Predispersed Solvent Extraction (POSE) was used to extract copper ions from dilute acidic aqueous solution. POSE is based on the principle that there is no need to comminute both phases. All that is necessary is to comminute the solvent phase prior to contacting it with the feed. This is done by converting the solvent into aphrons. which are micron-sized globules encapsulated in a soapy film. Since the aphrons are so small, it takes a long time for the solvent to rise to the surface under the influence of gravity alone. Therefore, the separation is expedited by piggy-back flotation of the aphrons on especially prepared gas bubbles, which are somewhat larger than aphrons and are called colloidal gas aphrons (CGA). Polyaphrons of various types were studied extensively. The apparatus used to generate the polyaphrons was upgraded. The residence time distribution of a liquid in the polyaphron generator was determined. The particle size distribution of polyaphrons was determined using photo-microscopy and sedimentation among other methods. Batch tests were done using both conventional and POSE. Results showed that POSE approaches equilibrium much faster than conventional extraction. Equilibrium isotherms were drawn and empirical equilibrium relationships were developed. The dynamics of the kinetics of the extraction was modeled using film theory. Equipment for the POSE process was built. Experiments were carried out in continuous mode and the process was optimized. An empirical statistical equation was developed for the extraction process in continuous mode. Depending on the aqueous to solvent ration, more than 99% copper can be extracted. / Ph. D.

Binary solubility data of hydrocarbon solids in supercritical fluids were correlated using the compressed gas model. Data included in the analysis were for solubilities of binary mixtures of napthalene, 2,3- and 2,6-dimethylnapthalene, benzoic acid, phenanthrene, anthracene and pyrene in both ethylene and carbon dioxide, and of napthalene, phenanthrene and anthracene in ethane. Two equations of state--the Peng-Robinson equation and the Lee-Kesler equation with Plocker, Knapp and Prausnitz mixing rules--were tested in conjunction with the compressed gas model, permitting a direct comparison of the two equations of state. The sensitivity of the model to changes in the parameters was analyzed for each equation of state. Prediction of the solubility data of five binary mixtures was attempted. The mixtures were hexamethyl benzene and fluorene in both ethylene and carbon dioxide, and diphenylamine in carbon dioxide. The binary attraction parameter (or"unlike pair energy parameter") of the Peng-Robinson equation was correlated with the heat of vaporization of the solid. The binary interaction parameter of Plocker, Knapp and Prausnitz (1978) mixing rules was correlated as they suggested for high-pressure vapor-liquid-equilibria. The most accurate predictions were obtained using the Lee-Kesler equation with Plocker, Knapp and Prausnitz mixing rules. Predictions of the solubilities of hexamethyl benzene and fluorene in carbon dioxide were accurate to within 30 percent error; results for hexamethyl benzene in ethylene were accurate to within 50 percent error; and results for fluorene in ethylene and diphenylamine in carbon dioxide were inaccurate. / Master of Science

In this work, we present two open literature databases, the VT-2005 Sigma Profile Database and the VT-2006 Solute Sigma Profile Database, that contain sigma profiles for 1,645 unique compounds. A sigma profile is a molecular-specific distribution of the surface-charge density, which enables the application of solvation-thermodynamic models to predict vapor-liquid and solid-liquid equilibria, and other properties. The VT-2005 Sigma Profile Database generally focuses on solvents and small molecules, while the VT-2006 Solute Sigma Profile Database primarily consists of larger, pharmaceutical-related solutes. We design both of these databases for use with the conductor-like screening model−segment activity coefficient (COSMO-SAC), a liquid-phase activity-coefficient model. The databases contain the necessary information to perform binary and multicomponent VLE and SLE predictions. We offer detailed tutorials and procedures for use with our programs so the reader may also use their own research on our research group website (www.design.che.vt.edu). We validate the VT-2005 Sigma Profile Database by pure component vapor pressure predictions and validate the VT-2006 Solute Sigma Profile Database by solid solubility predictions in pure solvents compared with literature data from multiple sources. Using both databases, we also explore the application of COSMO-SAC to solubility predictions in mixed solvents. This work also studies the effects of conformational isomerism on VLE and SLE property prediction. Finally, we compare COSMO-SAC solubility predictions to solubility predictions by the Non-Random Two-Liquid, Segment Activity Coefficient (NRTL-SAC) model. We find UNIFAC is a more accurate method for predicting VLE behavior than the COSMO-SAC model for many of the systems studied, and that COSMO-SAC predicts solute mole fraction in pure solvents with an average root-mean-squared error (log10(xsol)) of 0.74, excluding outliers, which is greater than the RMS error value of 0.43 using the NRTL-SAC model. / Master of Science

A sample of cellulose nitrate was to be fractionated into a series of fractions differing from each other with respect to the degree of polymerization. The method chosen was to be one which would give a large number of fractions, each one attaining as high a degree of homogeneity with respect to chain length as could be reached without too great refinement of procedure. The degree of polymerization of the fractions was to be determined by viscosity measurements using the Staudinger viscosity equation (109) and then using a suitable solvent, a quantitative determination of the solubility of each fraction was to be attempted. From any solubility data obtained an attempt was to be made to determine if any relationship existed between the degree of polymerization and the solubility. Solubility is dependent upon the nitrogen content of the nitrate. Therefore, the nitrogen content of each fraction was to be determined, in order to draw valid conclusions from the solubility data. / M.S.

No / Spherical crystallization involves crystallization and simultaneous agglomeration of a crystalline particle using an immiscible phase, which has preferential affinity for the crystal surface. Here, we report application of a spherical crystallization technique to the field of co-crystallization. Carbamazepine/saccharin (CBZ/SAC) co-crystals were generated using reverse antisolvent addition and agglomerated using different bridging liquids. Two crystal forms of CBZ/SAC co-crystals were formed, depending on the levels of supersaturation achieved during processing. The selective agglomeration of co-crystal occurred during the agglomeration stage, depending on the relative interaction between bridging liquid and the crystal surfaces. The computational investigation of isosteric heats of adsorption of the bridging liquids at the prominent crystal surfaces proved to be a useful tool in understanding the surface interactions. The spherical crystallization technique shows opportunity to generate co-crystals and its purification through selective agglomeration.

Many sources suggest a folklore procedure to determine if a smooth curve of genus 1 has a rational point. This procedure terminates conditionally on the Tate-Shafarevich conjecture. In this thesis, we provide an exposition for this procedure, making several steps explicit. In some instances, we also provide MAGMA implementations of the subroutines. In particular, we give an algorithm to determine if a smooth, genus 1 curve of arbitrary degree is locally soluble, we compute its Jacobian, and we give an exposition for descent in our context. Additionally, we prove there exists an algorithm to decide if smooth, genus 1 curve has a rational point if and only if there exists an algorithm to compute the Mordeil-Weil group of an elliptic curve. / Master of Science / It is unknown whether an algorithm can determine if an equation with rational coefficients has a solution in the rational numbers. This thesis examines the simplest class of such equations: those representing so called smooth curves of genus 1. We demonstrate that an algorithm can decide if these equations have a rational solution if and only if there is an algorithm that can compute all rational solutions given a single rational solution. A procedure exists for the latter, but its success relies on a conjecture. Assuming this conjecture, we explicitly construct the corresponding algorithm to decide if an equation representing a smooth curve of genus 1 has a rational solution.

The objectives of this work are to characterize and model the solvent-mediated phase transformation process of theophylline anhydrous crystals to the monohydrate crystals in an aqueous system. In order to model the transformation, the following processes are taken into account: (1) the dissolution kinetics of theophylline anhydrous crystals, (2) the kinetics of the formation of theophylline monohydrate nuclei, and (3) the growth kinetics of the monohydrate crystals. The driving forces for the above processes are determined from the concentration of theophylline in the solution and the solubilities of theophylline anhydrous and monohydrate. The solubilities of theophylline anhydrous and the monohydrate, and these three distinct processes along with the overall transformation phenomena were investigated in the present study. By using theophylline as a model compound we have gained some understanding of the kinetics of the solvent-mediated phase transformation between the metastable anhydrous form and the stable hydrated form of an organic compound and we were able to model the transformation process. By identifying the mechanisms for nucleation, growth of the hydrate form and the dissolution of the anhydrous form one can predict and control the transformation process. The growth kinetics of thymine monohydrate crystals at various temperatures are also investigated in the present study.

A new approach is developed for evaluating the mixing properties of binary solutions at high pressure. This involves solving Poisson's equation throughout three-dimensional cubic lattices, consistent with Thomas-Fermi-Dirac (TFD) theory. Zero temperature calculations are carried out for a variety of compositions and crystal structures in 3 pressure groups relevant to Jovian planetary interiors. Pseudopotentials based on the two-component-plasma model (with a uniform electron background) are fitted to the solid-state results, and are then used in liquid-state calculations using hard-sphere perturbation theory. TFD results for H-He solutions find critical temperatures (above which all compositions are soluble) to be ∿ 0, 500, and 1500°K at pressures of 10, 100, and 1000 Mbar, respectively. These temperatures are much lower than those obtained using free electron perturbation theory, where T(crit) ∿ 10,000°K at 10 Mbar. Thus, unlike the perturbation theory results, the TFD results predict that helium should be soluble in metallic hydrogen in the deep interiors of both Jupiter and Saturn, and our calculations give an indication of the degree of model-dependence in computing high pressure mixing properties. In addition, TFD calculations for H-C and H-O solutions find phase separation temperatures to be≲ 10⁴ °K for pressures ≲ 10³ Mbar. These temperatures are considerably lower than those found assuming a uniform electron distribution (where T(crit) ≳ 10⁵ °K), and suggest that H-C and H-O solutions should also be miscible in the metallic zones of Jupiter and Saturn.

Protein solubility plays an important role whether for biophysical and structural studies, or for production and delivery of therapeutic proteins. Poor solubility could lead to protein aggregation, which is an undesired physicochemical mechanism at any stage of recombinant proteins production. To date, more than half of all recombinant therapeutic proteins are produced in mammalian cells, mainly due to the high similarity of the final product to human protein structures. However, poor secretion can occur, due to misfolded proteins or aggregates leading to cellular stress and proteolysis. Another widely-used expression system is E. coli, which can offer a cost-efficient alternative. This system has an important limitation, since proteins tends to form insoluble protein aggregates in the cytoplasm upon heterologous overexpression. Several strategies are being implemented to improved soluble expression, ranging from culture conditions to solubility enhancing tags. However, there is no universal approach or technology that solves protein aggregation. In this thesis two recently published hypotheses from our group have been applied. One stated that soluble expression of proteins was inversely correlated with the size of the largest positively-charged patch on the protein surface. The second hypothesis (of protein solubility), arose from the finding that the relative content of lysine and arginine residues separated E. coli proteins by solubility. Both hypotheses arose from a study of an extensive dataset of experimental solubilities determined for cell-free expression of E. coli proteins. In combination with other widely used strategies, such as lowering expression temperature and inducer concentration, decreasing non-charged (hydrophobic) patches and addition of helical capping for increasing stability, a rational understanding for directed alteration of solubility in a variety of recombinant proteins has been explored. This includes three protein models to test: (i) recombinant human erythropoietin (rHuEPO) (one of the top selling therapeutics) (ii) recombinant 6-Phosphofructo-2-Kinase/fructose-2,6-bisphosphatase (rPFKFB3) (a product for which over-expression has been sought for characterisation and insight into possible cancer therapy) and (iii) a set of three selected E. coli proteins containing high ratios of lysines to arginines: thioredoxin-1 (TRX), cold shock-like protein cspB (cspB), and the histidine-containing phosphocarrier protein (HPr). It was found that single or multiple point mutations (changing amino acids from positive to negative charge or vice versa; or lysines to arginines) verified the predicted effect on rHuEPO, rPFKFB3, TRX, cspB, and HPr solubility (experimentally defined as the distribution between soluble and total fractions) for expression in E. coli. In addition, the redesigned set of rHuEPO transiently expressed in HEK 293-EBNA cells, suggesting that positively-charged patch size may also influence protein secretion. Further application of these computational and experimental approaches could provide a valuable tool in the design and engineering of proteins, with enhanced solubility, stability and secretion.

Thesis (Ph. D.)--School of Dentistry and Dept. of Chemistry. University of Missouri--Kansas City, 2004. / "A dissertation in oral biology and chemistry." Advisor: J. David Eick. Typescript. Vita. Description based on contents viewed Feb. 23, 2006; title from "catalog record" of the print edition. Includes bibliographical references (leaves 137-145). Online version of the print edition.