Title: Comlpexes of aminoalkylphosphineoxides Author: Bence Mészáros Department: Department of Inorganic Chemistry, Faculty of Science UK Supervisor: doc. RNDr. Vojt ch Kubí ek, Ph.D. Supervisor's e-mail address: kubicek@natur.cuni.cz Three selected aminoalkylphosphine oxides were synthesized: Aminomethyl(diphenyl)phosphine oxide, N-piperidylmethyl(diphenyl)phosphine oxide, N,N-diethylaminomethylbis(hydroxomethyl)phosphine oxide. All prepared substances were characterized by NMR spectroscopy and mass spectrometry. The aminomethyl(diphenyl)phosphine oxide and N-piperidylmethyl(diphenyl)phosphine oxide were obtained in the solid state as single crystals and their structure was determined by X-ray analysis. Acid-base and complexing properties of the studied compounds were studied by potentiometric titration and NMR titration. Protonation constants of all three compounds were obtained, stability constants were not determined because of the low solubility of the complexes in water or low stability of the complexes. The structure of the aminomethyl(diphenyl)phosphine oxide complex with Cu2+ was determined by X-ray analysis. Keywords: complexes, organophosphorus synthesis, phosphine oxides, acid-base and complexation properties

Reactions leading to cyclization on methylene bridges in PCPCP structure motif were investigated. It was found, that these reactions result in number of various isomers. Some of these isomers were characterized by NMR and MS spectroscopy, but none was isolated. Further, acid-base properties of bis(methylenephosphonato)phosphineic acid were investigated. Formation of complexes was studied with lithium(I), calcium(II), copper(II) and zinc(II) cations. Furthermore, interaction between bis(methylenephosphonato)phosphinic acid and ethylenediamine was investigated by NMR and potentiometric titration. The results show formation of H-bond-based adducts.

Relative changes are detectable in the blood of end-stage renal disease (ESRD) patients during hemodialysis (HD) treatment using optical spectroscopy. However, the potential impacts of several confounding factors that could affect the detection of these changes have not been evaluated. The objectives of this thesis were to: 1) investigate how the variations and/or changes in acid-base and oxygen parameters during HD treatment can affect the optical signature of whole blood of ESRD patients, 2) to investigate the effect of heparin on the optical properties of whole blood and its impact on our method. Blood samples were drawn from 23 ESRD patients at 5 time points during a 4 hour HD treatment and sent for blood gas and blood spectroscopy analyses. No significant correlations were found between the changes in the blood transmittance spectra and acid-base and oxygen parameters. This indicates that the perturbations in these parameters due to HD procedures do not confound the detection of changes in the blood transmittance spectra of ESRD patients during HD treatment. Additionally, the effect of heparin in modifying the optical properties of whole blood does not confound the detection of changes in the blood of ESRD patients due to HD treatment using whole blood-based optical spectroscopy. ANOVA revealed significant (P<0.05) measurable changes in the blood transmittance spectra of ESRD patients during HD treatment. Significant spectral differences (P<0.05) were found between ESRD patients. The lack of uniform spectral characteristics across patients is

The acid-base disturbances in Canine Parvoviral Enteritis (CPV) are not well described. In addition the mechanisms causing these perturbations have not been fully elucidated. The purpose of this study was to assess acid-base changes in puppies suffering from Canine Parvoviral Enteritis (CPV) using a Modified Strong Ion Model (SIM). The hypothesis of this study was that severe acid-base disturbances would be present and that the SIM would provide patho-mechanistic insights that would not be fully appreciated by the Henderson-Hasselbalch model. The study retrospectively analysed data obtained from 42 puppies with confirmed CPV and 12 healthy controls. The CPV group had been allocated a clinical score to allow classification of the data according to clinical severity. The effects of changes in free water, chloride, lactate, albumin and phosphate were calculated using a modification of the base excess algorithm. The data for each of these variables was compared to the control group. When the data were summated for each patient and correlated to each individual component, the most important contributor to the metabolic acid-base changes according to SIM was chloride (P < 0.001). Severely affected animals tended to have a hypochloraemic alkalosis, whereas mildly effected puppies had a hyperchloraemic acidosis (P = 0.0023). In conclusion the acid base disturbances in CPV are multifactorial and complex and the SIM provides more information regarding the origin of these changes. / Dissertation (MMedVet)--University of Pretoria, 2013. / gm2014 / Companion Animal Clinical Studies / unrestricted

Large quantities of tailings are produced during gold and coal mining activities. These tailings consist of ash dumps, waste rock dumps, in-pit deposits and any other heap, pile or accumulation of residue in the tailings or slimes dams. It has been reported that these tailings can have a significant impact on water quality in the vicinity of gold and coal residues in South Africa. Water quality deterioration in the vicinity of gold and coal mines in the Johannesburg and other areas has been reported. However, little information is available on the potential impact of residues on water quality near Roodepoort and Newcastle where gold and coal, respectively, are mined. The objective of this investigation was therefore to determine the potential impact of gold and coal mine residues on the environment in the vicinity of Roodepoort and Newcastle. Secondary objectives were to identify the metal constituents of gold and coal mine residues, to evaluate and define the current knowledge with regard to the short-term water quality impact of gold and coal residues in terms of concentration of metals leaching from the residues, to assess the potential impact of gold and coal tailings on the water environment within the study areas and to suggest methods to prevent pollution from taking place. Acid Base Accounting (ABA), Toxicity Characteristics Leaching (TCLP), Acid Rain Leaching Procedure (ARLP) and Inductively Plasma Coupled – Mass Spectrometry (IPC-MS) were used as tools to determine the potential impact of gold and coal tailings on the environment. Acid Base Accounting comprises two components that show the potential of the mine residue to produce acid mine drainage, that is, the total sulphur and the net neutralisation potential (NNP). It has been reported that any pyrite mine residue containing more than 0.5% total sulphur may generate acid mine drainage. Mine residues with a net neutralisation potential of less than zero ppt CaCO3 produce acid drainage. The acid base accounting results show that the gold and coal mine residues contain sulphur which has the potential to produce acid mine drainage. Lithium (Li), sodium (Na) magnesium (Mg), aluminium (Al), potassium (K), calcium (Ca), iron (Fe), manganese (Mn) and nickel (Ni) were identified to be present in the gold mine residue. The concentrations of some of the metals that leached from the gold residue according to the TCLP tests were as follows: Al (22 mg/L); Ca (242 mg/L); Fe (29 mg/L); Mn (88 mg/L) and Ni (87 mg/L). The metals that leached from the gold residue according to the ARLP results were as follows: Na (43 mg/L); Al (169 mg/L); Ca (246 mg/L); Fe (771 mg/L); Mn (16 mg/L) and Ni (11 mg/L). Higher concentrations of metals generally leached from the gold residue with the ARLP test than with the TCLP test. The sulphate concentration up-stream of the gold residue was determined at 225 mg/L. This concentration increased to 3 490 mg/L at the decanting point and to 11 577 mg/L downstream of the decanting point. The surface and possibly groundwater are therefore polluted with sulphates. Lithium (Li), sodium (Na), magnesium (Mg), aluminium (Al), potassium (K), calcium (Ca), iron (Fe), manganese (Mn) and nickel (Ni) were identified to be present in the coal mine residue. The concentrations of some of the metals that leached from the coal residue according to the TCLP tests were as follows: Al (3 mg/L); Ca (56 mg/L); Fe (0.21 mg/L); Mn (1 mg/L) and Ni (0.082 mg/L). The metals that leached from the coal residue according to the ARLP test results were as follows: Na (3 mg/L); Al (15 mg/L); Ca (136 mg/L); Fe (0.91 mg/L); Mn (1 mg/L) and Ni (0.07 mg/L). Higher concentrations of metals generally leached from the coal residue with ARLP test than with the TCLP test. The sulphate concentration up-stream of the coal residue was determined at 26 mg/L. This concentration increased to 3 615 mg/L at the decanting point and to 6 509 mg/L downstream of the decanting point. The surface and possibly groundwater are therefore polluted with sulphate. The upstream Na (26 mg/L), Ca (41 mg/L), Fe (0,02 mg/L), Mn (3 mg/L) and Ni (0.065 mg/L) concentrations were low in the case of the gold residues. These concentrations at the decanting point were: Na (289 mg/L); Ca (266 mg/L); Fe (0.2 mg/L); Mn (0.01 mg/L) and Ni (2 mg/L). Fifty metres downstream these concentrations were: Na (140 mg/L); Ca (389 mg/L); Fe (722 mg/L); Mn (395 mg/L) and Ni (15 mg/L). There was a significant increase in the metal concentration from up-stream of the gold residue, to the decanting point and further downstream of the gold residue. The surface and possibly ground water are therefore polluted by the metals leaching from the gold residue. The upstream Na (5 mg/L), Ca (8 mg/L), Fe (0,12 mg/L), Mn (0.015 mg/L) and Ni (0.05 mg/L) concentrations were low in the case of the coal residues. These concentrations at the decanting point were: Na (189 mg/L); Ca (337 mg/L); Fe (68 mg/L); Mn (13 mg/L) and Ni (0.06 mg/L). Fifty metres downstream these concentrations were: Na (65 mg/L); Ca (129 mg/L); Fe (0.48 mg/L); Mn (5 mg/L) and Ni (0.06 mg/L). There was a significant increase in the metal concentration from up-stream of the coal residue, to the decanting point and further downstream of the coal residue. The surface and possibly ground water are therefore polluted by the metals leaching from the coal residue. The gold and coal mine residues are polluting the surface and possibly ground water. Therefore, in order to ameliorate the current status within the Roodepoort and Newcastle catchments, mitigation and management measures such as that the residues should be covered and capped with soil material that would prevent infiltration of the oxygen and rain water into the soil, are recommended. A more comprehensive water quality analysis of the surroundings of the residues is also suggested to be able to better quantify the extent of the problem. Copyright / Dissertation (MSc)--University of Pretoria, 2011. / Chemical Engineering / Unrestricted

No description available.

Wood is often combined with other materials such as thermoplastics, adhesives and coatings. In general, combinations of wood and polymers especially in outdoor exposure have poor long-term durability. This behaviour can be related to an insufficient wood-polymer adhesion due to the low intrinsic compatibility between the wood substance and the polymers used. Another source for woodpolymer de-bonding is the high hygroscopicity of wood and great difference in hygro-thermal properties between the components. The basic conceptual idea related to this work is to reduce the hygrosensitivity of wood by applying different wood modification methods, in particular, acetylation, furfurylation and heat treatment. The effects of such chemical modifications of wood, also accompanied with ageing effects, on its adhesion properties with commonly used synthetic polymers are, however, not well understood. In this context, the over-all purpose of this thesis is to achieve a better understanding of wood-polymer adhesion and interfacial forces which also may guide us to tailor the interaction between modified wood and e.g. thermoplastics and adhesives. The main focus of this thesis is therefore to apply contact angle analysis based on the Chang-Qin-Chen (CQC) Lewis acid-base model in order to estimate the work of adhesion (Wa) between the wood, modified wood and certain polymers. Contact angle measurements on wood samples were performed based on the Wilhelm plate principle. Related to this, an effort was also made to characterize the studied modified wood surfaces according to morphology and chemical composition. The methods that have been used are low vacuum scanning electron microscopy (LV-SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Results show that so-called interaction parameters can be successfully estimated for prediction of Wa between wood and polymers using the applied CQC model. Furthermore, such wetting analysis was successfully related to spectroscopic findings of the chemical composition of the wood samples surface. Ageing effects, i.e. the time after preparation of the wood surface, play a central role for the surface characteristics. In most cases, ageing resulted in a significant decrease of Wa between wood and water and a moderate decrease between wood and thermoplastics. The surface characteristics of acetylated wood were, however, more stable over time compared to unmodified, furfurylated and heat treated wood. The predicted Wa with the adhesives for heat treated and acetylated wood was increased due to ageing. Future work is planned to involve studies in order to relate such predicted adhesion properties with the actual performance of various wood-polymer systems. / QC 20101108

No description available.

Most nuclease enzymes can hydrolyze phosphoester bonds (in DNA and RNA) by using metal ions cofactors that coordinate and activate water molecules in the enzymes' active sites. However, there are some hydrolase enzymes (including nucleases) that can function without the aid of metal ions. 2,6-Di(1H-imidazol-2-yl)phenol, a model compound for hydrolase enzyme, was synthesized by the reaction between ethylenediamine and dimethyl-3-carboxysalicylate, initially resulting in the formation of diimidazoline. The diimidazoline was subsequently aromatized to the diimidazole by dehydrogenation over palladium. The overall reaction yield was low; therefore, other dehydrogenation transformation reactions were tried but all failed to improve the yield. Converting this diimidazolphenol into diimidazolphenyl monophoshpate derivative was attempted but failed to give desired products. Synthesis of 2,2'-anthracene-1,8-diylbis-1H-imidazole, another model compound for hydrolase enzymes, was attempted using dimethyl-1,8-anthracenedicarboxylate, but synthesis was unsuccessful due to solubility problem.

A series of 2-substituted 8-hydroxyquinolines have been prepared and their reactions with a number of metal ions studied. Acid-dissociation constants and metal-chelate formation constants have been determined. 2-(2'-Hydroxyphenyl), 2-(2'-pyridyl) and 2-hydrazino-8-hydroxyquinoline function as terdentate ligands. The latter two ligands form a number of protonated complexes some of which are unusually stable. This stability is likely due to hydrogen bonding. / Thesis / Doctor of Philosophy (PhD)