Synthesis and characterization of hydroxyapatite modified with (9r)-9-hydroxystearic acid

(9R)-9-hydroxystearic acid (9R-HSA) has been proven to have antitumoral activity because it is shown to inhibit histone deacetylase 1, an enzyme which activates DNA replication, and the (R)-enantiomer has been shown to be more active than the (S)-enantiomer both in vitro and by molecular docking. Hydroxyapatite is the main mineral component of bone and teeth and has been used for over 20 years in prostheses and their coating because it is biocompatible and bioactive. The goal of incorporating 9R-HSA into hydroxyapatite is to have a material that combines the bioactivity of HA with the antitumoral properties of 9R-HSA. In this work, 9R-HSA and its potassium salt were synthesized and the latter was also incorporated into hydroxyapatite. The content of (R)-9-hydroxystearate ion incorporated into the apatitic structure was shown to be a function of its concentration in solution and can reach values higher than 8.5%. (9R)-9-hydroxystearic acid modified hydroxyapatite was extensively characterized to determine the effect of the incorporation of the organic molecule. This incorporation does not significantly alter the unit cell but reduces the size of both the crystals as well as the coherent domains, mainly along the a-axis of hydroxyapatite. This is believed to be due to the coordination of the negatively charged carboxylate group to the calcium ions which are more exposed on the (100) face of the crystal, therefore limiting the growth mainly in this direction. Further analyses showed that the material becomes hydrophobic and more negatively charged with the addition of 9R-HSA but both of these properties reach a plateau at less than 5% wt of 9R-HSA.

Geomorfologia del giacimento di orso delle caverne nella grotta di Govjestica, Valle di Praca, Bosnia-Ercegovina

In 2011 the GSB/USB caving group of Bologna has discovered, in the southern fossil branches of Govjestica cave (Valle di Praça, Bosnia) a fossil deposit of vertebrates containing bones of Ursus spelaeus, Capra ibex, Cricetulus migratorius and Microtus. On the basis of the U/Th ages of the bones, teeth and carbonate flowstone covering the fossils (60 ka), datings carried out in the laboratories of U-Series at Bologna, and on the disposition of the bones, a past connection between Govjestica and the nearby Banja Stjena cave is hypothesised. The closure of this passage has occurred suddenly through a collapse that has forced the last cave bears awakened from their winter sleep to stay blocked in Govjestica, and die. The connecting passage has later been covered with calcite flowstones and is no longer visible. This hypothesis is sustained by the rather scarce number of skeletons of cave bears found in Govjestica (a dozen of skulls against the often large amounts of cave bears found in similar caves): Govjestica cave, and especially the Room of the Bones in its southern part, has been used by cave bears only for a couple of centuries before these parts became inaccessible. Furthermore, the entrance of Banja Stjena cave was probably located close to or at the level of the Praça river, that has excavated its thalweg for around 20 metres in the last 60 ka.