X-Ray Diffraction and Multifrequency EPR Study of Radiation-Induced Room Temperature Stable Radicals in Octacalcium Phosphate.

Octacalcium phosphate (OCP) {Ca8H2(PO4)6×5H2O] has attracted increasing attention over the last decade as a transient intermediate to the biogenic apatite for bone engineering and in studies involving the processes of pathological calcification. In this work, OCP powders obtained by hydrolysis of dicalcium phosphate dehydrate were subjected to X- and γ-ray irradiation and studied by means of stationary and pulsed electron paramagnetic resonance at 9, 36 and 94 GHz microwave frequencies. Several types of paramagnetic centers were observed in the investigated samples. Their spectroscopic parameters (components of the g and hyperfine tensors) were determined. Based on the extracted parameters, the induced centers were ascribed to H0, CO33-, CO2- and nitrogen-centered (presumably NO32-) radicals. The spectroscopic parameters of the nitrogen-centered stable radical in OCP powders were found to be markedly different from those in hydroxyapatite. According to X-ray diffraction data, γ-ray irradiation allowed the phase composition of calcium phosphates to change; all minor phases with the exception of OCP and hydroxyapatite disappeared, while the OCP crystal lattice parameters changed after irradiation. The obtained results could be used for the tracing of mineralization processes from their initiation to completion of the final product, identification of the OCP phase, and to follow the influence of radiation processes on phase composition of calcium phosphates.

High-frequency pulsed ENDOR spectroscopy of the NV(-) centre in the commercial HPHT diamond.

This work reports direct 94GHz ENDOR spectroscopy of the (14)N nuclei in the NV(-) centre in single-crystal diamond. Roadmaps of ENDOR frequencies were measured and hyperfine/quadrupole interaction parameters were obtained, with AX,Y=-2.7MHz, AZ=-2.2MHz and P=-4.8MHz. The sign and value of each parameter was calculated using spin Hamiltonian matrix diagonalization, first and second order perturbation theory and confirmed experimentally. Magnetic field magnitude was measured by (13)C ENDOR signal with 0.02% precision or 0.5mT. The orientation of quadrupole, hyperfine and fine structure tensors are the same within error of experiment, g-factor is isotropic.

Optically Addressable Silicon Vacancy-Related Spin Centers in Rhombic Silicon Carbide with High Breakdown Characteristics and ENDOR Evidence of Their Structure.

We discovered a family of uniaxially oriented silicon vacancy-related centers with S=3/2 in a rhombic 15R-SiC crystalline matrix. We demonstrate that these centers exhibit unique characteristics such as optical spin alignment up to the temperatures of 250°C. Thus, the range of robust optically addressable vacancy-related spin centers is extended to the wide class of rhombic SiC polytypes. To use these centers for quantum applications it is essential to know their structure. Using high frequency electron nuclear double resonance, we show that the centers are formed by negatively charged silicon vacancies V_{Si}^{-} in the paramagnetic state with S=3/2 that is noncovalently bonded to the neutral carbon vacancy V_{C}^{0} in the nonparamagnetic state, located on the adjacent site along the SiC symmetry c axis.

Pb3+ radiation defects in Ca9Pb(PO4)6(OH)2 hydroxyapatite nanoparticles studied by high-field (W-band) EPR and ENDOR.

W-band pulsed EPR and ENDOR investigations of X-ray irradiated nanoparticles of synthetic hydroxyapatite Ca(9)Pb(PO(4))(6)(OH)(2) are performed. It is shown that in the investigated species lead ions probably replace the Ca(1) position in the hydroxyapatite structure.