Phosphorus-31 spin-lattice NMR relaxation in bone apatite and its mineral standards

Phosphorus-31 spin-lattice relaxation, both in the laboratory (B(0)=4.7 T) and rotating frame (B(1)=2.2 mT), was studied in the following samples: mineral of whole human bone (samples B1-B6), apatite prepared from bone (BHA), natural brushite (BRU), synthetic hydroxyapatite hydrated (HAh) and calcined (HAc), and synthetic carbonatoapatite of type B (CHA-B) with 9 wt% of CO(3)(2-). The T(1)(P) relaxation time was determined directly using the saturation recovery technique, while the T(1 rho)(P) relaxation time was measured via (1)H-->(31)P CP by incrementing the (31)P spin-lock. In order to avoid an effect of magic-angle spinning (MAS) on CP and relaxation, the experiments were carried out on static samples. The (31)P spin-lattice relaxation was discussed for trabecular and cortical bone tissue from adult subjects in comparison to the synthetic mineral standards. None of the reference materials has matched accurately the relaxation behaviour of the bone mineral. The most striking differences between the examined substances were observed for T(1)(P), which for human bone was sample dependent and appeared in the range 55-100 s, while for HAh, HAc, and CHA-B was 7.2, 10.0, and 25.8 s, respectively. Possible reasons of so large relaxation diversity were discussed. It has been suggested that T(1)(P) of apatites is to some extent dependent on the concentration of the structural hydroxyl groups, and this in turn is controlled by the material crystallinity. It was also found that T(1)(P) decreased on hydration by ca. 30%. For T(1rho)(P), both its magnitude and dependence on the CP contact time gave useful structural information. The dehydrated samples (HAc and BHA) had long T(1 rho)(P) over 250 ms. Those, which contained water, either structural (BRU) or adsorbed on the crystal surface (HAh, CHA-B, and B1-B6), had shorter T(1 rho)(P) below 120 ms. It was concluded that the effect of water on T(1 rho)(P) is much more pronounced than on T(1)(P). The interpretation has involved P-OH groups and adsorbed water, which cover the apatite crystal surface.