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Bioprocess inspired formation of calcite mesocrystals by cation-mediated particle attachment mechanism.
Wang Q
,
Yuan B
,
Huang W
,
Ping H
,
Xie J
,
Wang K
,
Wang W
,
Zou Z
,
Fu Z
.
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Calcite mesocrystals were proposed, and have been widely reported, to form in the presence of polymer additives via oriented assembly of nanoparticles. However, the formation mechanism and the role of polymer additives remain elusive. Here, inspired by the biomineralization process of sea urchin spine comprising magnesium calcite mesocrystals, we show that calcite mesocrystals could also be obtained via attachment of amorphous calcium carbonate (ACC) nanoparticles in the presence of inorganic zinc ions. Moreover, we demonstrate that zinc ions can induce the formation of temporarily stabilized amorphous nanoparticles of less than 20 nm at a significantly lower calcium carbonate concentration as compared to pure solution, which is energetically beneficial for the attachment and occlusion during calcite growth. The cation-mediated particle attachment crystallization significantly improves our understanding of mesocrystal formation mechanisms in biomineralization and offers new opportunities to bioprocess inspired inorganic ions regulated materials fabrication.
Figure 1. The evolution of pH (a) and Ca2+ ions activity (b) of the solution when varying amount of Zn2+ ions were present. (c) The weight fraction of calcite and vaterite in the refined phases of precipitates extracted at 3600 s. SEM images of the precipitates obtained via fast vacuum filtration at 3600 s when Zn/(Zn + Ca) was 0% (d), 2% (e), 5% (f), 10% (g) and 20% (h); the insets are corresponding low magnification images.
Figure 2. SEM (a), TEM (b), HAADF (c) images and EDX mapping (d) of Zn-ACC when Zn/(Zn + Ca) was 5%. (e) SEM image of calcite crystals at the early stage of crystallization when Zn/(Zn + Ca) was 5%. TEM (f), HAADF (g) images and EDX mapping (h) of nanoparticles extracted during crystallization. (i and j) Higher magnification SEM images of the crystal surface shown in (e). Insets in (b) and (f) are corresponding SAED patterns.
Figure 3. (a) TEM image of a thin lamella obtained from a calcite crystal that was extracted at the early stage of crystallization when Zn/(Zn + Ca) was 5%. The orange dotted square indicates the region for EDX mapping analysis in Fig. 4c and d. High resolution TEM image (b) and SAED pattern (c) of the central region of the crystal area 1 in (a). The green arrow in (b) indicates the presence of nanoparticles and pores. (d) SAED patterns in different areas marked in (a).
Figure 4. HAADF image (a) and EDX mapping (b) of the central region (region 1 in Fig. 3a). HAADF image (c) and EDX mapping (d) of the region that is framed by orange dotted square in Fig. 3a.
Figure 5. Schematic illustration of ACC crystallization pathways in the presence of zinc ions: (1) Zn-enriched ACC particles undergo partial dissolution and form Zn-enriched hollow amorphous particles. Simultaneously, smaller Zn-enriched amorphous particles are generated; (2) smaller Zn-enriched ACC nanoparticles form aggregates via particle aggregation; (3) nanoparticles in the aggregates arrange themselves and form the calcite nucleus; (4) calcite nucleus further grows via attachment of smaller Zn-enriched ACC nanoparticles and forms calcite mesocrystals.
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