Concentration dependence of 19F nuclear magnetic resonance decay shapes and second moments in bone mineral.

19F nuclear magnetic resonance (NMR) spin-echoes and free induction decays (FIDs) have been observed from samples of fluoridated trabecular canine bone powder, with fluoride concentrations ([F]) ranging from approximately 10 to 33 mg F/g Ca. Curve fitting of echo envelopes and FIDs was performed using a two-component model function, where one of the components incorporates the effects of one-dimensional dipolar coupling. This function provides a good match for both echo envelopes and FIDs. Estimates of the total second moment and its homonuclear (F-F coupling) component were obtained from the fitting procedure. Based on the second moment measurements, it is argued that 19F spins in bone mineral typically experience weaker heteronuclear dipolar coupling than those in the mineral hydroxyapatite (HAP), which is often considered to be a prototype for bone mineral.

Concentration dependence of fluorine impurity spin-lattice relaxation rate in bone mineral.

The concentration dependence of the fluoride ion spin-lattice relaxation rate has been observed by nuclear magnetic resonance experiments on samples of defatted and dried bone. The 19F spin-lattice relaxation rates increased linearly with the bone fluoride concentration. Different results were obtained from trabecular than from cortical bone. For the same macroscopic fluoride content per gram of bone calcium, the relaxation rate is significantly faster in cortical bone. Relaxation rates in cortical bone samples prepared from both rats and dogs were apparently controlled by the same species-independent processes. For samples from beagle dogs, the bulk fluoride concentrations measured by neutron activation analysis were 3.1 +/- 0.3 times greater in trabecular bone than in the corresponding cortical bone. The beagle spin-lattice relaxation data suggest that the microscopic fluoride concentrations in bone mineral were 1.8 +/- 0.4 times greater in trabecular bone than in cortical bone. It is concluded that the accumulation of fluoride impurities in bone mineral is non-uniform.

Field dependence of 19F NMR in rat bone powders.

The 19F NMR properties of fluoridated rat bone powder samples have been studied in several external magnetic fields. The results show a characteristic field dependence, related to the strength of chemical shift interactions compared to dipole-dipole interactions. While the free induction decay shape is relatively insensitive to the 19F bone mineral concentration, the spin-lattice relaxation time decreases with increasing 19F concentration. Multi-exponential spin-lattice relaxation processes indicate that there are at least two chemically inequivalent incorporation sites for fluorine in bone mineral. Evidence for clustering of 19F fluoride impurities in bone mineral is seen in Hahn echo experiments. Sample preparation and handling methods are shown to affect the values of some of the observed NMR parameters.

In vivo 19F spin relaxation in index finger bones.

19F free induction decay (FID) signals have been observed from the index fingers of four male and two female adult volunteers using a 27-MHz pulsed nuclear magnetic resonance spectrometer equipped with a split ring resonator probe. The value of the in vivo spin-lattice relaxation time T1 of the fluoride ions naturally accumulated in bone mineral has been determined to be 2.0 +/- 0.3 s. The shape of the observed FID signals in the inhomogeneous external magnetic field indicates that the F distribution is not uniform along the length of the finger. The fluoride ion content of the index finger (within a 65-mm length from its distal end) was measured with a sensitivity of +/- 0.5 mg F within a 30-min observation time.

In vivo measurement of accumulated bone fluorides by nuclear magnetic resonance.

We have developed a localized noninvasive nuclear magnetic resonance (NMR) method for determining the accumulated bone fluoride content in human index fingers. Using a 27 MHz "split-ring" resonator probe, we measure the total fluoride (F) content within a 6.5 cm length of the distal end of the index finger from a calibrated determination of the intensity of the observed 19F free induction decay (FID) signal. Since fluoride impurities accumulate almost exclusively in bone mineral, the 19F resonance signal is broadened by rigid lattice magnetic dipole-dipole interactions, causing the FID signal to have a relatively short lifetime of approximately 75 microseconds. This short signal lifetime, plus the weakness of the signal strength prevents conventional magnetic resonance imaging equipment from observing the 19F in bone mineral. Nevertheless, we have achieved an in vivo sensitivity of +/- 0.5 mg fluoride in an observation period of 30 min. Assuming an index finger has between 0.25 and 0.5 g of bone calcium, this sensitivity is just sufficient to detect fluorides in the index finger of most adults whose bone fluoride concentration is greater than 2.0 mg fluoride/g calcium (0.8 mg/g ash weight). We are particularly interested in using this new NMR technique to monitor the rate of bone fluoride accumulation in osteoporotic patients receiving therapeutic levels of fluoride in their diets.

In vivo analysis of bone fluoride content via NMR.

In vivo free induction decay signals have been detected from the fluoride ion (F) content of human finger bones by a 27 MHz pulsed single-coil nuclear magnetic resonance (NMR) spectrometer. The intensity of these dipolar-broadened NMR signals can be used to estimate the F content of the middle phalanx of the index finger. This NMR procedure is the first non-invasive method capable of monitoring bone F contents. The preliminary results we report were obtained from patients known by previous biopsies to have relatively high bone F concentrations in their pelvis. This new monitoring technique does not yet have adequate sensitivity or accuracy for routine clinical use. As a research technique, it has applications to the diagnosis of fluorosis (both industrial and endemic) as well as renal osteodystrophy, and to the establishment of optimal NaF does for the treatment of osteoporosis.