Benzimidazole and benzotriazole derivatives, 4-(2,3-Dihydrothieno[3,4-b][1,4] dioxin-5-yl)-7-(2,3-dihydrothieno[3,4b][1,4]dioxin-7-yl)-2-benzyl-1H-benzo[d] imidazole (BIm-Ed), 2-benzyl-4,7-di(thiophen-2-yl)-2H-benzo[d] [1,2,3] triazole (BBTS), and 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2Hbenzo[ d] [1,2,3] triazole (BBTES) were employed as photosensitizers for diaryliodonium salt photoinitiators in cationic photopolymerization of various epoxide and vinyl ether monomers. Diphenyliodonium hexafluorophosphate (Ph2I+PF6&macr / ) salt was used as the photoinitiator in this study. Extended conjugation and electron-rich moieties of the photosensitizers enabled the use of long wavelength UV and visible light emitting light sources in cationic photopolymerizations. Polymerizations were achieved at room temperature and monitored by optical pyrometry. Photopolymerization of a diepoxide monomer with ambient solar irradiation was examined.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1981. / Includes bibliographical references (p. 63-65).

Title from title page of PDF (University of Missouri--St. Louis, viewed Mar. 3, 2010). Includes bibliographical references.

Many vaccines require an adjuvant to induce a strong immune response. Aluminum–containing adjuvants have been approved by the United States Food and Drug Administration for human use for many years. There are two main aluminum-containing adjuvants, aluminum hydroxide and aluminum phosphate. Due to their favorable safety profile, aluminum-containing adjuvants have been widely used in human vaccines for decades. Many currently licensed and commercially available vaccines contain aluminum-containing adjuvants. However, aluminum-containing vaccine adjuvants suffer from two major limiting factors: (1) aluminum-containing adjuvants can only weakly or moderately potentiate antigen-specific antibody responses and are generally considered incapable of inducing cellular immune responses; (2) vaccines that contain aluminum-containing adjuvants require cold-chain refrigeration for storage and distribution, and may not be frozen, because freezing of the vaccine in dispersion causes irreversible coagulation that damages vaccines (e.g., loss in potency and stability). In this dissertation, the first limitation was addressed by reducing the size of the aluminum hydroxide from micrometers (3-10 micrometer) to nanometers of less than 200 nm, and the second limitation mentioned above was addressed by freeze-drying vaccines that contain aluminum salts as adjuvants into a dry powder using thin-film freeze-drying. In addition, using an improved experimental design, the vaccine adjuvant activities of nanoparticles of around 200 nm was compared to that of the nanoparticles of around 700 nm. The smaller 200 nm nanoparticles showed a more potent adjuvant activity than the larger nanoparticles. When dispersed in an aqueous medium, both aluminum hydroxide and aluminum phosphate are physically 1–20 micrometer particulates. There are data showing that particulate vaccine carriers of around 200 nm (or less) may be optimal in potentiating the immunogenicity of vaccines. Based on this finding, aluminum hydroxide nanoparticles of 112 nm were synthesized, and its adjuvant activity was compared to that of the traditional aluminum hydroxide adjuvant, which have particulates of 3-20 micrometer. Using ovalbumin and Bacillus anthracis protective antigen protein as model antigens, it was found that protein antigens adsorbed on the aluminum hydroxide nanoparticles induced stronger antigen-specific antibody responses than the same protein antigens adsorbed on the traditional aluminum hydroxide microparticles of around 9.3 µm. Importantly, the inflammation reactions induced by aluminum hydroxide nanoparticles in the injection sites were milder than that induced by microparticles. Simply reducing the particle size of the traditional aluminum hydroxide adjuvant in suspension from micrometers into nanometers represents a novel and effective approach to improve its potency. The second limitation was addressed by converting vaccines that contain an aluminum salt as an adjuvant from an aqueous dispersion into a dried powder using thin-film freeze-drying. There is evidence that aluminum-containing vaccines can be lyophilized to dry powders using high speed freezing methods. Thin-film freezing is a high speed freezing method with a freezing rate between 100 to 10,000 K/s, but the feasibility of using thin-film freeze-drying to freeze-dry vaccines that contain aluminum salts as adjuvants has not been tested before. In this dissertation, Using ovalbumin as a model protein antigen and aluminum hydroxide or aluminum phosphate as an adjuvant, it was confirmed that vaccines that are adjuvanted with aluminum hydroxide or aluminum phosphate can be freeze-dried with as low as 2% (w/v) of trehalose as a cryoprotectant by thin-film freeze-drying without causing vaccine aggregation while preserving the immunogenicity of the vaccine. Finally, the feasibility of using the thin-film freeze-drying method to freeze-drying vaccines that contain aluminum salts as adjuvants was further confirmed by drying a commercial aluminum salt-adjuvanted tetanus toxoid vaccine. Vaccines that contain aluminum salts as adjuvants may be converted to a dry powder using the thin-film freeze-drying method to avoid loss of potency due exposure to freezing conditions during transport and storage. / text

The design, synthesis, characterization, and applications of annulated bis(imidazolium) salts are described. New synthetic methodologies have been developed that allow access to a broad structural range of bis(imidazolium) salts. Initial studies focused on thee use of bis(imidazolium) salts as comonomers in the formation of mainchain organometallic polymers. Two distinct polymer scaffolds were synthesized, one featuring metal(II)dihalides in the main-chain, and the other featuring a chelated metal center. Ultimately, polymerizations were conducted under ambient atmosphere, proceeded in excellent overall yield, and provided main-chain organometallic polymers comprising Ni(II), Pd(II), and Pt(II) with molecular weights up to 106 Da. Departing polymer studies, focus was shifted toward the study of the physical and photophysical properties of the bis(imidazolium) salts. In few synthetic manipulations, a series of highly photoluminescent bis(imidazolium) salts were prepared whose substituents enable emission in solution, in the solid-state, and, uniquely, as free-flowing liquids. Importantly, these materials display excellent physical properties, such as low glass-transition temperatures (< 0 °C) and high thermal stabilities (> 300 °C). In addition, the bis(imidazolium) platform enabled access to two new fluorescent ionic liquid crystals, demonstrating an ability to also control mesomorphic properties of these materials. Further investigations were conducted regarding the photophysical properties of bis(imidazolium) salts. Focus was placed upon absorption and emission wavelength tunability, solvatochromism, red-edge excitation, and chemical stability. Through functional group modulation, the [lambda]em were varied from 329 -- 561 nm with [Phi]fs up to 0.91. Both the absorption and emission characteristics were found to display strong solventdependencies which were found to be strongly influenced by the nature of the bis(imidazolium) core. The red-edge effect was investigated for a series of bis(imidazolium) salts and was found to be similar between Br and BF4 salts, but distinctly different when MeSO4 anions were incorporated. The stability of an amphiphilic BBI was quantified in aqueous solutions of varying pH and > 85% of the emission intensity was retained after 2 h at pH levels of 3 -- 9.

- / Calcium salts are known as compounds and minerals and they have been extensively studied due to their rich morphology and applications. They are known as biominerals, cement additives. fillers, food additives etc. In the oil and gas production calcium sulfates, carbonates and silicates form tenaciously adhering scale deposits which may stop production if the problem is not tackled timely. The motivation for this work was the well known problem of sand production during oil recovery, which occurs when the production rate exceeds a critical value. The aim has been an attempt to develop an inexpensive and environmentally friendly method to consolidate soil and sand for building purposes. The work included in this thesis, is focused in the investigation of the physico-chemical conditions at which calcium salts precipitate acting as consolidating material for soil and sand. The marked differences in the physicochernical properties of the precipitating salts enabled us to investigate the relative efficiency of three different classes of calcium salts: sulfates, carbonates and phosphates. As a result. the present thesis is divided in three parts. In the first one, the spontaneous precipitation of calcium sulfate from supersaturated solutions and the inhibition by water soluble polymers was examined. Two kinds of polymers: three polyacrylates (PAA) with different molecular weights (2.000 (PAA1), 50,000 (PAA2) and 240.000 (PAA3)) and one co-polymer of polyacrylic with polystyrene sulfonate (PAA-PSS) were tested. Very low concentrations of all polymers tested, down to 6ppm, increased markedly the induction period preceding precipitation at supersaturations in which, in the absence of additives the precipitation was spontaneous. The “kinetic Langinuir” equation based on the assumption of Langmuir - type adsorption of the additives on the precipitating calcium sulfate dihydrate, gave satisfactory fit of the kinetic data. From the fit according to this model, the affinity constants for the polymer-gypsum surfaces were calculated. The order of the affinity was PSS>PAA3>PAA1>PAA2. The precipitation of calcium sulfate dihydrate in the presence of sand grains, resulted in crystals which formed weak bridges among the grains and the material in which precipitation took pace was rather poorly consolidated. The second part reports on the precipitation of calcium carbonate through the enzymatic production of carbonate ions. This newly proposed method is based upon the slow evolution of the supersaturation with respect to calcium carbonate in an aqueous environment, in which one of the components of the supersaturated solution (in our case carbonate) is slowly released by a source through the action of enzymes present in the aqueous medium. The work done concerning the development of the methodology of enzyme mediated calcium carbonate formation in aqueous media involved the following steps: (i) Investigation of the mechanism of urea (substrate) decomposition in the presence of jack bean urease (enzyme) through conductivity measurements. Urease exhibited a bell- shaped activity profile as a function of temperature with optimum value at 50CC. The reaction of urea decomposition in the presence of urease followed Michaelis-Menten type kinetics up to a concentration of about 250 mM. At concentrations exceeding 250 m.M, the reaction rate decreased as the carbonate source concentration increased, suggesting substrate inhibition. (ii) The effect of various parameters, such as temperature, enzyme and salts concentrations, the presence of sand etc. was studied upon the rate of precipitation and the morphology of the precipitate. The rate of precipitation increased with increasing temperature up to the optimum temperature of the enzyme activity. The experimental conditions identified through a series of batch type experiments were optimized for the consolidation of granular materials. Lab experiments done in loose sand packs have shown that consolidation may be achieved through bridges of calcium carbonate formed enzymatically. The consolidation efficiency was found to be strongly dependent on urease quality. Crude jack bean urease was more effective than refined one, due to impurities which promote calcitic rhombohedra to precipitate. Increasing the number of solution injections resulted in increased strength and reduced permeability, as expected. Resistance to uniaxial strength was found to be inversely proportional with temperature. The highest values were obtained for precipitates formed on sand grains at 25:C. The initial concentration of the supersaturated solutions were also found to affect the degree of consolidation, because of the different precipitation rates (higher at higher supersaturations) and of the amount of the material precipitated on the grains, which again was more, the higher the solution supersaturation with respect to calcium carbonate. Next, the heterogeneous nucleation and growth of calcite was investigated both in unstable and stable solutions at supersaturations sufficiently low to allow for the measurement of induction times preceding the onset of precipitation. In the unstable regions the induction times were inversely proportional and the rates of precipitation increased with the solution supersaturation. The high order dependence of the rates of precipitation on the solution supersaturation suggested a polynucleation mechanism. Fit of the induction time-supersaturation data according to this model yielded a value of 49 mJ/m2 for the surface energy of the calcite nucleus forming. In the stable domain of the supersaturations, seeded growth experiments showed a second order dependence on the rates of crystal growth of calcite seed crystals, while quartz seed crystals failed to induce nucleation. Raising supersaturation to reach the unstable domain showed interesting features: calcite seed crystals yielded crystal growth kinetics compatible with the polynucleation model, without any induction time contrary to the quartz seed crystals that triggered secondary nucleation. The kinetics data in the latter case were consistent with the polynuclear model and the surface energy for the newly forming embryo was calculated equal to 13 mJ/m2, confirming the fact that the process is dominantly heterogeneous. In the third part of this dissertation an attempt is presented to apply the idea of enzymatic precipitation of salts to the case of calcium phosphate formation. For this purpose, two kinds of phosphatases were tested for their PO4/3 release capacity from polyphosphates. Each type of the enzyme functioned at a different pH, so that a wide pH-range was covered (5.50-9.80). A seven-fold increase in the enzyme concentration resulted in the increase of the hydrolytic substrate decomposition percentage from 38% to 82% at pH 5.50. At pH 9.80, increasing the amount of alkaline phosphatase by a factor of five, the percentage of hydrolytic decomposition increased from 800o to 100%. The temperature dependence of the enzymes’ activity allowed for the determination of the maximum rate and the Michelis-Menten constant. At 25oC, Rmax and Kmwere calculated equal to 3.2x104 mol/h and 2.15x l0 mol/l for acid phosphatase, while the values for alkaline phosphatase were 5.9x10 mol/h and 4.26x10-3 mol/l, respectively. The activation energies were calculated to be 31 and 74 kJ/mol for acid and alkaline enzymes respectively. In terms of precipitation, the enzymic hydrolysis method is applicable for concentrations of the substrate and of the cation of the precipitating salt lower than 0.05 mol/l. For higher concentrations, insoluble complexes of Ca-substrate were formed and the precipitation of calcium phosphate was not favored. The presence of sand promoted both precipitation and hydrolysis when acid phosphatase was used, while with alkaline phosphatase the effect of the presence of sand was negligible. Consolidation experiments conducted in loose sand packs indicated that this method may be applicable only to stabilize sand with a few applications of the working solution, since the amount of the precipitate is small for the concentration levels suggested by the results of the present work. For strong consolidation, and for the composition of the solutions suggested in this work, a large number of injections is needed.

In order to make thermal solar power compete with the traditional sources of energy, the efficiency must increase and one way of doing it is by changing the operating fluid. Among the alternate fluids is the use of molten salts as a part of the process; either for thermal storage and later utilization for electrical production during the hours without sun or as a substitute of the operating fluid to provide higher temperatures resulting in better efficiency. The difficulty of using molten salts is the lack of physical properties in literature; such as viscosity, boiling point, vapor pressure and volumetric absorption of solar radiation, thus making the selection of a suitable salt a very difficult endeavor. As a part of the Multidisciplinary Research Initiative (MURI) of the Department of Energy in the project of High Operating Fluids, this work will focus on the optical properties of the molten salts (volumetric absorption). The objective of this Thesis is to design, build and test a device capable of measuring the light attenuation coefficient; which is directly related to volumetric absorption of solar radiation, as well as determine the attenuation coefficient of various eutectic systems for the ternary salt mixture of ZnCl2, NaCl and KCl. Based on the little existent literature, a device capable of measuring the attenuation coefficient was designed, built, validated and tested. This was done by projecting a stable beam of light simulating sun radiation through the molten salt sample and to a spectrometer with a wavelength range going from 400 nm to 1000 nm with operating temperatures going from 350oC to 600oC. This device is capable of controlling the thickness, from 1 to 60 mm, of the molten salt sample by a computer controlled linear stage with an accuracy of 0.1mm. Quartz was used as a container for the molten salts because of its high melting point and transparency. A ceramic heater was used as a heat source, which can heat up the sample to temperatures up to 1200 oC if necessary. Two validation tests for the device were done by measuring the light attenuation coefficient of clear water and extra virgin olive oil and then they were compared to the ones in literature. The eutectic systems were tested next; the results characterized the attenuation coefficient as a function of wavelength and temperature, something that no other experimental work has done before for this specific fluid. These values will help to determine an optimal operating fluid for high temperature thermal applications.

Glancing angle laser induced fluorescence was used to monitor the kinetics of the photodegradation of chlorophyll at the surface of various salt solutions. The loss was measured using varying wavelengths of actinic radiation in the presence and absence of gas phase ozone. The loss rate of illuminated chlorophyll was faster on salt water surfaces than fresh water surfaces, both in the presence and absence of ozone. On salt water surfaces, the dependence of the loss rate on [O3(g)] was different under illuminated conditions than in the dark. This was further investigated by measuring the excitation spectra and the dependence of chlorophyll loss on the concentration of salts at the salt water surface. The possible production of reactive halogen atoms is the likely reason for the observed enhancement. The following results provide evidence of photosensitized oxidation of halogen anions, in the UV-visible range of the spectrum, resulting in halogen atom release.

In many acid, highly leached South African soils, Na levels are very low. Applications of Na to highly leached soils may be advantageous in some situations as Na has been shown to interact with soil acidity, P availability, and K nutrition of plants. It was found that an increased level of Na at constant anion concentration in the soil solution resulted in lower soil solution pH and Al3 + activity, and improved maize root penetration into an acid subsoil (pot trial). In another pot trial, Na did not improve lucerne root growth into the same subsoil. In a field trial on a limed, low-Na soil with severe subsoil acidity, the effects off our rates of Na, three Na carriers, and three rates of gypsum on maize growth were compared. In three out of four seasons grain yield responses to the Na applications were positive, and of a similar magnitude to the response to gypsum (455-925 kg ha). In another field trial with maize, responses to Na (of up to 1027 kg grain ha) were recorded in two out of three years on plots with topsoil acid saturations of greater than 45%. The reason for the responses to Na was probably improved subsoil rooting as a result of modified soil solution composition in the presence of Na. In a field trial with Italian rye grass on an acid, highly weathered soil, the effect of sodium applications were investigated at different levels of lime and K. In the first season, 200 kg ha Na as NaCl increased dry matter yield from 11289 kg ha to 12815 kg ha , Sodium responses were possibly due to enhanced P uptake, or Na substitution for K, or a combination of the two mechanisms. No consistent lime x Na interaction was observed. Potassium and Na applications affected the mineral balance of the herbage produced. Potassium depressed herbage Ca, Mg and Na concentrations, and Na depressed herbage Ca and Mg where herbage K was low, but had no effect on herbage K. Where soil P and K reserves are marginal, rye grass pastures may benefit from Na applications. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 2000.

Glancing angle laser induced fluorescence was used to monitor the kinetics of the photodegradation of chlorophyll at the surface of various salt solutions. The loss was measured using varying wavelengths of actinic radiation in the presence and absence of gas phase ozone. The loss rate of illuminated chlorophyll was faster on salt water surfaces than fresh water surfaces, both in the presence and absence of ozone. On salt water surfaces, the dependence of the loss rate on [O3(g)] was different under illuminated conditions than in the dark. This was further investigated by measuring the excitation spectra and the dependence of chlorophyll loss on the concentration of salts at the salt water surface. The possible production of reactive halogen atoms is the likely reason for the observed enhancement. The following results provide evidence of photosensitized oxidation of halogen anions, in the UV-visible range of the spectrum, resulting in halogen atom release.