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.

[Calcification of atherosclerotic plaques and assessment of their stability]. / Kal'tsifikatsiia ateroskleroticheskikh bliashek i otsenka ikh stabil'nosti.

Presented herein is a review of the literature concerning mechanisms of calcification of atherosclerotic plaques (ASP), showing molecular mechanisms of interaction of processes of calcification with the factors inducing instability of ASPs (anti-inflammatory cytokines, neoangiogenesis, increased level of matrix metalloproteinases, etc.), also describing the effect of the value of volume of scope of calcification on stability of ASPs, followed by discussing the problems related to the role of biominerals (hydroxyapatite calcium phosphate) and Mn2+ in calcification of ASPs and their impact upon stability of the plaque.

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.

Identification of Fe3+-Li+ complexes in ZnO by means of high-frequency EPR/ENDOR spectroscopy.

Theoretical prediction of a high Curie temperature in ZnO doped with Mn, Fe, and other transition metals has stimulated the investigation of these materials by many research groups. Although charge-compensated Fe(3+) centers in ZnO:Fe have been observed by means of EPR and have been known for decades, conclusions on the chemical nature of these defects are still contradictory. Originally, these centers were treated as Fe(3+)-Li(+) complexes with both ions occupying adjacent cationic sites. Recently, however, the centers were interpreted as a substitutional Fe(3+) ion with a vacancy at an adjacent zinc or oxygen site (Fe-VZn or Fe-VO). In order to determine the chemical nature of the impurity associated with Fe(3+), electron-nuclear double resonance (ENDOR) spectroscopy was used. ENDOR measurements reveal NMR transitions corresponding to nuclei with g-factor gN=2.171 and spin I=3/2. This unambiguously shows presence of Li as a charge compensator and also resolves contradictions with the theoretical prediction of the Fe-VO formation energy. The electric field gradients at the (7)Li nuclei (within the Fe(3+)-Li(+) complexes) were estimated to be significantly lower than the gradient at undistorted Zn sites.

[Manganese in atherogenesis: detection, origin, and role].

The role of transition metal ions in atherogenesis is controversial; they can participate in the hydroxyl radical generation and catalyze the reactive oxygen species neutralization reaction as cofactors of antioxidant enzymes. Using EPR spectroscopy, we revealed that 70% of the samples of aorta with atherosclerotic lesions possessed superoxide dismutase activity, 100% of the samples initiated Fenton reaction and demonstrated the presence of manganese paramagnetic centers. The sodA gene encoding manganese-dependent bacterial superoxide dismutase was not found in the samples of atherosclerotic plaques by PCR using degenerate primers. The data obtained indicates the perspectives of manganese analysis as a marker element in the express diagnostics of atherosclerosis.

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.

High-frequency EPR and ENDOR spectroscopy on semiconductor nanocrystals.

EPR and ENDOR experiments at 95 GHz on ZnO nanoparticles reveal the presence of shallow donors related to interstitial Li and Na atoms. The experiments allowed, for the first time, to probe the effect of confinement on the shape of the electronic wave function. In addition, it is observed that the 67Zn nuclear spins become polarized upon saturation of the EPR transition. This Overhauser effect is induced by the zero-point vibrations of the phonon system in the nanoparticles.

ENDOR spectroscopy at 275 GHz.

A pulsed ENDOR spectrometer operating at a microwave frequency of 275 GHz is described. The results demonstrate that this type of spectroscopy can now be performed routinely at this high microwave frequency. The advantages compared to conventional EPR frequencies are the high spectral resolution, time resolution, and sensitivity.

A continuous-wave and pulsed electron spin resonance spectrometer operating at 275 GHz.

An electron paramagnetic resonance (EPR) spectrometer is described which allows for continuous-wave and pulsed EPR experiments at 275 GHz (wavelength 1.1 mm). The related magnetic field of 9.9 T for g approximately 2 is supplied by a superconducting solenoid. The microwave bridge employs quasi-optical as well as conventional waveguide components. A cylindrical, single-mode cavity provides a high filling factor and a high sensitivity for EPR detection. Even with the available microwave power of 1 mW incident at the cavity a high microwave magnetic field B1 is obtained of about 0.1 mT which permits pi/2-pulses as short as 100 ns. The performance of the spectrometer is illustrated with the help of spectra taken with several samples.