TY - JOUR A1 - Barheine, Sabrina A1 - Hayakawa, S. A1 - Jäger, Christian A1 - Shirosaki, Y. A1 - Osaka, A. T1 - Effect of disordered structure of boron-containing calcium phosphates on their in vitro biodegradability N2 - This study proposes a new guideline for designing biodegradable apatite ceramics. Boron-containing hydroxyapatite (BHAp) particles were prepared by a high-temperature solid-state reaction processing method and were characterized in terms of their chemical composition, apatite lattice defects and in vitro biodegradability. Solid-state nuclear magnetic resonance analysis showed that boron-incorporation into hydroxyapatite (HAp) derived by thermo-chemical reactions between borate and calcium phosphate phases led to disordered phases (BCaP) of a CaO–P2O5–B2O3–OH system covering the crystalline HAp core. X-ray diffraction analysis indicated that the BCaP phase must consist mainly of a crystalline oxyboroapatite (OBAp) phase. An in vitro biodegradability test showed that BHAp degraded quicker than HAp or ß-tricalcium phosphate. The biodegradability of BHAp particles can be controlled by boron incorporation into a HAp lattice leading to the formation of a disordered OBAp phase. KW - Boron KW - Hydroxyapatite KW - Calcium phosphate KW - NMR KW - Biodegradability KW - Disorder KW - Oxyboboapatite PY - 2011 DO - https://doi.org/10.1111/j.1551-2916.2011.04400.x SN - 0002-7820 SN - 1551-2916 VL - 94 IS - 8 SP - 2656 EP - 2662 PB - Blackwell Publishing CY - Malden AN - OPUS4-26244 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hayakawa, S. A1 - Jäger, Christian A1 - Sakai, A. A1 - Tsuru, K. A1 - Osaka, A. A1 - Fujii, E. A1 - Kawabata, K. T1 - Preparation and characterization of boron-containing hydroxyapatites T2 - Bioceramics 20 CY - Nantes, France DA - 2007-10-24 PY - 2007 AN - OPUS4-15058 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hayakawa, S. A1 - Sakai, A. A1 - Tsuru, K. A1 - Osaka, A. A1 - Fujii, E. A1 - Kawabata, K. A1 - Jäger, Christian T1 - Preparation and Characterization of Boron-containing Hydroxyapatite N2 - Boron-containing hydroxyapatite (BHAp) particles were synthesized by the wet chemical processing method and subsequent thermal treatment at the temperature ranging from 700-1200°C, and examined the effect of boron introduction on the microstructure of BHAp. The local structure around boron and phosphorus in the BHAp was analyzed by solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The heat-treatment above 700°C induced the thermal decomposition of HAp to β-TCP and then the chemical reaction between HAp and B(OH)3 was induced above 900°C, resulting in the formation of boron-substituted HAp particles accompanied by the formation of β-TCP and its transformation to α-TCP above 1200°C. KW - Hydroxyapatite KW - Boron KW - Structure KW - NMR KW - Thermal treatment PY - 2008 SN - 1013-9826 VL - 361-363 SP - 191 EP - 194 PB - Trans Tech Publ. CY - Aedermannsdorf AN - OPUS4-17584 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Barheine, Sabrina A1 - Hayakawa, S. A1 - Osaka, A. A1 - Jäger, Christian T1 - Surface, interface, and bulk structure of borate containing apatitic biomaterials N2 - Nuclear magnetic resonance (NMR) has been used for a detailed investigation of the borate incorporation in apatitic biomaterials prepared by high-temperature solid-state reaction sintering. The NMR data clearly show that crystalline hydroxyapatite (HAp) does exist, but it contains only about 30% of the entire phosphate content of the sample. The main phosphate content of about 70% forms a disordered calcium phosphate phase (BCaP) that accommodates the borate units in two structurally different trigonal BO33- groups besides some minor linear BO2- units. The average chemical composition of BCaP was estimated from the NMR spectra. Furthermore, a structural model of these particles is proposed, where HAp forms the crystalline core of these crystals covered by the disordered BCaP, suggesting that the BCaP phase is responsible for the adhesion properties of organic molecules like proteins and not HAp that is the only significant crystalline phase (XRD). Furthermore, the presence of an interface between HAp and BCaP is discussed based on various NMR experiments, including a triple-resonant 11B-31P cross-polarization edited 31P NMR spectrum with subsequent 31P{1H} REDOR (Rotational Echo DOuble Resonance) dephasing. PY - 2009 DO - https://doi.org/10.1021/cm900204q SN - 0897-4756 SN - 1520-5002 VL - 21 IS - 14 SP - 3102 EP - 3109 PB - American Chemical Society CY - Washington, DC AN - OPUS4-19723 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hayakawa, S. A1 - Kanaya, T. A1 - Tsuru, K. A1 - Shirosaki, Y. A1 - Osaka, A. A1 - Fujii, E. A1 - Kawabata, K. A1 - Gasqueres, G. A1 - Bonhomme, C. A1 - Babonneau, F. A1 - Jäger, Christian A1 - Kleebe, H.-J. T1 - Heterogeneous structure and in vitro degradation behavior of wet-chemically derived nanocrystalline silicon-containing hydroxyapatite particles N2 - Nanocrystalline hydroxyapatite (HAp) and silicon-containing hydroxyapatite (SiHAp) particles were synthesized by a wet-chemical procedure and their heterogeneous structures involving a disordered phase were analyzed in detail by X-ray diffractometry (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The effects of heterogeneous structure on in vitro biodegradability and the biologically active Ca(II)- and Si(IV)-releasing property of SiHAp particles were discussed. The 29Si NMR analysis revealed that the Si(IV) was incorporated in the HAp lattice in the form of Q0 (SiO4-4 or HSiO3-4) species, accompanied by the formation of condensed silicate units outside the HAp lattice structure, where the fraction and amount of Q0 species in the HAp lattice depends on the Si content. The 31P and 1H NMR results agreed well with the XRD, TEM and FTIR results. NMR quantitative analysis results were explained by using a core–shell model assuming a simplified hexagonal shape of HAp covered with a disordered layer, where Si(IV) in Q0 was incorporated in the HAp lattice and a disordered phase consisted of hydrated calcium phosphates involving polymeric silicate species and carbonate anions. With the increase in the Si content in the HAp lattice, the in vitro degradation rate of the SiHAps increased, while their crystallite size stayed nearly unchanged. The biologically active Ca(II)- and Si(IV)-releasing ability of the SiHAps was remarkably enhanced at the initial stage of reactions by an increase in the amount of Si(IV) incorporated in the HAp lattice but also by an increase of the amount of polymeric silicate species incorporated in the disordered phase. KW - Silicate KW - Calcium phosphate KW - Hydroxyapatite KW - Degradation KW - Apatite formation PY - 2013 DO - https://doi.org/10.1016/j.actbio.2012.08.024 SN - 1742-7061 VL - 9 IS - 1 SP - 4856 EP - 4867 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-27319 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Barheine, Sabrina A1 - Hayakawa, S. A1 - Osaka, A. A1 - Jäger, Christian T1 - A NMR investigation of borate incorporation in apatitic biomaterials N2 - The incorporation of ions in the lattice of hydroxyapatite alters significantly its structure. Particularly, if anions such as trigonal borate units are accommodated in the lattice severe distortions must occur around the substitution site because of different geometric shape, electric charge and anion size. Solid-state NMR has been used to investigate this problem in detail for a hydroxyapatite sample synthesized by high temperature solid state reaction. The results clearly verify the existence of network distortions. Indeed, only about 1/3 of the total phosphate content forms crystalline hydroxyapatite (also found in XRD) whereas the residual amount is contained in two different phosphate sites with 31P chemical shifts of 5.5 ppm and 2.3 ppm, but broad resonances lines suggesting disorder. Furthermore, a novel proton signal at -0.6 ppm was found which is directly associated with the borate incorporation. No specific correlation of the two structurally different borate units with the two phosphate groups is found. KW - Apatite KW - Borate KW - Biomaterials KW - Solid-state NMR PY - 2009 UR - http://www.scientific.net/0-87849-353-0/205/ DO - https://doi.org/10.4028/3-908453-07-0.205 SN - 1013-9826 VL - 396-398 SP - 205 EP - 208 PB - Trans Tech Publ. CY - Aedermannsdorf AN - OPUS4-18914 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -