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Biominerals often form within a matrix of biomacromolecules in high-salinity environments, yet the relationships for how macromolecules and ionic strength influence the crystallization of sparingly soluble salts (e.g., CaCO₃) are not established. Developing a physical picture of these controls is hindered by the traditional assumption that background electrolytes are inert. In this study, we investigate calcite nucleation onto two model organic matrix polysaccharides, chitosan and alginate, in a series of ionic strength solutions (65 – 600 mM NaCl). Chitosan is near-neutral (at pH 8.5) and analogous to the structural polysaccharide chitin. In contrast, alginate has a strong negative charge akin to the many anionic biopolymers in the organic matrix. By measuring the rate of calcite nucleation onto these materials and fitting classical nucleation theory to the data, we find the interfacial free energy (γ_net) and the kinetic prefactor depend upon ionic strength for both polysaccharides. The thermodynamic barrier to nucleating calcite onto alginate strongly depends on ionic strength, while calcite nucleation onto chitosan shows a similar but weaker dependence. Parallel molecular dynamics (MD) simulations were conducted to examine ion (Ca²⁺, Na⁺, HCO₃⁻, Cl⁻) and water interactions with models of a carboxylated polysaccharide and a chitosan material. The MD predictions indicate that at higher ionic strength, the polysaccharide-solution interface is increasingly stabilized by progressively higher concentrations of Na⁺ and Cl⁻. Stronger Na⁺ interactions with the polysaccharide are observed in the carboxylated system. The numbers of H₂O and HCO₃⁻ in the Ca²⁺ hydration sphere decrease with increasing ionic strength, while the number of Cl⁻ increases for both polysaccharides. The evidence suggests the increase in interface stabilization by Na⁺ and Cl⁻ increases γ_net through reductions in the polysaccharide-solution interfacial energy. We predict the effect of higher salinity is enhanced for alginate because Na⁺ interactions with COO⁻ groups make it more difficult for Ca²⁺ to displace near-surface water and/ or Na⁺. Relatively weak Na⁺-chitosan molecular interactions lead to a lesser dependence on ionic strength. Calcite nucleation rates were also measured onto chitosan in a series of sodium halide solutions (NaCl, NaBr, NaI) and onto alginate in a series of chloride salts (LiCl, NaCl, CsCl) at constant ionic strength. CaCO₃ nucleation in the presence of electrolytes with the strongest hydration properties presents the lowest γ_net. Values of γ_net increase in the order Cl⁻<Br⁻<I⁻ and Li⁺<Na⁺<Cs⁺ for nucleation onto chitosan and alginate, respectively. The findings demonstrate that background electrolytes can modulate the energy barrier to CaCO₃ nucleation through tunable effects at the polysaccharide-solution interface. / Master of Science / Skeletal structures often form within an organic matrix of polysaccharides, proteins, and lipids. An ongoing challenge is to determine the roles of these biopolymers and their surroundings during the onset and growth of biominerals. In this study, we use two characterized polysaccharide materials as models for the organic matrix where calcium carbonate (CaCO3) biomineralization takes place to investigate the role of salinity in nucleation kinetics. By measuring the rate of CaCO3 nucleation onto chitosan (neutral) and alginate (carboxylated) and fitting classical nucleation theory to the data, we find the thermodynamic and kinetic controls on nucleation rate are dependent upon sodium chloride (NaCl) concentration for both polysaccharides. Although NaCl is considered an inert electrolyte, the thermodynamic barrier to nucleating calcite onto alginate strongly depends on its concentration. Chitosan shows a similar but weaker dependence. Simulations of the polysaccharide-NaCl environment show the polysaccharide-solution interface is increasingly stabilized by Na+ and Cl-, thus increasing the difficulty for a crystal nucleus to displace surface water and ions. The effect of higher salinity is enhanced for alginate due to stronger Na+ interactions with carboxyl groups. We also find the energetics of CaCO3 nucleation onto polysaccharides in the presence of electrolytes are dependent upon type of electrolyte. The relations suggest functional groups interact with background electrolytes (e.g., NaCl) to modulate activity and function at the polysaccharide-water interface during CaCO3 crystallization processes.

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We report diffraction experiments on some representative Fast Ion Conductors. The structures of anhydrous stoichiometric deuterium (DAl₁₁O₁₇) and silver (AgAl ₁₁O₁₇) beta aluminas have each been determined at four temperatures in the range 4 . 2K - 773K using powder neutron diffraction (PND) data. In DAl₁₁O₁₇, a strong D-O(5) hydroxyl linkage is maintained at all four temperatures .For AgAl₁₁O₁₇ at 4.2K,we have observed, for the first time in metal beta aluminas, a completely ordered cation distribution. The material, which was prepared by a new route, is accurately stoichiometric. At 298K,the silver atoms have become somewhat delocalised and by 773K they are organised in a highly diffuse manner. Single crystal neutron diffraction was used to elucidate the proton distributions in ammonium beta alumina, (NH₄) _1.25Al₁₁- 0_17.125, and the two derivatives (NH₄) _0.78H_0.25Al₁₁0₁₇ and 'HA1₁₁- 0₁₇.In the parent compound, the positions and orientations of the two independant (NH⁺₄) species are such that all protons are involved in favourable hydrogen-bonding schemes. In formation of the first derivative, one of these sites becomes completely depopulated. Our results clarify the thermal behaviour of (NH₄) _1.25Al₁₁0_17.125 and we propose schemes by which stoichiometric beta aluminas are formed from this precursor and the related (H₃0)_1+x- Al₁₁0_17.+x/2. The crystal structures of I-Ag₃PO₄(25°C and 375°C) , II-Ag₃PO₄(650°C) ,II-Na₃PO₄ (γ) (400°C) and the solid solutions Na_3(1-x)Al_xPO₄are described. The high-temperature forms are considered in relation to the fluorite structure and mechanisms for the ionic conduction of these phases are proposed. A single crystal X-ray diffraction study of β-Ag₂SO₄ (25°C) reveals that it is isostructural with thenardite, V-Na ₂SO₄.The high-temperature modifications a-Ag₂SO₄ (490°C) and α-K₂SO₄ (620°C) have been characterised using PND data. A PND experiment on silver (I) fluoride confirms that it adopts the rocksalt structure and we find no firm evidence for a significant population of defects.

The role that aquatic actinomycetes play, in the production of tastes and odors in water supplies has been investigated since 1948. The ability of these organisms to produce by-products in lakes and streams, which renders the water unpalatable, is of considerable public health importance. It is desirable that the waterworks industry has as much information as possible concerning the factors that contribute to the growth of these organisms. Since it appears that the aquatic actinomycetes may be isolated from most fresh-water sources, the problem of diversified environments and nutritional requirements offers an excellent field of investigation. The fresh-waters of the world contain variable quantities of electrolytes that may determine in part the biological activity of these organisms. The unsolved questions in this instance are concerned with the electrolytes present and their quantitative effects on the growth and development of these forms.

Thesis (M. Sc.)--University of Hong Kong, 1970. / Typewritten.

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published_or_final_version / abstract / toc / Chemistry / Doctoral / Doctor of Philosophy