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Coherent coupling of defect spins with surrounding nuclei along with the endowment to read out the latter, are basic requirements for an application in quantum technologies. We show that negatively charged boron vacancies (VB-) in electron-irradiated hexagonal boron nitride (hBN) meet these prerequisites. We demonstrate Hahn-echo coherence of the VB- electron spin with a characteristic decay time Tcoh = 15 us, close to the theoretically predicted limit of 18 us for spin defects in hBN. Modulation in the MHz range superimposed on the Hahn-echo decay curve are shown to be induced by coherent coupling of the VB- spin with the three nearest 14N nuclei through a nuclear quadrupole interaction of 2.11 MHz. Supporting DFT calculation confirm that the electron-nuclear coupling is confined to the defective layer. Our findings allow an in-depth understanding of the electron-nuclear interactions of the VB- defect in hBN and demonstrate its strong potential in quantum technologies.

International audience; The nitrogen-vacancy (NV) center in 3C-SiC, the analog of the NV center in diamond, has recently emerged as a solid-state qubit with competitive properties and significant technological advantages. Combining first-principles calculations and magnetic resonance spectroscopy we provide thorough insight in its magneto-optical properties. By applying resonantly excited electron paramagnetic resonance spectroscopy, we identified the zero-phonon absorption line of the 3 A 2 → 3 E transition at 1289 nm (within the telecom Oband) and measured its phonon sideband, the analysis of which reveals a Huang-Rhys factor of S = 2.85 and a Debye-Waller factor of 5.8 %. The low temperature spin-lattice relaxation time was found to be exceptionally long (T 1 = 17 s at 4 K). All these properties make NV in 3C-SiC a strong competitor for qubit application. In addition, the strong variation of the zero-field splitting in the range of 4K to 380K allows its application for nanoscale thermal sensing.

One of the exciting applications of electron-spin-based quantum sensing is the detection of distant nuclear spins of external molecular species. Here, we explore the application of a metal-organic framework (MOF) material as a host matrix for sensing spin centers. As a sensor, we employ inherent Cu

We present an X- and Q-band continuous wave (CW) and pulse electron paramagnetic resonance (EPR) study of a manganese doped [NH4][Zn(HCOO)3] hybrid framework, which exhibits a ferroelectric structural phase transition at 190 K. The CW EPR spectra obtained at different temperatures exhibit clear changes at the phase transition temperature. This suggests a successful substitution of the Zn2+ ions by the paramagnetic Mn2+ centers, which is further confirmed by the pulse EPR and 1H ENDOR experiments. Spectral simulations of the CW EPR spectra are used to obtain the temperature dependence of the Mn2+ zero-field splitting, which indicates a gradual deformation of the MnO6 octahedra indicating a continuous character of the transition. The determined data allow us to extract the critical exponent of the order parameter (β = 0.12), which suggests a quasi two-dimensional ordering in [NH4][Zn(HCOO)3]. The experimental EPR results are supported by the density functional theory calculations of the zero-field splitting parameters. Relaxation time measurements of the Mn2+ centers indicate that the longitudinal relaxation is mainly driven by the optical phonons, which correspond to the vibrations of the metal–oxygen octahedra. The temperature behavior of the transverse relaxation indicates a dynamic process in the ordered ferroelectric phase.

The metal–organic framework HKUST-1 is an attractive material for gas storage and gas separation applications because of its large surface area and high pore volume, and the presence of coordinatively unsaturated (cus) cupric ion sites. We investigated the interaction of alkenes and alkanes (ethene, 1-butene, ethane, and butane) with Cu2+ ions in their Zn-doped variant Cu2.97Zn0.03(btc)2 by continuous-wave electron paramagnetic resonance spectroscopy. Powder and single-crystal experiments revealed a characteristic change of cupric ion coordination from square planar to square pyramidal for the adsorption of ethylene and 1-butene and confirmed the formation of adsorption complexes at the cus sites of the Cu2+ ion in the mixed metal ion Cu–Zn paddle wheel (PW) units. Quantum chemical calculations based on density functional theory established a weak specific interaction between alkene π-orbitals and Cu2+ ions in a side-on coordination geometry. In contrast, no direct interaction between alkanes and the meta...

Optically addressable spin-triplet defects in silicon carbide, such as divacancies and negatively charged nitrogen vacancy $({\mathrm{NV}}^{\ensuremath{-}})$ allow to develop modern quantum technologies operating in the near-infrared range based on the well-developed semiconductor material. Here, by means of both high-frequency (94 GHz) pulsed electron paramagnetic resonance (EPR) and electron-nuclear double Rresonance (ENDOR) techniques the ground state properties of the negatively charged ${\mathrm{NV}}^{\ensuremath{-}}$ defect in $4H$-SiC were studied. We experimentally determined the ordering of the ground state spin sublevels and established the sign of the zero-field splitting to be positive as predicted by theory. Analysis of nuclear magnetic resonance transitions in ENDOR spectra allowed to determine the sign, symmetry, and absolute values of the hyperfine interaction of the ${\mathrm{NV}}^{\ensuremath{-}}$ defect electron spin with $^{14}\mathrm{N}$ nuclear spin as ${\mathit{A}}_{\ensuremath{\parallel}}=\ensuremath{-}1.142\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$ and ${\mathit{A}}_{\ensuremath{\perp}}=\ensuremath{-}1.184\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$. The absolute value of the nuclear quadrupole interaction constant reflecting an interaction between the $^{14}\mathrm{N}$ nuclear electric quadrupole moment with the electric field gradient was determined to be $|{\mathit{C}}_{q}|=2.44\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$. This large value is compatible with a threefold coordinated $^{14}\mathrm{N}$ nucleus with uniaxial symmetry and proves conclusively the existence of a nearestneighbor ${\mathrm{N}}_{\mathrm{C}}{\mathrm{V}}_{\mathrm{Si}}$ pair in the material. For this ${\mathrm{NV}}^{\ensuremath{-}}$ defect, an ensemble (Hahn-echo) coherence time of ${\mathit{T}}_{\text{2}}=49\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{s}$ was measured, a value which is in the range previously reported for silicon vacancy spin ensembles and slightly longer than ${\mathit{T}}_{\text{2}}=40\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{s}$ measured here on the divacancy spin ensemble.

Polarons in dielectric crystals play a crucial role for applications in integrated electronics and optoelectronics. In this work, we use density-functional theory and Green's function methods to explore the microscopic structure and spectroscopic signatures of electron polarons in lithium niobate (LiNbO3). Total-energy calculations and the comparison of calculated electron paramagnetic resonance data with available measurements reveal the formation of bound polarons at Nb_Li antisite defects with a quasi-Jahn-Teller distorted, tilted configuration. The defect-formation energies further indicate that (bi)polarons may form not only at Nb_Li antisites but also at structures where the antisite Nb atom moves into a neighboring empty oxygen octahedron. Based on these structure models, and on the calculated charge-transition levels and potential-energy barriers, we propose two mechanisms for the optical and thermal splitting of bipolarons, which provide a natural explanation for the reported two-path recombination of bipolarons. Optical-response calculations based on the Bethe-Salpeter equation, in combination with available experimental data and new measurements of the optical absorption spectrum, further corroborate the geometries proposed here for free and defect-bound (bi)polarons.

The spin-orbit coupling in solid state spin qubits allows for the lifting of spin degeneracy in the absence of an external magnetic field. The paper presents a theoretical framework to address this zero-field splitting in extended periodic systems, unravels its microscopic origin, and showcases its implications for coherent electrical control.

Whereas intrinsic defects in silicon carbide (SiC) have been widely considered for qubit applications, transition metals in this material have not yet been recognized as alternative systems. We have investigated the magneto-optical properties of the ${\mathrm{V}}^{3+}$ center in $4H\text{-SiC}$ by electron paramagnetic resonance (EPR) and photo-EPR spectroscopy in view of their possible application in quantum technology. We show that they fulfill all the requirements for such applications: a high-spin $S=1$ ground state, optically induced ground-state spin polarization of more than 70%, long spin-lattice relaxation times of the order of a second, as well as associated zero-phonon photoluminescence emission lines in the range of 1.8 \ensuremath{\mu}m. Further, the zero-field splitting parameter $D$ is temperature dependent and increases between $T=4\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and $T=292\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ linearly with a rate of 440 kHz/K, allowing potential nanoscale temperature sensing. These properties make the vanadium acceptor an extremely promising candidate for qubit applications with optical properties in the telecommunication optical range.

Atomlike defect levels in silicon carbide (SiC) polytypes have been proposed and proven to be an excellent platform for various quantum technology applications. Single-photon emitters, coherent control at room temperature, and temperature and magnetic field sensing at the nanoscale have already been demonstrated for the case of vacancy and divacancy defects in SiC and more recently proposed for negatively charged NV centers. NV centers, which allow a better control of their generation, offer in addition a further shift of the spectral range in the near infrared, i.e., in the $O$- and $S$-band telecom range. We demonstrate here that the association of high resolution optical spectroscopy and electron paramagnetic resonance spectroscopy combined with first-principles calculations allow the identification of the microscopic structure of the six distinct NV centers in $6H\ensuremath{-}\mathrm{SiC}$ and the assignment of their associated zero-phonon photoluminescence lines. Time resolved photo-EPR measurements at $T=4\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ show that NV centers in $6H\ensuremath{-}\mathrm{SiC}$ present spin lattice relaxation times of several seconds. These excellent qubit properties should enable their application and implementation in quantum information devices.

Structural characterization of metalloporphyrins in complex systems, such as native hydrocarbons, has been the focus of scientific and industrial interests for many years. We describe electron–nuclear double resonance (ENDOR) of crude oil from the well without any additional sample treatment (i.e., in the native environment) in the magnetic field of about 3.4 T and temperature of 50 K by applying microwave pulses at 94 GHz (W band) and radio frequency pulses at near the proton Larmor frequencies of 144 MHz to probe the paramagnetic vanadyls. By means of density functional theory calculations, ENDOR features are explained and ascribed to certain vanadyl porhyrin structural forms known to be present in crude oil.

Continuous wave X-band electron paramagnetic resonance (EPR) and density functional theory (DFT) were successfully applied to explore the incorporation and coordination state of the Cu2+ ions in the [Cd0.98Cu0.02(prz-trz-ia)] porous metal-organic frameworks. EPR measurements on powder samples and single crystals provided the full electron Zeeman g and copper hyperfine ACu interaction tensors including the orientation of their principal axes frames. DFT computations allowed for a detailed interpretation of the experimental results in terms of coordination symmetry and binding properties of the paramagnetic Cu2+ ions. Cupric ions were found to substitute Cd2+ ions in the dinuclear Cd-Cd units where they experience a noticeably distorted elongated pyramidal coordination environment formed by three nitrogen and two oxygen atoms from three linker molecules.

An accurate description of the two-electron density, crucial for magnetic coupling in spin systems, provides in general a major challenge for density functional theory calculations. It affects, e.g., the calculated zero-field splitting (ZFS) energies of spin qubits in semiconductors that frequently deviate significantly from experiment. In the present work (i) we propose an efficient and robust strategy to correct for spin contamination in both extended periodic and finite-size systems, (ii) verify its accuracy using model high-spin molecules, and finally (iii) apply the methodology to calculate accurate ZFS of spin qubits (NV$^-$ centers, divacancies) in diamond and silicon carbide. The approach is shown to reduce the dependence on the used exchange-correlation functional to a minimum.

Nanodiamond (ND) hosting nitrogen-vacancy (NV) centers is a promising platform for quantum sensing applications. Sensitivity of the applications using NV centers in NDs is often limited due to presence of paramagnetic impurity contents near the ND surface. Here, we investigate near-surface paramagnetic impurities in NDs. Using high-frequency (HF) electron paramagnetic resonance spectroscopy, the near-surface paramagnetic impurity within the shell of NDs is probed and its g-value is determined to be 2.0028(3). Furthermore, HF electron-electron double resonance-detected nuclear magnetic resonance spectroscopy and a first principle calculation show that a possible structure of the near-surface impurity is the negatively charged vacancy V-. The identification of the near-surface impurity by the present investigation provides a promising pathway to improve the NV properties in NDs and the NV-based sensing techniques., Comment: 21 pages, 6 figures

Spin-spin zero-field splitting (ZFS) is a sensitive spectroscopic signature accessable by electron paramagnetic resonance. It is the key fingerprint used for the identification of high-spin defect centers in semiconducting host materials and for the characterization of their electronic structure. In recent years, much progress has been made in developing an efficient first-principles methodology for ZFS calculations that help in the interpretation of experimental data. Here we address the negatively charged nitrogen-vacancy center (NV\(^-\)) in diamond. It is used as a test system to explore the accuracy and efficiency of spin-spin zero-field splitting calculations on massively parallel computing systems.

The interplay between Mn ions and corrole ligands gives rise to complex scenarios regarding the metal centers' electronic properties expressing a range of high oxidation states and spin configurations. The resulting potential of Mn-corroles for applications such as catalysts or fuel cells has recently been demonstrated. However, despite being crucial for their functionality, the electronic structure of Mn-corroles is often hardly accessible with traditional techniques and thus is still under debate, especially under interfacial conditions. Here, we unravel the electronic ground state of the prototypical Mn-5,10,15-tris(pentafluorophenyl)corrole complex through X-ray spectroscopic investigations of ultrapure thin films and quantum chemical analysis. The theory-based interpretation of Mn photoemission and absorption fine structure spectra (3s and 2p and L2,3-edge, respectively) evidence a Mn(III) oxidation state with an S = 2 high-spin configuration. By referencing density functional theory calculations with the experiments, we lay the basis for extending our approach to the characterization of complex interfaces.

Mn-catalyzed oxidation of the Ashalcha heavy oil in porous media was examined. We used manganese(III) tris(acetylacetonate) as a convinient oil-soluble precatalyst that decomposes to catalytically active species during the temperature ramping. Reaction kinetics in the heavy oil oxidation with air indicated that the presence of the manganese ions changes the mechanism of the oxidation process, especially in the high-temperature region. To study precatalyst transformations in detail, we suggested the approach of combining X-ray powder diffraction (XRPD), thermal analysis, non-isothermal kinetic methods, and electron paramagnetic resonance (EPR). A comprehensive study of the decomposition of pure manganese(III) tris(acetylacetonate) and the subsequent comparison of its behavior to that in porous media in the presence of the oil allows us to shed light on some aspects of the mechanism of catalytic oxidation.

The effect of codoping of hydroxyapatite (HAP) nanocrystals with average sizes of 35 ± 15 nm during “wet” synthesis by CO 3 2− carbonate anions and Mn2+ cations on relaxation characteristics (for the times of electron spin–spin relaxation) of the NO 3 2− nitrate radical anion has been studied. By the example of HAP, it has been demonstrated that the electron paramagnetic resonance (EPR) is an efficient method for studying anion–cation (co)doping of nanoscale particles. It has been shown experimentally and by quantummechanical calculations that simultaneous introduction of several ions can be energetically more favorable than their separate inclusion. Possible codoping models have been proposed, and their energy parameters have been calculated.

For high-spin centers, one of the key spectroscopic fingerprints is the zero-field splitting (ZFS) addressable by electron paramagnetic resonance. In this paper, an implementation of the spin-spin contribution to the ZFS tensor within the projector augmented-wave (PAW) formalism is reported. We use a single-determinant approach proposed by M. J. Rayson and P. R. Briddon [Phys. Rev. B 77, 035119 (2008)], and complete it by adding a PAW reconstruction term which has not been taken into account before. We benchmark the PAW approach against a well-established all-electron method for a series of diatomic radicals and defects in diamond and cubic silicon carbide. While for some of the defect centers the PAW reconstruction is found to be almost negligible, in agreement with the common assumption, we show that in general it significantly improves the calculated ZFS towards the all-electron results.

Constrained density-functional theory (DFT) calculations show that the recently observed optically induced insulator-metal transition of the In/Si(111)(8×2)/(4×1) nanowire array (Frigge et al., Nature 544:207, 2017) corresponds to the non-thermal melting of a charge-density wave (CDW). Massively parallel numerical simulations allow for the simulation of the photo-excited nanowires and provide a detailed microscopic understanding of the CDW melting process in terms of electronic surface bands and selectively excited soft phonon modes. Excited-state molecular dynamics in adiabatic approximation shows that the insulator-metal transition can be as fast as 350 fs.

Continuous wave X-band electron paramagnetic resonance (EPR) and density functional theory (DFT) were successfully applied to explore the incorporation and coordination state of the Cu

A computational analysis of the Overhauser effect is reported for the proton, methyl carbon, and carbonyl carbon nuclei of liquid acetone doped with the nitroxide radical TEMPOL. A practical methodology for calculating the dynamic nuclear polarization (DNP) coupling factors by accounting for both dipole-dipole and Fermi-contact interactions is presented. The contribution to the dipolar spectral density function of nuclear spins that are not too far from TEMPOL is computed through classical molecular dynamics (MD) simulations, whereas the contribution of distant spins is included analytically. Fermi contacts are obtained by subjecting a few molecules from every MD snapshot to ab initio quantum mechanical calculations. Scalar interaction is found to be an essential part of the (13)C Overhauser DNP. While mostly detrimental to the carbonyl carbon of acetone it is predicted to result in large enhancements of the methyl carbon signal at magnetic fields of 9 T and beyond. In contrast, scalar coupling is shown to be negligible for the protons of acetone. The additional influence of proton polarization on the carbon DNP (three-spin effect) is also analyzed computationally. Its effect, however, is concluded to be practically insignificant for liquid acetone.

The interplay of oppositely charged substitutions in the structure of hydroxyapatite (HAp) nanopowders is investigated on the atomic level by pulsed electron paramagnetic resonance (EPR) technique and ab initio density functional theory calculations. Benefits of EPR to determine Mn(2+) ions in nano-HAp samples are demonstrated. A simple approach based on the measurements of electron spin relaxation times allowed observing the strong influence of fast-relaxing Mn(2+) ions on the relaxation characteristics of the nitrate ions (NO3(-)/NO3(2-)) incorporated in trace amounts. Based on the results of ab initio calculations, we show the propensity of Mn(2+) and NO3(-)/NO3(2-) to associate within the HAp crystal lattice. This could have a direct impact on the functional properties of the material especially to resorption and ion exchange. Furthermore, such an effect can increase a propensity of undesired impurities to incorporate into the doped nanocrystals.

The structural properties of crude oils and asphaltenes, especially related to the dynamics of their aggregation, have been investigated by different experimental and theoretical methods during the last few decades. However, there are only a few works devoted to study the dynamics of asphaltenes in a native hydrocarbon environment. In this report, we illustrate a possibility to use electron paramagnetic resonance (EPR) spectra of vanadyl porphyrins in asphaltenes for the qualitative and quantitative analysis of their rotational mobility in the crude oil samples. On the basis of the simulation of the EPR spectra, a simple semi-empirical parameter sensitive to the transition between motional regimes is proposed. This mobility parameter can be potentially useful for the prediction and analysis of the thermal influence on heavy oil reservoirs during hydrocarbon production. It is found that the rotational correlation time of the complexes in heavy oil samples changes discontinuously with the temperature. The o...

Incorporation of the nitrogen-containing impurities in hydroxyapatite (HAp) powders with the sizes of the crystallites of (20–50) nm was studied using first-principles modeling combined with the multi-frequency (9 and 94 GHz) electron paramagnetic resonance (EPR) methods. It is shown that the observed EPR spectra are undoubtedly due to the presence of the bulk radiation-induced NO3 2− radicals. This conclusion is based on spin-polarized density functional theory calculations of spectroscopic parameters within gauge-including projector augmented wave framework followed by the exact comparison of the simulated EPR and electron–nuclear double resonance spectra with the experimental findings. In addition, a comprehensive analysis of the simulated properties allows us to suggest that the paramagnetic centers preferably occupy PO4 3− sites in the HAp structure.

Specimens of powders of hydroxyapatite (Ca10(PO4)6(OH)2) with average crystallite sizes in the range of 20–50 nm synthesized by the wet precipitation method have been investigated by the multifrequency (9 and 94 GHz) electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) methods. In specimens subjected to X-ray irradiation at room temperature, EPR signals that are caused by nitrogen compounds have been observed. Numerical calculations performed in terms of the density functional theory show that the observed EPR signal is caused by the occurrence of paramagnetic centers, the structure of which is NO 3 2− and which replace the positions of PO 4 3− in the hydroxyapatite structure.

We demonstrate the application of the combined experimental-computational approach for studying the anionic impurities in hydroxyapatite (HAp). Influence of the carbonation level (x) on the concentration of the NO3(2-) radicals in the HAp nanocrystals of Ca10-xNax(PO4)6-x(CO3)x(OH)2 with x in the range 0x2 and average sizes of 30 nm is investigated by different analytical methods including electron paramagnetic resonance (EPR). Stable NO3(2-) radicals are formed under X-ray irradiation of nano-HAp samples from NO3(-) ions incorporated in trace amounts during the wet synthesis process. Density functional theory (DFT) based calculations show energetic preference for the PO4 group substitution by NO3(-) ions. Comparison of the calculated and experimental spectroscopic parameters (g and hyperfine tensors) reveals that EPR detects the NO3(2-) radicals located in the positions of the PO4 group only. It is shown that with the increase in x, the carbonate ions substitute the NO3(2-)/NO3(-) ions. DFT calculations confirm that carbonate incorporation in HAp structure is energetically more favorable than the formation of the nitrate defect.

Density functional theory based calculations within the framework of the plane-wave pseudopotential approach are carried out to define the phonon spectrum of hydroxyapatite Ca10(PO4)6(OH)2 (HAp). It allows to describe the temperature dependence of the electronic spin-lattice relaxation time T1e of the radiation-induced stable radical NO32- in HAp, which was measured in X-band (9 GHz, magnetic field strength of 0.34 T) in the temperature range T = (10-300) K. It is shown that the temperature behavior of T1e at T > 20 K can be fitted via two phonon Raman type processes with the Debye temperature of 280 K evaluated from the phonon spectrum., 6 pages, 3 Figures

The role of transition metal ions in atherogenesis is controversial; they may be involved in hydroxyl radical generation and can also catalyze the reactive oxygen species neutralization reaction as cofactors of antioxidant enzymes. Using EPR spectroscopy, we revealed that 70% of aorta specimens with atherosclerotic lesions possessed superoxide dismutase activity, 100% of the specimens 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 indicate prospects of manganese analysis as a marker element in the express diagnostics of atherosclerosis.

Understanding the factors that influence pollutant transformation in the presence of ferric (oxyhydr)oxides is crucial to the efficient application of different remediation strategies. In this study we determined the effect of goethite, hematite, magnetite and ferrihydrite on the transformation of 2,4,6-trinitrotoluene (TNT) by Yarrowia lipolytica AN-L15. The presence of ferric (oxyhydr)oxides led to a small decrease in the rate of TNT removal. In all cases, a significant release of NO2− from TNT and further NO2− oxidation to NO3− was observed. A fraction of the released NO2− was abiotically decomposed to NO and NO2, and then NO was likely oxidized abiotically to NO2 by O2. ESR analysis revealed the generation of superoxide in the culture medium; its further protonation at low pH resulted in the formation of hydroperoxyl radical. Presumably, a fraction of NO released during TNT degradation reacted with superoxide and formed peroxynitrite, which was further rearranged to NO3− at the acidic pH values observed in this study. A transformation and reduction of ferric (oxyhydr)oxides followed by partial dissolution (in the range of 7–86% of the initial Fe(III)) were observed in the presence of cells and TNT. Mössbauer spectroscopy showed some minor changes for goethite, magnetite and ferrihydrite samples during their incubation with Y. lipolytica and TNT. This study shows that i) reactive oxygen and nitrogen species generated during TNT transformation by Y. lipolytica participate in the abiotic conversion of TNT and ii) the presence of iron(III) minerals leads to a minor decrease in TNT transformation. Electronic supplementary material The online version of this article (doi:10.1186/s13568-014-0094-z) contains supplementary material, which is available to authorized users.

Synthesized by the wet chemical precipitation technique hydroxyapatite powders (HAp) with the sizes of the crystallites of (20-50) nm and 1000 nm were analyzed by different analytical methods. By means of electron paramagnetic resonance (EPR) it is shown that during the synthesis process nitrate anions from the reagents (by-products) could incorporate into the HAp structure. The concentration of the stable NO32- radicals detected after X-ray irradiation of the product at room temperature does not decrease even after annealing up to 400 oC. The relaxation times and EPR parameters of the axially symmetric NO32- paramagnetic centers are measured with high accuracy. Increased sensitivity and resolution of high-frequency EPR (95 GHz) allows to reveal additional paramagnetic centre(s) which origin is discussed. Analyses of electron-nuclear double resonance (ENDOR) spectra from 1H and 31P nuclei and ab-initio density functional theory (DFT) calculations allow suggesting that the paramagnetic centers and nitrate anions as the precursors of NO32- radicals preferably occupy PO43- site in the HAp structure., 10 pages, 5 figures

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.

We present a comparative study of samples of aorta walls from male patients with atherosclerosis and hydroxyapatite powders with the average size of crystallites of 30 nm synthesized by the wet precipitation technique by using 94 GHz pulsed EPR. Origin of the observed paramagnetic centers is discussed. Supported by the electron microscopy and microanalysis, it is shown that EPR spectra from the calcified biological tissues correlates with those obtained in inorganic hydroxyapatites. The hypothesis about the important role of (nano)hydroxyapatite in formation of the mineral deposits and atherosclerotic plaque instability is further sustained.

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.