The sorption of lead by synthetic hydroxyapatite (HA) from solutions containing Pb2+ initial concentrations up to 1770 mg L(-1) was studied. X-ray diffractometry (XRD) associated with Rietveld methodology for refining the spectra pattern was used in order to characterize the mechanisms of lead uptake. It is shown that the dissolution of hydroxyapatite is followed by the formation of a solid solution, Pb(10-x)Ca(x)(PO4)6(OH)2, with Pb ions mostly occupying Ca(II) sites. The Ca/Pb molar ratio of this solid solution decreases continuously until it reaches the structure of a pure hydroxypyromorphite. The cell parameters and the crystallite mean size behavior of both mineral phases reinforce the hypothesis that hydroxypyromorphite, PbHA, formation is the end of a process in which Pb(10-x)Ca(x)(PO4)6(OH)2 crystallites are continuously dissolved and recrystallized producing crystals with lower calcium content. Combination of Inductively Coupled Plasma spectrometry (ICP), chemical analysis, and XRD results permitted the conclusion that lead ions are not completely immobilized by precipitating Pb(10-x)Ca(x)(PO4)6(OH)2. Additional surface mechanisms also contribute to Pb2+ uptake. During Pb2+ sorption process, pH variations of the solution phase showed a more complex pattern than previously reported. Contribution of surface mechanisms, in addition to the hydroxyapatite dissolution, could explain this behavior.
First-principles modeling combined with experimental methods were used to study hydroxyapatite in which Sr2+ is substituted for Ca2+. Detailed analyses of cation-oxygen bond distributions, cation-cation distances, and site 1-oxygen polyhedron twist angles were made in order to provide an atomic-scale interpretation of the observed structural modifications. Density functional theory periodic band-structure calculations indicate that the Ca2+ to Sr2+ substitution induces strong local distortion on the hydroxyapatite lattice: the nearest neighbor Sr-O bond structures in both cationic sites are comparable to pure SrHA, while Sr induces more distortion at site 2 than site 1. Infrared vibrational spectroscopy (FTIR) and extended X-ray absorption fine structure (EXAFS) analysis suggest increasing lattice disorder and loss of OH with increasing Sr content. Rietveld refinement of synchrotron X-ray diffraction patterns shows a preference for the Ca1 site at Sr concentrations below 1 at.%. The ideal statistical occupancy ratio Sr2/Sr1=1.5 is achieved for approximately 5 at.%; for higher Sr concentrations occupation of the Ca2 site is progressively preferred.
The sputter deposited NiZn ferrite thin films were studied as a function of annealing temperature. The magnetization showed a monotonic increase with increasing annealing temperature. The coercivity shows a minimum at annealing temperature of 400 °C and shows a value of 14 Oe. Transmission electron microscopy study indicated that the grain size increases from ∼3 nm for the as-deposited case to ∼15 nm for the film annealed at 800 °C. The observed coercivity behavior could be attributed to the defects present in the films, the change in cation distribution, and the grain growth.
Hydroxyapatite (HA), a stable and biocompatible material for bone tissue therapy, may present a variable stoichiometry and accept a large number of cationic substitutions. Such substitutions may modify the chemical activity of HA surface, with possible impact on biocompatibility. In this work, we assessed the effects of calcium substitution with diverse divalent cations (Pb(2+), Sr(2+), Co(2+), Zn(2+), Fe(2+), Cu(2+), or Mg(2+)) on the biological behavior of HA. Physicochemical analyses revealed that apatite characteristics related to crystallinity and calcium dissolution/uptake rates are very sensitive to the nature of cationic substitution. Cytocompatibility was evaluated by mitochondrial activity, membrane integrity, cell density, proapoptotic potential, and adhesion tests. With the exception of Zn-HA, all the substituted HAs induced some level of apoptosis. The highest apoptosis levels were observed for Mg-HA and Co-HA. Cu-HA was the only material to impair simultaneously mitochondrial activity, membrane integrity, and cell density. The highest relative cell densities after exposure to the modified HAs were observed for Mg-HA and Zn-HA, while Co-HA significantly improved cell adhesion onto HA surface. These results show that changes on surface dissolution caused by cationic substitution, as well as the increase of metal species released to biological media, were the main responsible factors related to alterations on HA biocompatibility.
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