Narrowly distributed crystal orientation in biomineral vaterite

Biominerals formed by animals provide skeletal support, and many other functions. They were previously shown to grow by aggregation of amorphous nanoparticles, but never to grow ion-by-ion from solution, which is a common growth mechanism for abiotic crystals. We analyze vaterite CaCO3 multi crystalline spicules from the solitary tunicate Herdmania momus, with Polarization dependent Imaging Contrast PIC mapping, scanning and aberration corrected transmission electron microscopies. The first fully quantitative PIC mapping data, presented here, measured 0{\deg} 30{\deg} angle spreads between immediately adjacent crystals. Such narrowly distributed crystal orientations demonstrate that crystallinity does not propagate from one crystal to another 0{\deg} angle spreads, nor that new crystals with random orientation 90{\deg} nucleate. There are no organic layers at the interface between crystals, hence a new, unknown growth mechanism must be invoked, with crystal nucleation constrained within 30{\deg}. Two observations are consistent with crystal growth from solution: vaterite microcrystals express crystal faces, and are smooth at the nanoscale after cryo fracture. The observation of 30{\deg} angle spreads, lack of interfacial organic layers, and smooth fracture figures broadens the range of known biomineralization mechanisms and may inspire novel synthetic crystal growth strategies. Spherulitic growth from solution is one possible mechanism consistent with all these observations.Comment: Chemistry of Materials 201

Biomineral mesostructure

Biominerals formed by animals are most frequently calcium carbonate or phosphate polycrystalline materials with complex hierarchical structures. This article will focus on the 10-nm–10-µm scale, termed “mesoscale,” at which the “mesostructure” differs greatly across biominerals, is relevant to their mechanical properties, and reveals formation mechanisms in sea urchin teeth, mollusk shell prisms and nacre, human enamel, and coral skeletons. This article will conclude by focusing on important unanswered questions to inspire future research. Graphical abstract: [Figure not available: see fulltext.]

See-Through Teeth, Clearly

The teeth of the deep-sea dragonfish are sharp, hard, stiff, and transparent. Here we compare them to other teeth and their structure, which may determine both light scattering and mechanical behavior of teeth in diverse animals

Role of the Mineral in the Self-Healing of Cracks in Human Enamel

Human enamel is an incredibly resilient biological material, withstanding repeated daily stresses for decades. The mechanisms behind this resilience remain an open question, with recent studies demonstrating a crack-deflection mechanism contributing to enamel toughness and other studies detailing the roles of the organic matrix and remineralization. Here, we focus on the mineral and hypothesize that self-healing of cracks in enamel nanocrystals may be an additional mechanism acting to prevent catastrophic failure. To test this hypothesis, we used a molecular dynamics (MD) approach to compare the fracture behavior of hydroxyapatite (HAP) and calcite, the main minerals in human enamel and sea urchin teeth, respectively. We find that cracks heal under pressures typical of mastication by fusion of crystals in HAP but not in calcite, which is consistent with the resilience of HAP enamel that calcite teeth lack. Scanning transmission electron microscopy (STEM) images of structurally intact ("sound") human enamel show dashed-line nanocracks that resemble and therefore might be the cracks healed by fusion of crystals produced in silico. The fast, self-healing mechanism shown here is common in soft materials and ceramics but has not been observed in single crystalline materials at room temperature. The crack self-healing in sound enamel nanocrystals, therefore, is unique in the human body and unique in materials science, with potential applications in designing bioinspired materials

Loss of biological control of enamel mineralization in amelogenin-phosphorylation-deficient mice

Amelogenin, the most abundant enamel matrix protein, plays several critical roles in enamel formation. Importantly, we previously found that the singular phosphorylation site at Ser16 in amelogenin plays an essential role in amelogenesis. Studies of genetically knock-in (KI) modified mice in which Ser16 in amelogenin is substituted with Ala that prevents amelogenin phosphorylation, and in vitro mineralization experiments, have shown that phosphorylated amelogenin transiently stabilizes amorphous calcium phosphate (ACP), the initial mineral phase in forming enamel. Furthermore, KI mice exhibit dramatic differences in the enamel structure compared with wild type (WT) mice, including thinner enamel lacking enamel rods and ectopic surface calcifications. Here, we now demonstrate that amelogenin phosphorylation also affects the organization and composition of mature enamel mineral. We compared WT, KI, and heterozygous (HET) enamel and found that in the WT elongated crystals are co-oriented within each rod, however, their c-axes are not aligned with the rods' axes. In contrast, in rod-less KI enamel, crystalline c-axes are less co-oriented, with misorientation progressively increasing toward the enamel surface, which contains spherulites, with a morphology consistent with abiotic formation. Furthermore, we found significant differences in enamel hardness and carbonate content between the genotypes. ACP was also observed in the interrod of WT and HET enamel, and throughout aprismatic KI enamel. In conclusion, amelogenin phosphorylation plays crucial roles in controlling structural, crystallographic, mechanical, and compositional characteristics of dental enamel. Thus, loss of amelogenin phosphorylation leads to a reduction in the biological control over the enamel mineralization process