Polymorph-selective crystallization of calcium carbonate inspired by biomineralization.

Abstract

This dissertation primarily examines bioinspired mineralization, focusing on the polymorph-selective crystallization of calcium carbonate. (1) The effect of epitaxy on the polymorphic control of calcium carbonate was studied with aragonite-type inorganic substrates. The critical epitaxial mismatch for aragonite growth, when conditions disfavor aragonite, seems to be less than 7.1%. Larger epitaxial strain appeared to prohibit aragonite formation even though the substrates had the same crystal structure. The epitaxy required for aragonite nucleation seems to be more precise than that often suggested for biological systems. (2) Polymers of different aqueous-solution properties were tested to observe the effect on the crystallization of calcium carbonate. Near exclusive formation of aragonite was attained through the inhibition of more stable calcite with poly(vinyl alcohol). The contributing characteristics of poly(vinyl alcohol) seemed to be its ability to hydrogen bond and its tendency to adsorb non-specifically onto solid surfaces. Similar inhibition activity is suggested for various biomacromolecules involved in biogenic aragonite formation of mollusks, with the biomacromolecules acting in the same way as poly(vinyl alcohol). (3) Polymer surfaces imprinted by aragonite-type crystals (strontium carbonate) were studied as substrates for the crystallization of calcium carbonate. Only calcite formed under vaterite-, aragonite-, and calcite-favorable conditions. This result seemed to arise from the nature of functional groups, rather than from the molecular structure of the imprint. Interaction between the functional groups and calcium carbonate is suggested to have enhanced the crystallization rate, resulting in the rapid formation of the thermodynamically stable calcite irrespective of the bulk crystallization conditions. (4) A catechol-based monomer was synthesized in the course of developing a dental adhesive, which mimics the functionalities of mussel adhesive proteins. The coupling behavior of the monomer to hydroxyapatite, a mineral component of dentin, was studied. (5) Multiple denaturation of fibrillar collagen was reexamined with a highly sensitive differential scanning calorimeter. Multiple states of collagen were recognized by the appearance of several denaturation peaks: oxidized tropocollagen, intact tropocollagen, immature fibrils, and mature fibrils. The immature fibrils were identified as an intermediate state of collagen assembly, since it disappeared with time at constant temperature.