Two double-hydrophilic block copolymers, each comprising a nonionic block and an anionic block comprising pendent aromatic sulfonate groups, were used as additives to modify the crystallization of CaCO3. Marked morphological changes in the CaCO3 particles were observed depending on the reaction conditions used. A poly(ethylene oxide)-b-poly(sodium 4-styrenesulfonate) diblock copolymer was particularly versatile in effecting a morphological change in calcite particles, and a continuous structural transition in the product particles from polycrystalline to mesocrystal to single crystal was observed with variation in the calcium concentration. The existence of this structural sequence provides unique insight into the mechanism of polymer-mediated crystallization. We propose that it reflects continuity in the crystallization mechanism itself, spanning the limits from nonoriented aggregation of nanoparticles to classical ion-by-ion growth. The various pathways to polycrystalline, mesocrystal, and single-crystal particles, which had previously been considered to be distinct, therefore all form part of a unifying crystallization framework based on the aggregation of precursor subunits.
A major goal in materials science is to develop bioinspired functional materials based on the precise control of molecular building blocks across length scales. Here we report a protein-mediated mineralization process that takes advantage of disorder–order interplay using elastin-like recombinamers to program organic–inorganic interactions into hierarchically ordered mineralized structures. The materials comprise elongated apatite nanocrystals that are aligned and organized into microscopic prisms, which grow together into spherulite-like structures hundreds of micrometers in diameter that come together to fill macroscopic areas. The structures can be grown over large uneven surfaces and native tissues as acid-resistant membranes or coatings with tuneable hierarchy, stiffness, and hardness. Our study represents a potential strategy for complex materials design that may open opportunities for hard tissue repair and provide insights into the role of molecular disorder in human physiology and pathology.
Synchrotron X-ray microtomography (XMT) was used to measure the linear attenuation coefficient (LAC) for 1.9-µm sidelength voxels within approximal brown spot lesions and sound human enamel. XMT demonstrated three-dimensional features, notably sheets with ∼30 µm periodicity having low LAC, identified as regions of demineralization corresponding to Retzius lines. Quantitative three-dimensional measurements of mineral concentration, derived from LAC with assumption of a single model composition, were consistent with previous measurements of sound and carious enamel from microradiographic projections. The uncertainty in measurements of mineral concentration and mineral fraction volume was investigated by modelling enamel with a range of composition and component densities. This analysis showed that, although mineral concentration can be determined from LAC with an error of <0.2 g cm–3, the variation in pore fraction volume within caries lesions cannot be reliably determined from X-ray attenuation measurements alone.
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