Papers by Author: Christian Jaeger

Abstract: 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.

Abstract: The results of a combined structural characterisation (XRD, IR, NMR, SEM, TEM) of a phosphate containing Mg-Ca silicate and a phosphate containing Na-Ca silicate glass samples are presented. The structural results are also compared with in vitro tests carried out in simulated body fluids for checking bioactivity.

Abstract: 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.

Abstract: Silicon substituted Hydroxyapatite coatings were prepared by Pulsed Laser Deposition from targets made of mixtures of Hydroxyapatite with Si powder at different concentrations. The properties of the Si-HA coatings with several degrees of Si substitution were analyzed by different techniques such as FTIR, XRD, XPS and solid-state NMR. It was found that the Si incorporation causes an amorphization of the structure together with a loss of carbonate groups. Furthermore, the Si atoms are incorporated in the form of SiO4 4- groups, and H(PO4)2- appears as the predominant phosphate group.

Abstract: Solid-state Nuclear Magnetic Resonance (NMR) has been used for a detailed structural analysis of different amorphous calcium phosphate (ACP) and hydroxyapatite (HAp) samples. For ACP the NMR data reveal the presence of hydrogenphosphate units in much larger quantities as known previously also showing differences between the samples. Furthermore, phosphate units close to water and a third group (yet unknown) are found in the spectra. A novel proposal has been established to explain the Ca-deficiency in nanocrystalline HAp. It consists of a crystalline core of stoichiometric composition which contains only 50% of the total phosphate amount. The residual phosphate is contained in a disordered surface layer with about 1 nm thickness. Most importantly, this surface layer contains hydrogenphosphate groups to a large extend and carbonate units. A Ca/P ratio of 1.52 is obtained from the NMR data which is very close to the value of 1.51 of the chemical analysis. Thus, NMR allows the investigation of the disordered mineral-protein interface and first examples concerning bone and nacre are presented and discussed.