Analytical Chemistry · 2021 · 22 citations · 39 references
Natural SciencesMaterials EngineeringMaterials ScienceCrystal StructureNanomaterialsPhysical ChemistryCalcium Phosphate MaterialsCrystallization ProcessesMacromolecular AssemblyMineral GenesisNucleationSelf-assembly Of NanomaterialsCrystal Structure MetastabilityCrystallizationMineral Phase CompositionNanostructured Calcium Phosphates
studies in an extensive array of research fields, from biomineralization to surface and corrosion sciences. We show that these solutions undergo dynamic nanoscopic conformational rearrangements on the timescale of minutes to hours, even though they are commonly considered stable or metastable. In particular, we find and characterize nanoscale inhomogeneities made of calcium phosphate (CaP) aggregates that emerge from homogeneous SBFs within a few hours and evolve into prenucleation species (PNS) that act as precursors in CaP crystallization processes. These ionic clusters consist of ∼2 nm large spherical building units that can aggregate into suprastructures with sizes of over 200 nm. We show that the residence times of phosphate ions in the PNS depend critically on the total PNS surface. These findings are particularly relevant for understanding nonclassical crystallization phenomena, in which PNS are assumed to act as building blocks for the final crystal structure.
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<i>Principles of Nuclear Magnetic Resonance in One and Two Dimensions</i>
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