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Langmuir, Vol.33, No.8, 2059-2067, 2017
Biologically Analogous Calcium Phosphate Tubes from a Chemical Garden
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 (PO43-) was quantified and changes in pH were monitored to explain the preferential formation of tubes within a PO43- 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 (mu-XRF) revealed hydroxyapatite (HA, Ca-10(PO4)(6)(OH)(2)) and dicalcium phosphate dihydrate (DCPD, CaHPO4 center dot 2H(2)O) phases organized in a hierarchical manner. Notably, the tubule diameters ranged from 100 to 150 mu m, an ideal size for the permeation of vasculature in biological hard tissue.