Biologically Analogous Calcium Phosphate Tubes from a Chemical Garden

• Published in: Langmuir 2017-02, Vol.33 (8), p.2059-2067
• Main Authors: Hughes, Erik A. B, Williams, Richard L, Cox, Sophie C, Grover, Liam M
• Format: Article
• Language: English
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/acs.langmuir.6b04574

Calcium phosphate (CaPO4) tubes with features comparable to mineralized biological microstructures, such as Haversian canals, were grown from a calcium gel/phosphate solution chemical garden system. A significant difference in gel mass in response to high and low solute phosphate equivalent environments existed within 30 min of solution layering upon gel (p = 0.0067), suggesting that the nature of advective movement between gel and solution is dependent on the solution concentration. The transport of calcium cations (Ca2+) and phosphate anions (PO4 3–) was quantified and changes in pH were monitored to explain the preferential formation of tubes within a PO4 3– concentration range of 0.5–1.25 M. Ingress from the anionic solution phase into the gel followed by the liberation of Ca2+ ions from the gel was found to be essential for acquiring self-assembled tubular CaPO4 structures. Tube analysis by scanning electron microscopy (SEM), X-ray diffraction (XRD), and micro X-ray florescence (μ-XRF) revealed hydroxyapatite (HA, Ca10(PO4)6(OH)2) and dicalcium phosphate dihydrate (DCPD, CaHPO4·2H2O) phases organized in a hierarchical manner. Notably, the tubule diameters ranged from 100 to 150 μm, an ideal size for the permeation of vasculature in biological hard tissue.