aerobic count of <5 cfu/cm2. All indicator micro-organisms were only isolated from control items with the exception of one item during one week. The use of copper-containing materials for surfaces in the hospital environment may therefore be a valuable adjunct for the prevention of HCAIs and requires further evaluation.

A computational approach to measuring the correlation between expertise and social media influence for celebrities on microblogs

Existing approaches of social influence analysis usually focus on how to develop effective algorithms to quantize users' influence scores. They rarely consider a person's expertise levels which are arguably important to influence measures. In this paper, we propose a computational approach to measuring the correlation between expertise and social media influence, and we take a new perspective to understand social media influence by incorporating expertise into influence analysis. We carefully constructed a large dataset of 13,684 Chinese celebrities from Sina Weibo (literally 'Sina microblogging'). We found that there is a strong correlation between expertise levels and social media influence scores. In addition, different expertise levels showed influence variation patterns: high-expertise celebrities have stronger influence on the 'audience' in their expertise domains.

Copper complexes as a source of redox active MRI contrast agents

The study reports an advance in designing copper-based redox sensing MRI contrast agents. Although the data demonstrate that copper(II) complexes are not able to compete with lanthanoids species in terms of contrast, the redox-dependent switch between diamagnetic copper(I) and paramagnetic copper(II) yields a novel redox-sensitive contrast moiety with potential for reversibility.

Hydroxyl radical generation by cactus-like copper oxide nanoporous carbon catalysts for microcystin-LR environmental remediation

Copper oxide supported on nanoporous activated carbon (CuO-NPAC) is reported for the aqueous phase catalytic degradation of cyanotoxin microcystin-LR (MC-LR). The loading and spatial distribution of CuO throughout the NPAC matrix strongly influence the catalytic efficiency. CuO-NPAC synthesis was optimized with respect to the copper loading and thermal processing, and the physicochemical properties of the resulting materials were characterized by XRD, BET, TEM, SEM, EPR, TGA, XPS and FT-IR spectroscopy. EPR spin trapping and fluorescence spectroscopy showed in situ ˙OH formation via H2O2 over CuO-NPAC as the catalytically relevant oxidant. The impact of reaction conditions, notably CuO-NPAC loading, H2O2 concentration and solution pH, is discussed in relation to the reaction kinetics for MC-LR remediation.

Formation and investigation of nanostructured thin films

Small devices, in the range of nanometers, are playing a major role in today's technology. The field of nanotechnology is concerned with materials and systems whose structures and components exhibit novel and significantly improved physical, chemical and biological properties, phenomena and processes due to their small nanoscale size. Researches more and more are finding that structural features in the range of about 1 to 100 nanometers behave quite differently than isolated molecules (1 nanometer) or bulk materials. For comparison, a 10 nanometer structure is 1000 times smaller than the diameter of a human hair. The virtues of working in the nanodomain are increasingly recognized by the scientific community and discussed in the popular press. The use of such devices is expected to revolutionize our industries and lives. ^ This work mainly focuses on the fabrication, characterization and discovery of new nanostructured thin films. This research consists of the design of a new high-deposition rate nanoparticle machine for depositing nanostructured films from beams of nanoparticles and investigation film's unique optical and physical properties.^ A high-deposition rate nanoparticle machine was designed, built and successfully tested. Different nanostructured thin films were deposited from Copper, Gold, Iron and Zirconium targets with the grain size of between 1 to 20 nm under different conditions. Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), and x-ray diffraction (XRD) confirmed nanoscale grain size structures of deposited films. The optical properties of the nanostructured films deposited from copper, Iron and Zirconium targets were significantly different from optical properties of bulk and thin films. Zr, Cu and Fe films were transparent. Gold films revealed an epitaxial contact with the silicon substrate with interesting crystal structures. ^ The new high-deposition rate nanoparticle machine was able to deposit new nanostructured films with different properties from bulk and thin films reported in the literatures. ^

Analysis of manganese deposits from the Pacific Ocean

Sea floor dredging by the H.M.S. Challenger, the U.S.S. Albatross, the U.S.S. EPC(R) 857, and vessels of the Scripps Institution of Oceanography shows that extensive deposits of manganese nodules are on the deep sea floor and that crusts of manganese dioxide cover many seamounts. Sea floor photography reveals that in some places these crusts are quite continuous and the nodules are closely packed. These crusts and nodules are fully oxidized and hydrated mixtures of man¬ganese and iron plus earthy impurities. Also, relatively high concen¬trations of the trace elements nickel, copper, and cobalt are present.

Castles in the air: the life, times and influence of the Reverend Moses Harvey (1820-1901).

The period from 1874 to 1901 was a time of significant transition in the economic and political life of Newfoundland. Twenty years into responsible government and with Confederation on the backburner, the colony’s politicians turned their attention to economic diversification, landward development and carving out the island’s place in the British Empire. The period saw both economic prosperity and retrenchment; the construction of a trans-insular railway; the adoption of policies to foster agriculture, forestry, manufacturing and mining; and diplomatic efforts to resolve France’s outstanding claims on the northwest coast of the island. At the same time, the government made an attempt to intervene directly in its primary industry, the fisheries. It created a Fisheries Commission in 1889 that recommended conservation measures and artificial propagation as ways to restore the health of some of the island’s fish stocks. They also proposed new methods of curing, packaging and marketing Newfoundland’s cod, as well as a complete overhaul of the truck system. A major player in both the public and private debates surrounding all of these subjects was the Reverend Moses Harvey. Along with being minister of the Free Church of Scotland in St. John’s, Harvey was one of Newfoundland’s most active promoters in the late nineteenth century. He served as the media mouthpiece for both Prime Minister William Whiteway and Prime Minister Robert Thorburn; editing the Evening Mercury – the official organ of the Liberal Party and then the Reform Party – from 1882 to 1883 and 1885 until 1890. As well, Harvey wrote regular columns on Newfoundland issues for newspapers in London, New York, Boston, Montreal, Toronto, and Halifax. He also produced numerous books, articles, encyclopedia entries, and travel guides outlining the island’s attractions and its vast economic potential. In short, Harvey made a significant contribution in shaping the way residents and the outside world viewed Newfoundland during this period. This thesis examines late nineteenth-century Newfoundland through the writing of Moses Harvey. The biographical approach offers a fuller, more nuanced account of some of the major historical themes of the period including the politics of progress, opening up the interior, railway construction and attitudes toward the fisheries. It also provides an insider’s prospective on what led to some of the major political decisions, policy positions or compromises taken by the Whiteway and Thorburn governments. Finally, a more detailed review of Harvey’s work exposes the practical and political differences that he had with people like D.W. Prowse and Bishop Michael Howley. While these so-called “boomers” in Newfoundland’s historiography agreed on broad themes, they parted ways over what should be done with the fisheries and how best to channel the colony’s growing sense of nationalism.

The geological and microbiological controls on the occurrence, mobility and concentration of Se and Te in coal and black shales

© 2016 Institute of Materials, Minerals and Mining and The AusIMM Published by Taylor & Francis on behalf of the Institute and The AusIMM

Chemical composition of nodules from two locations in the Pacific Ocean using different methods

Manganese nodules recovered in the Pacific Ocean by the U. S. Bureau of Mines and by DeepSea Ventures Ltd. are studied for their chemical composition using X microprobe and X-ray fluorescence methods.

Systematics of African Amphicyonidae, with descriptions of new material from Napak (Uganda) and Grillental (Namibia)

The Early Miocene Napak XV locality (ca 20.5 Ma), Uganda, has yielded an interesting assemblage of fossils, including the very well represented amphicyonid Hecubides euryodon. The remarkable find of a nearly complete mandible, unfortunately with poorly preserved dentition, together with new dental remains allow us to obtain a better idea about the morphology and variability of this species. Additionally, we describe a newly discovered mandible of Hecubides euryodon from the Grillental-VI locality (Sperrgebiet, Namibia), which is the most complete and diagnostic Amphicyonidae material found in this area. Comparisons with Cynelos lemanensis from Saint Gérand le Pouy (France), the type locality, and with an updated sample of the species of amphicyonids described in Africa leads us to validate the genus Hecubides. Hecubides would be phylogenetically related to the medium and large size species of Amphicyonidae from Africa, most of them now grouped into the genera Afrocyon and Myacyon, both endemic to this continent.

Los emigrantes en las áreas mineras y las ciudades de Hispania: religión, identidades y difusión cultural

En el presente artículo analizamos los desplazamientos de cultos indígenas hispanos desde distintas áreas de la Península Ibérica hacia los principales lugares de inmigración en Hispania: las áreas mineras y las ciudades. Proponemos que estos grupos de emigrantes rendían culto en su nueva residencia a las deidades que veneraban en sus regiones de procedencia como un medio de preservar su cohesión social y su identidad cultural. La dureza de la vida laboral en las áreas mineras reforzaba la necesidad de fortalecer los lazos culturales.

A Comparative Study of Copper Chalcogenide Nanocrystals as Agents for Photothermal Therapy

Thesis (Master's)--University of Washington, 2016-08

Contextual text mining

With the dramatic growth of text information, there is an increasing need for powerful text mining systems that can automatically discover useful knowledge from text. Text is generally associated with all kinds of contextual information. Those contexts can be explicit, such as the time and the location where a blog article is written, and the author(s) of a biomedical publication, or implicit, such as the positive or negative sentiment that an author had when she wrote a product review; there may also be complex context such as the social network of the authors. Many applications require analysis of topic patterns over different contexts. For instance, analysis of search logs in the context of the user can reveal how we can improve the quality of a search engine by optimizing the search results according to particular users; analysis of customer reviews in the context of positive and negative sentiments can help the user summarize public opinions about a product; analysis of blogs or scientific publications in the context of a social network can facilitate discovery of more meaningful topical communities. Since context information significantly affects the choices of topics and language made by authors, in general, it is very important to incorporate it into analyzing and mining text data. In general, modeling the context in text, discovering contextual patterns of language units and topics from text, a general task which we refer to as Contextual Text Mining, has widespread applications in text mining. In this thesis, we provide a novel and systematic study of contextual text mining, which is a new paradigm of text mining treating context information as the ``first-class citizen.'' We formally define the problem of contextual text mining and its basic tasks, and propose a general framework for contextual text mining based on generative modeling of text. This conceptual framework provides general guidance on text mining problems with context information and can be instantiated into many real tasks, including the general problem of contextual topic analysis. We formally present a functional framework for contextual topic analysis, with a general contextual topic model and its various versions, which can effectively solve the text mining problems in a lot of real world applications. We further introduce general components of contextual topic analysis, by adding priors to contextual topic models to incorporate prior knowledge, regularizing contextual topic models with dependency structure of context, and postprocessing contextual patterns to extract refined patterns. The refinements on the general contextual topic model naturally lead to a variety of probabilistic models which incorporate different types of context and various assumptions and constraints. These special versions of the contextual topic model are proved effective in a variety of real applications involving topics and explicit contexts, implicit contexts, and complex contexts. We then introduce a postprocessing procedure for contextual patterns, by generating meaningful labels for multinomial context models. This method provides a general way to interpret text mining results for real users. By applying contextual text mining in the ``context'' of other text information management tasks, including ad hoc text retrieval and web search, we further prove the effectiveness of contextual text mining techniques in a quantitative way with large scale datasets. The framework of contextual text mining not only unifies many explorations of text analysis with context information, but also opens up many new possibilities for future research directions in text mining.

Effects of various salt purity levels on lipid oxidation and sensory characteristics of ground turkey and pork

Salt use in meat products is changing. Consumers desire sea salt which may also contain trace metals and the government is demanding a reduction in sodium. Therefore a need exists to understand how varying impurity levels in salt affect meat quality. This study evaluated the effects of various salt preparations on lipid oxidation, sensory characteristics, protein extractability, and bind strength of ground turkey and pork. This study was a completely randomized design with 5 treatment groups and 6 replications in 2 species. Ground, turkey and pork meat was formulated into one hundred and fifty gram patties with sodium chloride (1%) containing varying amounts of metal impurities (copper, iron, and manganese). Samples were randomly assigned to frozen storage periods of 0, 3, 6, and 9 weeks. After storage, samples were packaged in PVC overwrap and stored under retail display for 5 days. Samples were evaluated for proximate analysis to ensure the fat content was similar for all of the starting material.Thiobarbituric acid reactive substances (TBARS) were determined on raw and cooked samples to evaluate lipid oxidation. A trained six member sensory panel evaluated the samples at each storage period for saltiness, off flavor, and oxidized odor. Break strength was conducted using a Texture Analyzer and compared with salt soluble proteins (increasing salt concentrations) to evaluate protein extractability characteristics. Statistical analyses were conducted using the MIXED procedure of SAS within repeated measures over time where appropriate. No significant differences were observed among the salt treatments for raw and cooked TBARS when the control group was removed (P>0.05). Sensory panelists detected increased levels of off flavor and oxidized odor over the entire storage duration. Less force was required to break the patties from the control group when compared with the salt treatments (P<0.05). As salt concentration increased salt-soluble protein extraction increased, but there was no effect of salt type. Overall, no meaningful statistical differences among the various salt treatments were observed for all of the parameters evaluated for turkey and pork. Salt at a 1% inclusion rate containing varying levels of copper, iron, and manganese impurities in ground turkey thigh meat and ground pork served as a prooxidant. However, if a meat processor uses a 1% inclusion rate of salt in turkey and pork regardless of impurities included, it is unlikely that differences in shelf life or protein functionality would be observed.