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Space exploration is perhaps one of the most difficult tasks ever undertaken since the existence of mankind. International Space Station (ISS) is a unique instrument for advanced technology research that is not possible anywhere else. Tissue engineering in a space environment where “turnoff” gravity can be done is the most emerging field with high-value targets. The microgravity conditions allow the designing of novel biomaterials that cannot be produced on Earth but benefit Earth. Developing and manufacturing a biomaterial to address a space-based challenge could lead to novel biomaterials that will bring important applications in clinical medicine on Earth and/or for long-duration space missions. Up to today, there are only a handful of emerging biomaterials that have been tested in space, none of which have been used for their eventual function. This work is reporting on advances in space technology via the 3D magnetic assembler approach to have furthered the development of synthetic bone tissue constructs on board the ISS Russia Segment during the expeditions 61/62 with clear evidence of their function in preclinical conditions on Earth. The results have demonstrated both high levels of osteoinductive and - conductivity as well as a ultimate rate of tissue regeneration of space bone grafts.

High-frequency pulsed electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) were used to determine electron nuclear interactions on remote ligand shells of silicon and carbon in spin-3/2 color centers with an optically induced high-temperature spin alignment in hexagonal $4H$-, $6H$-, and rhombic $15R$-silicon carbide (SiC) polytypes. The EPR and ENDOR experimental data relate unambiguously to spin-3/2 centers in which the optically induced alignment of the spin-level populations occurs. The identification is based on resolved ligand hyperfine interactions with carbon and silicon nearest, next-nearest, and the more distant neighbors and on the determination of the unpaired electron spin densities. The hyperfine interactions with $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei are unambiguously separated due to the selective population of the fine-structure levels with certain values of ${\mathrm{M}}_{\mathrm{S}}$. The signs of these interactions and, as a result, the signs of oscillating spin density at $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei, are determined. On the basis of the EPR and optically induced ENDOR measurements, signs of the fine-structure splitting for all the centers were demonstrated, which made it possible to establish the character of optically induced spin alignment, including the inverse populations of the spin levels for these centers. The values of hyperfine interaction with $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei, including those remote from the localization of the spin-3/2 center, are tabulated, which can be used by a number of algorithms in quantum information processing as long-term memory.

The presence of paramagnetic species such as vanadyl complexes (VO2+) and free carbon radicals in petroleum disperse systems (PDSs) such as crude oil, bitumen, or kerogen causes significant interes...

A high-frequency/high-magnetic field (94 GHz/3.3 T) electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) study of monocrystalline nanodiamonds (ND) is carried out. Influence of the hydrogen and fluorine modification of the ND surface on EPR and ENDOR signals from the superficial and bulk paramagnetic centers is observed. The effect shows that the ND bulk paramagnetic centers could serve as the intrinsic probe of ND surface modification despite deep localization, shielding from the environment and two-layered surface of the diamond nanoparticle.

This article presents the results of a study of radiation-induced defects in various synthetic calcium phosphate (CP) powder materials (hydroxyapatite—HA and octacalcium phosphate—OCP) by electron paramagnetic resonance (EPR) spectroscopy at the X, Q, and W-bands (9, 34, 95 GHz for the microwave frequencies, respectively). Currently, CP materials are widely used in orthopedics and dentistry owing to their high biocompatibility and physico-chemical similarity with human hard tissue. It is shown that in addition to the classical EPR techniques, other experimental approaches such as ELDOR-detected NMR (EDNMR), electron spin echo envelope modulation (ESEEM), and electronnuclear double resonance (ENDOR) can be used to analyze the electron–nuclear interactions of CP powders. We demonstrated that the value and angular dependence of the quadrupole interaction for14 N nuclei of a nitrate radical can be determined by the EDNMR method at room temperature. The ESEEM technique has allowed for a rapid analysis of the nuclear environment and estimation of the structural positions of radiation-induced centers in various crystal matrices. ENDOR spectra can provide information about the distribution of the nitrate radicals in the OCP structure. © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Published under the CC BY 4.0 license., Authors would like to thank the Russian Foundation for Basic Research, project no. 18-29-11086. Institute of Solid State Physics, University of Latvia as the Center of Excellence received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01–2016-2017- TeamingPhase2 under grant agreement No. 739508, project CAMART2.

Coherent spin manipulations of spin-$\frac{3}{2}$ color center ensembles in 6H-SiC crystal have been studied in high magnetic fields using methods of pulsed electron paramagnetic resonance, Rabi oscillations, and pulsed electron-electron double resonance under optical alignment conditions of the spin level populations. Rabi oscillation experiments show room temperature coherent control of these spin-$\frac{3}{2}$ color center ensembles in strong magnetic fields. A sharp decrease of the spin-lattice relaxation time ${T}_{1}$, \ensuremath{\sim}40 times, was observed in 6H-SiC at magnetic field of \ensuremath{\sim}3.5 T with increasing temperature from 100 to 300 K, while the spin-spin relaxation time ${T}_{2}$ is only shortened by \ensuremath{\sim}1.3 times. With an increase in the magnetic field, the times ${T}_{1}$ and ${T}_{2}$ were shown to decrease. The relaxation time ${T}_{1}$ in the case of magnetic field directed along the axis of the spin-$\frac{3}{2}$ center is \ensuremath{\sim}2 times longer than ${T}_{1}$ in magnetic field perpendicular to this axis. Relaxation times of the spin center in crystal grown with a reduced concentration of an isotope $^{29}\mathrm{Si}$ are significantly longer than crystal, with the natural content of isotopes. With a decrease in the $^{29}\mathrm{Si}$ content in our experiments by a factor of \ensuremath{\sim}5, the effective nuclear spin bath in SiC is reduced by a factor of \ensuremath{\sim}2. In a zero magnetic field resonance, transitions are allowed as magnetic dipole transitions with frequency ${\ensuremath{\omega}}_{0}$ which correspond to the zero-field splitting. In zero magnetic field and in fixed magnetic fields, the Rabi frequency was shown, using so-called ``Feynman-Vernon-Hellwarth transformation,'' to be ${\ensuremath{\omega}}_{R}=|\ensuremath{\gamma}|{B}_{1}$. In pulsed electron-electron double resonance experiments, a change in the intensity of the electron spin echo signal corresponding to one of the spin-allowed fine structure transitions is recorded depending on the sweep of the second frequency. The experiments show the possibility to coherently detect the optical spin alignment between ${M}_{S}=\ifmmode\pm\else\textpm\fi{}\frac{3}{2}$ via optically pumped silent ${M}_{S}=\ifmmode\pm\else\textpm\fi{}\frac{1}{2}$ sublevels of the spin-$\frac{3}{2}$ color centers, including a detection of Rabi oscillations.

For bone replacement materials, osteoconductive, osteoinductive, and osteogenic properties are desired. The bacterial resistance and the need for new antibacterial strategies stand among the most challenging tasks of the modern medicine. In this work, brushite cements based on powders of Zinc (Zn) (1.4 wt%) substituted tricalcium phosphate (β-TCP) and non-substituted β-TCP were prepared and investigated. Their initial and final phase composition, time of setting, morphology, pH evolution, and compressive strength are reported. After soaking for 60 days in physiological solution, the cements transformed into a mixture of brushite and hydroxyapatite. Antibacterial activity of the cements against Enterococcus faecium, Escherichia coli, and Pseudomonas aeruginosa bacteria strains was attested. The absence of cytotoxicity of cements was proved for murine fibroblast NCTC L929 cells. Moreover, the cell viability on the β-TCP cement containing Zn2+ ions was 10% higher compared to the β-TCP cement without zinc. The developed cements are perspective for applications in orthopedics and traumatology.

Calcium phosphates (CaP) based materials are widely recognized as the most suitable matrix for bone tissue engineering. The cationic and anionic substitutions of CaP structure by the elements and groups of biological importance seem to be the effective ways to improve the properties of CaP-based substances to achieve the material’s desired parameters. Various analytical and biochemical methods are used for controlling their chemical content, structure, morphology, etc. Unfortunately, magnetic resonance techniques are usually not even considered as necessary tools for CaP inspection. Some aspects of application of the commercially realized electron paramagnetic resonance (EPR) approaches for characterization of CaP powders and ceramics (including the nanosized materials) such as hydroxyapatite and tricalcium phosphates of biogenic and synthetic origins containing intrinsic impurities or intentional dopants are demonstrated. Among them (1) conventional approaches; (2) high-frequency approaches – for measuring small amount of material; (3) pulsed methods – to study size effects, effects of the co-doping by different sorts of ions, to determine the location of paramagnetic centers, etc. The key features and advantages of the EPR techniques for CaP based materials characterization that could complement the data obtained with the recognized analytical methods are stressed.

We present a detailed study of electron/nuclear interaction in a specific crude oil by continuous-wave and pulsed EPR, electron–nuclear double resonance (ENDOR) at W-band (94 GHz), and fast field-c...

Temperature dependencies of electron paramagnetic resonance spectra of intrinsic paramagnetic vanadyl complexes and dynamical viscosity for two heavy crude oils and asphalt samples are measured. Transitions between the different motional conditions (from the rigid to the fast motion regimes) are observed. The rotational correlation times (in the model of the isotropic diffusion) are extracted. It is shown that the characteristic temperatures for the motional regime transitions are mainly defined by the asphaltenes’ content. From our analysis it follows that the thermal treatment leads to the destruction of the asphaltene complexes onto the 4–5 small pieces. The results indicate that paramagnetic vanadyl complexes are the sensitive intrinsic probes to study qualitatively and quantitatively structural transformations of aspahltenes of heavy crude oils in-situ.

Optically addressable spins in wide-bandgap semiconductors are a promising platform for exploring quantum phenomena. While colour centres in three-dimensional crystals such as diamond and silicon carbide were studied in detail, they were not observed experimentally in two-dimensional (2D) materials. Here, we report spin-dependent processes in the 2D material hexagonal boron nitride (hBN). We identify fluorescence lines associated with a particular defect, the negatively charged boron vacancy ($${\mathrm{V}}_{\mathrm{B}}^ -$$), showing a triplet (S = 1) ground state and zero-field splitting of ~3.5 GHz. We establish that this centre exhibits optically detected magnetic resonance at room temperature and demonstrate its spin polarization under optical pumping, which leads to optically induced population inversion of the spin ground state—a prerequisite for coherent spin-manipulation schemes. Our results constitute a step forward in establishing 2D hBN as a prime platform for scalable quantum technologies, with potential for spin-based quantum information and sensing applications. An ensemble of spins associated with an intrinsic defect of two-dimensional hexagonal boron nitride is shown to be optically addressable, allowing spin polarization of its triplet ground state and providing evidence of spin coherence.

Nanopowders of aluminum-substituted (0-20 mol %) hydroxyapatite (HA) with the average size of 40-60 nm were synthesized by the precipitation method from nitrate solutions. A series of samples were studied by various analytical tools to elucidate the peculiarities of Al introduction. Electron paramagnetic resonance and pulsed electron-nuclear double resonance data demonstrate that incorporation of Al resulted in a decrease in the concentration of impurity carbonate anions and lead to an increase in the number of protons in the distant environment of the impurity nitrogen species. Density functional theory calculations show that the Al3+ incorporation is accompanied by the local positional rearrangement and the distortion of anion channel geometry. An in vitro test conducted on MG-63 cells demonstrates the cytocompatibility and magnification of the surface matrix characteristics with Al doping.

Crystal field parameters for two nonequivalent positions Ca (I) and Ca (II) for hydroxyapatite (HAp) crystals from the density functional theory (DFT) are calculated. Calculations are compared with the experimental electron paramagnetic resonance (EPR) spectra (registered at two microwave frequencies) for the synthesized Mn-HAp powders Ca9.995Mn0.005(PO4)6(OH)2. It is found that in the investigated species, the manganese is redistributed between both calcium sites with prevalence in Ca (I). Agreement between the calculated and experimental data proves that crystal field parameters in HAp can be calculated in the classical DFT model using the distributed electron density.

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.

The combined W-band pulsed light-induced multiresonance ESR/ENDOR/TRIPLE technique and DFT calculation have been applied to study the 1H hyperfine coupling and electron spin density distribution on PPV cation and PC61BM anion radicals in (PPVs):PC61BM blends. The sign of calculated electron spin density populations of protons delocalized on polymer and fullerene side chain has been confirmed experimentally by means of TRIPLE in frozen solution at the temperature of 20 K.

A series of 12 asphaltene samples extracted from heavy oils and the oxidized bitumen of different origin has been studied with high-frequency W-band (94 GHz) pulsed electron paramagnetic resonance (EPR) spectroscopy. Transverse (T2e) and longitudinal (T1e) relaxation times of the free radical (FR) and the vanadyl porphyrin (VO2+) were measured for each sample. A significant contribution of the spectral diffusion to T2e has been revealed and ascribed to the dipole–dipole interaction between the FR and VO2+. This indicates that the distance between the FR and VO2+ does not exceed a few nanometers, which means, in turn, that VO2+ can participate in construction of the asphaltene aggregates via the intermolecular interactions.

Light-induced X,W-band Electron Spin Resonance (LESR) study of double-crystalline donor-acceptor block copolymers (BCPs) comprised of poly-3-hexylthiophene as the donor and poly-perylene bisimide acrylate as the acceptor segments is presented. It is suggested that, while the intrinsic light-induced charge separation efficiency in the BCPs registered by LESR could be more efficient than in bulk heterojunction solar cells based on the P3HT/PCBM blends, the photovoltaic performance of the BCPs is limited significantly by the incorrect orientation of crystalline π-stack morphology of (poly-perylene bisimide acrylate) domains.

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.

Nitrogen and nitrogen-vacancy paramagnetic defects in crystals and nanocrystals of diamonds, as well as paramagnetic centers localized on the surface of nanoparticles, were studied by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) methods. The spin optical polarization effect is explained qualitatively by the action of nondiagonal components of the Zeeman interaction, leading to mixing of the wave functions of the ground state. Relaxation-time dependencies are shown for NV− centers. High-frequency (94 GHz) EPR studies of nanodiamonds resolved spectrally three components related to defects in the crystalline core of a nanoparticle, on its surface and in the surface layer. Examples of ENDOR application for control of diamond nanoparticles surface modification by hydrogen and fluoride are demonstrated.

The hardware-software complex based on the homebuild nuclear magnetic/quadrupole resonance spectrometer “Kazan-N ova II”, which allows to determine the authenticity of nitrogen-containing drugs by a nondestructive method is considered in the article. The possibility to distinguish the drugs from different manufacturers using their NQR spectra is shown, which makes it possible to use this device as a scanner of the authenticity of medicinal products, as well as for the formation of a database of reference spectra.

The search for adequate markers of atherosclerotic plaque (AP) instability in the context of assessment of the ischemic stroke risk in patients with atherosclerosis of the carotid arteries as well as for solid physical and chemical factors that are connected with the AP stability is extremely important. We investigate the inner lining of the carotid artery specimens from the male patients with atherosclerosis (27 patients, 42–64 years old) obtained during carotid endarterectomy by using different analytical tools including ultrasound angiography, X-ray analysis, immunological, histochemical analyses, and high-field (3.4 T) pulse electron paramagnetic resonance (EPR) at 94 GHz. No correlation between the stable and unstable APs in the sense of the calcification is revealed. In all of the investigated samples, the EPR spectra of manganese, namely, Mn2+ions, are registered. Spectral and relaxation characteristics of Mn2+ions are close to those obtained for the synthetic (nano) hydroxyapatite species but differ from each other for stable and unstable APs. This demonstrates that AP stability could be specified by the molecular organization of their hydroxyapatite components. The origin of the obtained differences and the possibility of using EPR of Mn2+as an AP stability marker are discussed.

We report a detailed study of electron longitudinal and transverse spin relaxation times for Li donors in monoisotopic 28Si over the temperature range 4–20 K using continuous wave and pulsed electron paramagnetic resonance. Comparison of the obtained spin-lattice relaxation times for the states of the isolated donor center and lithium complex LiO showed that due to the presence of orbital degeneracy, relaxation is faster for single lithium than for the LiO complexes with the nondegenerate ground state. For the isolated lithium center in silicon the relaxation is well described by Blume-Orbach process, with the parameters of the spin-orbit coupling ~ 1·10-6 meV compare to Orbach process for LiO complex with spin-orbit coupling parameter ~ 1.5·10-2 meV.

The pulsed W-band (the microwave frequency of 94 GHz, magnetic field of 3.4 T) electron paramagnetic resonance (EPR) comparative studies of a series of 20 atherosclerotic plaques (AP) obtained during carotid endarterectomy in patients with atherosclerosis is presented. The AP stability was established by ultrasound angiography. In all of the obtained species EPR spectra due to the presence of Mn2+ ions in a crystal matrix of hydroxyapatites (HAp) is observed. The existence of HAp in plaque fragments is confirmed by X-ray diffraction analyses. The spectral parameters of Mn2+ are ascribed to two possible locations in the HAp constituent of the atherosclerotic plaques. The difference in the electronic relaxation times of T 2e for Mn2+ ions in stable and unstable plaques is observed that can indicate the more homogeneous distribution of Mn2+ in stable plaques as compared to unstable species. The results can be potentially used for the understanding the mechanisms of pathological calcifications and AP stability.

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...

Different aspects of applications of electron paramagnetic resonance (EPR) based techniques including high frequency (HF) electron spin echo (ESE), electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) approaches to study diamond nanostructures are examined.

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.

Progress in the synthesis and applications of nanomaterials including nanocatalysts demands a use of precise analytical tools for their surface characterization. Continuous wave (cw) and pulsed electron paramagnetic resonance (EPR) techniques, including electron–nuclear double resonance (ENDOR) have been applied to study paramagnetic complexes formed by adsorption of 9,10-anthraquinone (AQ) as probe molecule by the surface of γ-Al2O3. Up to three different paramagnetic complexes (11-line pattern and two single EPR lines) could be separated in our experiments. Their spectroscopic characteristics are extracted. It is shown that at very high concentration (ca. 10 wt %) of AQ, the obtained EPR signal is close to the single line and can be incorrectly interpreted as due to the EPR signal of AQ itself or due to the lower catalytic activity of the investigated surface. That fact should be taken into account by using AQ as a probe of the surface catalytic activity. Mims and Davies ENDOR experiments confirm the re...

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.

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy VN) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.

Different aspects of applications of electron paramagnetic resonance (EPR) based techniques including high frequency (HF) electron spin echo (ESE), electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) approaches to study diamond nanostructures are examined.

A combined magnetic resonance, photoluminescence, photo-conductivity, and Raman scattering study of ZnO is presented. Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy identify substitutional Al as a binding core of a shallow, effective-mass-like donor in ZnO. Based on the correlation between the EPR and photoluminescence data it is shown that recombination of an exciton bound to Al gives rise to the 3360.7 meV photoluminescence line (I 6 ). A Is → 2p donor transition at 316 cm -1 is detected in photoconductivity and Raman spectra.

Electron paramagnetic resonance (EPR) and electron spin echo (ESE) at X-band and at high-frequency W-band (95 GHz) have been used to study defects in natural diamond nanocrystals, detonation nanodiamond (ND) with a size of ∼4.5 nm and detonation ND after high-temperature, high-pressure sintering with a size of ∼8.5 nm. Atomic nitrogen centers N 0 and nitrogen pairs N 2 + have been detected and identified and their structure has been unambiguously determined by means of the high frequency EPR and ESE in natural diamond nanocrystals. In detonation ND and detonation ND after sintering atomic nitrogen centers N 0 have been discovered in nanodiamond core. In addition EPR signal of multi-vacancy centers with spin 3/2 seems to be observed in diamond core of detonation ND.

Silicon oxide aerogel samples irradiated with x rays at room temperature have been analyzed using the electron paramagnetic resonance method. It has been found that three types of paramagnetic centers appear: paramagnetic centers with a g factor of 2.0035, centers associated with the presence of protons in SiO2 globules, and centers in the adsorbed film on the aerogel surface. The fast (Tfast = 30 h) and slow (Tslow = 70 d) processes have been revealed in the recombination of these centers.

In the present work the NMR relaxation of the gaseous 3He inside carbonizate pores was investigated at temperature 1.5 K. The carbonizates synthesized from fructose and wood of the tropical tree astronium were used. The dependences of the 3He relaxation rates T1 and T2 on the gas pressure and the amount of the 3He atoms adsorbed on the surface of pore walls were measured. The analysis of obtained results reveals the existence of the 3He phases inside carbonizate—adsorbed solid layers, liquid and gas.

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

Structural features and dynamical behaviour of the copper(ii) bis-complexes with glycine, d-alanine, d-valine, l-serine, l-aspartic acid, l-glutamic acid, l-lysine, l-proline, and sarcosine were studied by combined EPR and NMR relaxation methods. The cis and trans isomers were unambiguously assigned and characterized by EPR data. It was found that addition of a salt background has an influence on the cis-trans isomer equilibrium in favour of the formation of the cis isomer. By comparison of NMRD, DFT computations, and structural data it was shown that only one water molecule is coordinated in the axial position of these complexes. The increased exchange rates of this molecule found for Cu(l-Asp)2(2-), Cu(l-Glu)2(2-), Cu(l-LysH)2(2+), and Cu(l-Pro)2 were attributed to its pushing out by side chain groups of the ligands. By simulation of NMRD profiles an increase of lifetimes of the copper(ii) 2nd coordination sphere water molecules was revealed in the presence of additional carboxylic, alcoholic, or ammonium groups of the ligands, as well as the pyrrolidine ring of proline. The very short lifetimes of the 2nd coordination sphere water molecules (4-13 ps at 298 K) were explained in terms of the Frank-Wen structural model by the existence of cavities which draw in quickly enough water molecules from the 2nd coordination sphere.

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

Rotational dynamics of the copper(II) bis-complexes with glycine and L-aspartic acid has been studied by EPR and NMR relaxation methods in aqueous solutions at several temperatures. Dynamical parameters obtained by EPR were compared with nuclear magnetic relaxation dispersion (NMRD) results and were found to be in a good agreement. From EPR data dominating trans isomer for Cu(Gly)2 and cis isomer for Cu(L-Asp)2 2- was found. On the basis of distance of closest approach of protons to central ion inferred from NMRD and crystal structure data the average slope angles of axial water molecule to equatorial plane were calculated and axial coordination of only one water molecule in the Cu(L-Asp)2 2- complex was established.

The coherence times of dopant pentavalent chromium ions in CaWO₄ single crystal (0.0006at.% Cr(5+)) were investigated both theoretically and experimentally. Temperature dependences of spin-lattice relaxation time T₁ and phase memory time T(M) were measured in the temperature range 6-30 K at high (94 GHz, W band) and low (3.5 GHz, S band) frequencies of electron spin resonance. It follows from T(M) calculations that phase relaxation of Cr(5+) ion arises mainly from magnetic dipole interactions between the chromium ions. Anomalously fast damping of Rabi oscillations is detected in both S- and W-band experiments. It is shown that this phenomenon is caused by microwave field inhomogeneity inside the resonator. Relations between the damping time of Rabi oscillations, Rabi frequency and the crystal sample size are obtained. Lumped-element resonators and smaller sample dimensions are suggested to lower spin dephasing during transient nutations.

EPR, NMR relaxation methods, and DFT calculations were jointly used to investigate the structural and dynamical characteristics of solvation shells of copper(II) complexes with iminodiacetic acid, glycylglycine, and glycyglycylglycine in comparison with the copper(II) bis-glycinate studied previously. A strong trans influence of deprotonated peptide nitrogen was revealed in EPR spectra parameters of copper(II) complexes with oligopeptides. With models of the experimental NMRD data and literature X-ray structural information, it was suggested that only one water molecule coordinates in axial position of copper(II) complexes with glycine and di- and triglycine (Cu(Gly)2, Cu(GGH(-1)), and Cu(GGGH(-2))(-)), and the copper ion in these complexes is pentacoordinated, while in the iminodiacetate complex, Cu(IDA), both apical positions can be occupied by solute molecules. The obtained structural results were confirmed by DFT calculations of structures of studied compounds using different functionals and basis sets. It was shown that the donor ability of equatorial ligands and trans influence have an effect on the characteristics of the axial water bond. With increasing donor strength of equatorial ligands, pentacoordination of copper(II) complexes in water solutions becomes more preferable.