A sustainable one-pot method to transform seashell waste calcium carbonate to osteoinductive hydroxyapatite micro-nanoparticles

We have developed a straightforward, one-pot, low-temperature hydrothermal method to transform oyster shell waste particles (bCCP) from the species Crassostrea gigas (Mg-calcite, 5 wt% Mg) into hydroxyapatite (HA) micro/nanoparticles. The influence of the P reagents (H3PO4, KH2PO4, and K2HPO4), P/bCCP molar ratios (0.24, 0.6, and 0.96), digestion temperatures (25-200 & DEG;C), and digestion times (1 week-2 months) on the transformation process was thoroughly investigated. At 1 week, the minimum temperature to yield the full transformation significantly reduced from 160 & DEG;C to 120 & DEG;C when using K2HPO4 instead of KH2PO4 at a P/bCCP ratio of 0.6, and even to 80 & DEG;C at a P/bCCP ratio of 0.96. The transformation took place via a dissolution-reprecipitation mechanism driven by the favorable balance between HA precipitation and bCCP dissolution, due to the lower solubility product of HA than that of calcite at any of the tested temperatures. Both the bCCP and the derived HA particles were cytocompatible for MG-63 human osteosarcoma cells and m17.ASC murine mesenchymal stem cells, and additionally, they promoted the osteogenic differentiation of m17.ASC, especially the HA particles. Because of their physicochemical features and biological compatibility, both particles could be useful osteoinductive platforms for translational applications in bone tissue engineering

[Tl₇]^7– Clusters in Mixed Alkali Metal Thallides Cs_7.29K_5.71Tl₁₃ and Cs_3.45K_3.55Tl₇

Investigations in the ternary system Cs–K–Tl resulted in the unexpected formation of new ternary thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7. Single crystal X-ray structure analyses of both compounds reveal the presence of isolated Tl cluster units. Cs7.29K5.71Tl13 crystallizes in the monoclinic space group C2/c (a = 30.7792(9) Å, b = 11.000(2) Å, c = 14.0291(4) Å, β = 112.676(4)°, Z = 4) and contains [Tl6]6– and [Tl7]7– clusters as thallium subunits. Cs3.45K3.55Tl7 crystallizes in the tetragonal space group I41/a (a = 13.6177(2) Å, c = 25.5573(8) Å, Z = 8) and contains [Tl7]7– clusters exclusively. The formation of Cs7.29K5.71Tl13 is obtained after slow cooling in addition to that of Cs3.45K3.55Tl7 and can be suppressed by quenching the stoichiometric mixture. First dissolution experiments in liquid ammonia suggest thallium and amide as final oxidation products. Full relativistic band structure calculations of Cs4K3Tl7 and Cs8K5Tl13 showed a (pseudo) band gap around EF for both compounds