Transition metal catalysts for the controlled radical polymerisation of vinyl monomers

The research described in this thesis concerns the synthesis of transition metal coordination complexes and their activity in the controlled radical polymerisation (CRP) of styrene, methyl methacrylate and vinyl acetate. In the first, introductory chapter, the literature pertaining to the main reported CRP systems is reviewed. The second chapter focuses on a family of novel α-diimine Fe(II) complexes bearing a conjugated acenaphthene backbone. The ligand-dependent catalytic behaviour in the atom transfer radical polymerisation (ATRP) of styrene is discussed, and the reaction conditions are varied to shed light on the system features. In the Chapter 3 the synthesis, characterisation and screening for reverse ATRP of the Fe(III) trichloride derivatives, as well as of two monodentate imino Fe(III) trichloride complexes, are described. A relationship between measured spin state and catalytic behaviour is highlighted. The fourth chapter reports the synthesis of bis-salicylaldimino Cr(II) complexes and their activity in the controlled radical polymerisation of styrene and vinyl acetate. The observed rearrangement of the latter monomer in the presence of chromium complexes is also examined. The fifth and final experimental chapter extends the studies carried out on bissalicylaldimino Cr(II) complexes to other transition metals, namely iron and cobalt. Chapter 6 gives the experimental details for Chapters 2-4. Crystallographic data for all X-ray diffraction structures presented in this thesis are collated in Chapter 7

The Global Warming Potential of Building Materials: An Application of Life Cycle Analysis in Nepal

open6siThis paper analyzes the global-warming potential of materials used to construct the walls of 3 building types—traditional, semimodern, and modern—in Sagarmatha National Park and Buffer Zone in Nepal, using the life-cycle assessment approach. Traditional buildings use local materials, mainly wood and stone, while semimodern and modern buildings use different amounts of commercial materials, such as cement and glass wool. A comparison of the greenhouse gas emissions associated with the 3 building types, using as the functional unit 1 m2 of wall, found that traditional buildings release about one-fourth of the greenhouse gas emissions released by semimodern buildings and less than one-fifth of the emissions of modern buildings. However, the use of thermal insulation in the modern building walls helps to reduce the energy consumption for space heating and consequently to reduce the global warming potential. In 25 years, the total global warming potential of a traditional building will be 20% higher than that of a modern building. If local materials, such as wood, are used in building construction, the emissions from production and transportation could be dramatically reduced.openBhochhibhoya, Silu; Zanetti, Michela; Pierobon, Francesca; Gatto, Paola; Maskey, R. K.; Cavalli, RaffaeleBhochhibhoya, Silu; Zanetti, Michela; Pierobon, Francesca; Gatto, Paola; Maskey, R. K.; Cavalli, Raffael

Grinding Test on Tremolite with Fibrous and Prismatic Habit

The main objective of this work is the evaluation of the morphology change in tremolite particles before and after a grinding process. The crushing action simulates anthropic alteration of the rock, such as excavation in rocks containing tremolite during a tunneling operation. The crystallization habit of these amphibolic minerals can exert hazardous eects on humans. The investigated amphibolic minerals are four tremolite samples, from the Piedmont and Aosta Valley regions, with dierent crystallization habits. The habits can be described as asbestiform (fibrous) for longer and thinner fibers and non-asbestiform (prismatic) for prismatic fragments, also known as “cleavage” fragments. In order to identify the morphological variation before and after the grinding, both a phase contrast optical microscope (PCOM) and a scanning electron microscope (SEM) were used. The identification procedure for fibrous and prismatic elements is related to a dimensional parameter (length–diameter ratio) defined by the Health and Safety Executive. The results highlight how mineral comminution leads to a rise of prismatic fragments and, therefore, to a potentially safer situation for worker and inhabitants

Vinyl-Asbestos Floor Risk Exposure in Three Different Simulations

Vinyl floors are widely used in public areas for their low cost and easy cleaning. From 1960 to 1980, asbestos was often added to improve vinyl floor performances. The Italian Ministerial Decree (M.D.) 06/09/94 indicates asbestos vinyl tiles as non-friable materials and, therefore, few dangerous to human health. This work aims to check through three different experimental tests if asbestos floor tiles, after decades of use, maintain their characteristics of compactness and non-friability. The effect of a small stone fragment stuck in the sole of rubber shoes was reproduced by striking the vinyl floor with a crampon. A vinyl tile was broken into smaller pieces with the aid of pliers to simulate what normally happens when workers replace the floors or sample it to verify the presence of asbestos. The third test reproduced the abrasion of the tile surface due to the dragging of furniture or heavy materials or sand grains that remain attached to the soles of shoes. The tests were carried out in safe conditions, working under an extractor hood with a glove box. Airborne sampling in the hood obtained the concentration of asbestos fibers produced in each test. The simulation tests performed confirms the possible release of fibers if the vinyl tiles are cut, abraded or perforated, as indicated by the Italian M.D

Interaction between <i>Mycobacterium tuberculosis</i>, <i>Mycobacterium bovis</i>, <i>Mycobacterium avium</i> subspecies <i>paratuberculosis</i> with the enteric glia and microglial cells

Background We investigated the interaction of Mycobacterium avium subspecies paratuberculosis, M. bovis and M. tuberculosis and different glial cells (enteric glial and microglial cells) in order to evaluate the infecting ability of these microorganisms and the effects produced on these cells, such as the evaluation of cytokines expression. Results Our experiments demonstrated the adhesion of M. paratuberculosis to the enteroglial cells and the induction of IL-1A and IL-6 expression; M. tuberculosis and M. bovis showed a good adhesive capability to the enteric cell line with the expression of the following cytokines: IL-1A and IL-1B, TNF-α, G-CSF and GM-CSF; M. bovis induced the expression of IL-6 too. The experiment performed with the microglial cells confirmed the results obtained with the enteroglial cells after the infection with M. tuberculosis and M. bovis, whereas M. paratuberculosis stimulated the production of IL-1A and IL-1B. Conclusion Enteroglial and microglial cells, could be the target of pathogenic mycobacteria and, even if present in different locations (Enteric Nervous System and Central Nervous System), show to have similar mechanism of immunomodulation

Identification of dangerous fibers: some examples in Northern Italy

The presence of asbestiform minerals has to be foreseen in the planning of infrastructural activities: Asbestos can be a component of sedimentary rocks or of mafic and ultra mafic metamorphic rocks. Surveys and core drilling, in addition to providing important information on the quality of the rock and its geotechnical characteristics, allow for a prediction of the presence of asbestiform minerals in the areas affected by mining or infrastructural activities. During the excavation, workers can be exposed to the asbestos risk, therefore, the control of the air quality and of the excavated materials are fundamental for the safety of involved people. In this work some problems we met in the analysis of airborne filters and bulk samples from sites in northern Italy are presented. The asbestos fibers present in rocks as accessory minerals, are often different in habit and dimension from the well-known asbestos fibers used as industrial minerals and moreover can be erroneously identified as minerals morphologically and chemically similar present in the same rock or environment. In the case of tunnel muck it could be contaminated by substances used for the excavation that could modify colours and optical properties of asbestos minerals. In the PCOM (Phase Contrast Optical Microscope) analysis chrysotile, sepiolite and antigorite, due to their different refraction index, when the fibers have dimension > 0,5 micron and aren’t contaminated by lubricant can be easely identified even if the morphology of chrysotile is very similar to that of sepiolite. In Electron Scanning Microscope (SEM) the discrimination between chrysotile and antigorite on the airborne filters is not always possible because the fibers of thin dimensions show similar habit and spectrum. In the case of the tremolite amphibole, morphology changes from prismatic to fibrous depending on its origin (p.eg. Monastero, Val Grana, Verrayes, Brachiello). Both prismatic and asbestiform tremolite (Gamble and Gibbs, 2007; Addison and McConnel, 2007) may show inhalable elements with width less than 3 micron, length more than 5 micron and width length ratio 1:3, whose dangerousness (fiber coming from fibrous tremolite or the cleavage fragments coming from prismatic tremolite) could be different and it is object of epidemiologic studies

The cDNA of the neutrophil antibiotic Bac5 predicts a pro-sequence homologous to a cysteine proteinase inhibitor that is common to other neutrophil antibiotics.

Bac5 is a 5-kDa proline- and arginine-rich antibiotic, stored as inactive precursor (proBac5) in the large granules of bovine neutrophils. A full-length cDNA encoding the precursor form of Bac5 has been cloned. The encoded protein (pre-proBac5) has a calculated mass of 20,031 Da and a pI of 9.21. This comprises a putative signal peptide of 29 amino acid residues and a 101-residue pro-sequence that precede the mature antibiotic. The pro-sequence is acidic and may neutralize the highly cationic Bac5, thus accounting for the inactivation of the antibiotic activity observed in in vitro experiments. The structure of mature Bac5 agrees closely with the amino acid sequence previously determined, with an additional tripeptide tail predicting carboxyl-terminal amidation. A valyl residue is deduced at the cleavage site for the proteolytic maturation of proBac5, consistent with a previous observation showing elastase as the enzyme involved in this processing step. The region upstream of Bac5 reveals high identity to corresponding regions of two neutrophil antimicrobial polypeptides, CAP18 from rabbit and bovine indolicidin. The COOH-terminal sequences of these antibiotics are completely unrelated. The proregion also exhibits remarkable similarity to pig cathelin, an inhibitor of cathepsin L, indicating a common evolutionary origin

Tuberculosis in Sardinia: An investigation into the relationship between natives and immigrants

AbstractObjective/background: Tuberculosis (TB) has had a recrudescence in the last few decades in Italy as a result of many factors, among which migration from countries where TB is endemic is one of them. In Sardinia, a major island of Italy, there was no knowledge of the mechanisms of transmission of TB in the immigrant subpopulation and the impact it may have on the native subpopulation and on the community as a whole. Therefore, a molecular epidemiological study was carried out to get a clearer picture of the number and genetic features of Mycobacterium tuberculosis strains isolated from immigrants and from natives in Sardinia. Methods: Two groups of clinical isolates of M. tuberculosis, one collected from immigrants and the other one from Sardinians, were analyzed in this study. The genotyping was executed through the variable number tandem repeat-mycobacterial interspersed repetitive units technique and a first-line antimycobacterial drug-susceptibility test was also carried out. Results: Thirty-six clinical isolates from immigrants and 25 from Sardinians were analyzed. Variable number tandem repeat-mycobacterial interspersed repetitive units technique showed that all of them belonged to different strains and there was a quite high allelic diversity among them. Moreover, data collected allowed the finding of, with a good approximation, the phylogenetic relations among the strains isolated and the best-known phylogenetic groups. Conclusion: The study pointed out that since every strain is different, there was no TB transmission in any of the subpopulations and between immigrants and natives. This showed that the presence of immigrants was not a risk factor for contracting TB in the community

Chemical Composition and Antimicrobial Activities of Essential Oil of Stachys Glutinosa L. from Sardinia

The oil composition of Stachys glutinosa L. from two different areas of Sardinia was analyzed by GC/MS. The oil from Gallura plants was characterized by the four main constituents: terpinen-4-ol (12.7%), α-terpinyl acetate (10.6%), trans-cadina-1(6),4-diene (8.5%), and α-terpineol (8.4%) whilst α-cedrene (19.2%), α-terpineol (18.5%), terpinen-4-ol (12.6%), and α-terpinyl acetate (8.6%) were the main compounds in the oil from Ulassai plants. The oils showed good bacteriostatic activities against Vibrio cholerae (MIC 0.6%), all the Candida tested (1.25%) and Rodotorula rubra (2.5%). There were also bactericidal activities against Candida glabrata (1.25 %) and Rodotorula rubra (2.5%)