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Том 50, № 4 (2019)

Original Paper

Ultra-Narrow Low-Field Nuclear Spin Resonance in NV Centers in a Bulk Diamond Crystal

Dmitriev A., Vershovskii A.

Аннотация

Negatively charged nitrogen vacancy (NV) color centers in diamond crystals have been intensively studied in the last few decades with the use of the optically detected magnetic resonance method which usually implies resonance excitation using a DC or pulsed drive field in the gigahertz range (MW field). Various techniques for multi-frequency MW excitation of magnetic resonance in the nuclear structure of 14N atoms in NV centers were developed. Most of them use MW excitation in combination with RF modulation or direct RF excitation of nuclear transition. Here, we report on the possibility to detect ultra-narrow resonances in the nuclear structure of 14N using the ODMR methods with single-frequency DC RF excitation of the nuclear transition at 4.95 MHz. The resonances detected in a bulk sample in weak (0–10 mT) magnetic fields show approximately 7 kHz width HWHM, corresponding to T2* = 23 μs, and they seem to be insensitive to the magnetic field direction. These resonances may be of interest for solid-state quantum information processing, as well as for quantum magnetometry, especially in biological and medical applications where a strong MW drive field may be undesirable. We demonstrate that optical pumping can be used to create and detect not only the electron orientation, but also the nuclear one, even in the state with a zero electron spin projection. This allows sensitive non-pulsed detection methods like coherent population trapping to be applied to nuclear spins.

Applied Magnetic Resonance. 2019;50(4):599-604
pages 599-604 views

NMR Spectra of 1-Vinylimidazole, Transformed by Paramagnetic Complexes

Voronov V., Ushakov I., Funtikova E.

Аннотация

The NMR spectra of 1-vinylimidazole, transformed by the additives of paramagnetic complexes of manganese, cobalt, nickel and copper chlorides with this azole, have been studied. It is shown that the coordination atom in a solution has octahedral surrounding, four ligand molecules being located in the equatorial position. The nature of hyperfine coupling in the above complexes is evaluated by comparison of the experimental constants of hyperfine coupling with theoretically calculated spin densities of unpaired electrons on s-orbitals in the vinylpyrrole radical, which is isostructural to the molecule of 1-vinylimidazole. It is found that in the complexes of cobalt, nickel and copper, the molecules of 1-vinylimidazole are coordinated to the central ion by the pyridine N-3 atom. Therefore, paramagnetic shifts observed for the specified complexes are mainly caused by unpaired spin density delocalized in \( \sigma \)- system of the ligand molecule. Notably, in the paramagnetic complex of manganese, hyperfine coupling is transferred both through \( \sigma \)- and \( \pi \)- systems of the 1-vinylimidazole molecule. Localization of the unpaired spin density is due to the fact that molecules of this azole can also be coordinated by the pyrrole N-1 atom at a certain range of temperatures. In its turn, the specified possibility is explained by non-planar structure of a heterocycle in 1-vinylimidazole.

Applied Magnetic Resonance. 2019;50(4):569-577
pages 569-577 views

Influence of Morphology of LaF3 Nano-crystals on Fluorine Dynamics Studied by NMR Diffusometry

Gulina L., Schikora M., Privalov A., Weigler M., Tolstoy V., Murin I., Vogel M.

Аннотация

Ionic dynamics in nano-structured 2D superionic conductors LaF3 obtained by a synthesis at the gas–solution interface has been analyzed using 19F NMR Static Field Gradient (SFG) diffusometry in a temperature range up to 800 K. The fluorine diffusion in 2D materials is significantly higher as compared to that in bulk LaF3 and is strongly dependent on the nano-crystalline sheet thickness. Its decrease from 18 nm to 6 nm leads to an increase of mobility by almost two orders of magnitude, resulting in an overall mobility enhancement of more than three orders of magnitude compared to mono-crystalline LaF3. Moreover, the activation energy is reduced from 1.2 eV for mono-crystals to 0.23 eV for 6 nm thin nano-crystalline powder samples.

Applied Magnetic Resonance. 2019;50(4):579-588
pages 579-588 views

Multiplet-Matched Filtering of 103Rh Signal Using Information Contained in 31P Spectrum of AA′XX′ 31P–103Rh Spin System

Podkorytov I., Cherkasova T., Kayfadzhyan E., Varshavsky Y.

Аннотация

Splitting parameters measured in the sensitive 31P part of an AA′XX′ 31P–103Rh spectrum make it possible to perform a multiplet-matched digital filtering of the weak 103Rh free induction decay signal. Compared to the conventional matched exponential weighting, this multiplet-matched filtering has provided a gain of 1.8 ± 0.4 in the signal-to-noise ratio of the experimental rhodium spectrum. The maximum gain predicted theoretically is equal to 2.

Applied Magnetic Resonance. 2019;50(4):563-568
pages 563-568 views

The Metabolic Profile of Stable Ischemic Heart Disease by Serum 1H NMR

Titma T., Shin M., Ludwig C., Günther U., Pikta M., Zemtsovskaja G., Viigimaa M., Tanner R., Samoson A.

Аннотация

Ischemic heart disease (IHD) is the most common cause of death in the world. Metabolic profiling is an innovative and reliable new method to detect more sensitive biomarkers identifying altered health conditions specifically among the variety of patients with different risk factors. We evaluated the metabolic profile of filtered serum of stable IHD patients (ICD10 codes I20 and I25.2, ischemic heart disease without or with previous myocardial infarction respectively) using proton nuclear magnetic resonance spectroscopy (NMR). The filtered venous serum from age- and gender-matched stable IHD patients ICD10 coded I20 (n = 13), I25.2 (n = 6) and control individuals (n = 19) were analyzed using one-dimensional proton nuclear magnetic resonance (1H NMR) spectroscopy. These spectra were used for metabolic profiling and concentration calibration (Chenomx Inc.) followed by statistical analysis using one-way ANOVA and principal component analysis (PCA). Chemometrics analysis showed a significant distinction between the patients and control individuals. The stable IHD patients were exemplified by the increased concentration of acetylacetate, choline, betaine, formate, pyruvate and by the decreased concentration of alanine, creatine, glycine, histidine, lactate, proline, urea and other biomolecules. The major implications found in the serum of IHD patients are related to energy metabolism and potentially altered microbiome. PCA of 1H NMR detected serum metabolites exhibit a significant difference of stable IHD patients and control individuals. These data demonstrate that metabolomics approach may be useful for the early detection of stable IHD, for detection of synergistic pathways involved in the development of altered health conditions, and molecular understanding of particular health condition. The differences of the detected metabolic profile of ischemic patients with or without previous myocardial infarction appear to be minor. This relatively inexpensive, non-invasive and reproducible approach may be useful for the molecular understanding and early prevention of IHD, improvement of surveillance and therapy. The study emerges the need for future investigations using larger cohort and possible longitudinal sight.

Applied Magnetic Resonance. 2019;50(4):527-539
pages 527-539 views

Features of Development and Applications of Compact EPR Analyzers

Bogachev Y., Knyazev M., Nikitina A.

Аннотация

In this research, new compact electron paramagnetic resonance (EPR) equipment design features are described. This equipment is developed both for research and for practical applications. The described instrumentation can be characterized by high performance, low cost, reliability and simplicity, open architecture, small size, a wide range of functional modules and units. Various functional schemes of homodyne and autodyne type EPR analyzer microwave units have been analyzed. We developed and experimentally investigated two cavities optimal functional scheme for autodyne type EPR analyzer. Among discussed original instrumentation developments, there are compact magnet systems based on electromagnets and permanent magnets with high uniformity of magnetic field. Specifications of a new compact EPR equipment and a list of applications are presented. One of the most important industrial applications of autodyne type EPR analyzer is considered in detail.

Applied Magnetic Resonance. 2019;50(4):605-617
pages 605-617 views

63,65Cu NQR Spectra and Spin–Lattice Relaxation in Thermoelectric CuAlO2

Ogloblichev V., Matukhin V., Arapova I., Schmidt C., Khusnutdinov R.

Аннотация

The 63,65Cu nuclear quadrupole resonance spectra and spin–lattice relaxation rate (1/T1) have been measured in the semiconductor compound CuAlO2. The value of the nuclei quadrupole interaction constant QCC = 56.24(6) MHz (T = 298 K) has been obtained. The broad maximum has been found in the temperature dependence of 1/T1 in the low-temperature region (below 276 K). This maximum can be associated with the presence of energy levels in the forbidden band. The activation energy has been estimated in CuAlO2 [EA = 45(2) meV], assuming the activation character of the mobility of holes.

Applied Magnetic Resonance. 2019;50(4):619-625
pages 619-625 views

MR Relaxation Studies of Hemoglobin Aggregation Process in Sickle Cell Disease: Application for Diagnostics and Therapeutics

Lores Guevara M., Naranjo J., Mirabal C.

Аннотация

Sickle cell disease (SCD) is a blood disorder, which has been studied using different research methods including linear birefringence, electronic microscopy, viscosity determination, Electron Paramagnetic Resonance and Nuclear Magnetic Resonance. We summarized in this paper the contribution of proton magnetic relaxation, to the study of the behavior of the protons from protein and water as a consequence of hemoglobin S (HbS) polymerization. Spin–Lattice (T1) and Spin–Spin (T2) relaxation times have been sensitive to the agglutination of the HbS, having a decreasing behavior because of this process. T2 has shown a stronger sensitivity, decreasing immediately during deoxygenation in red blood cells (RBC) of patients homozygous for HbS and in pure HbS solution with intracellular concentration. In the HbS solutions with hemoglobin concentration below 208 mg/mL and heterozygous RBC, during induced deoxygenation, the Spin–Spin relaxation time was characterized by a delay time before polymerization, a decrease during aggregation and a further stabilization; the same occurs in the HbS solutions under spontaneous deoxygenation. The fast exchange of water molecules between the bound and free state, as well as the dipolar interaction between the protons inside the water molecules, were utilized to explain the relaxation times behavior; an increase in the correlation time of the strongly bound water was found. Contradictory results were observed between the experimental behavior obtained for T1 and those results predicted theoretically. T2 behavior showed utility to evaluate the clinical state of the SCD patients and the effect of vanillin and Hydroxyurea on the HbS polymerization.

Applied Magnetic Resonance. 2019;50(4):541-551
pages 541-551 views

Spin–Lattice Relaxation and Diffusion Processes in Aqueous Solutions of Gadolinium-Based Upconverting Nanoparticles at Different Magnetic Fields

Kristinaityte K., Zalewski T., Kempka M., Sakirzanovas S., Baziulyte-Paulaviciene D., Jurga S., Rotomskis R., Valeviciene N.

Аннотация

We investigated the influence of gadolinium (Gd)-based upconverting nanoparticles (UCNPs) on water spin–lattice relaxation (T1) and diffusion at different magnetic field strengths (0.4 T and 9.4 T). Our findings show that smaller NPs (12 nm compared to 19 nm) were more favourable for proton relaxivity. We also demonstrate that using simplified Solomon–Bloembergen–Morgan (SBM) model we can associate two measured diffusion coefficients with processes occurring near the surface of UCNPs and in bulk water. Using the relationship between relaxation and diffusion, we can estimate not only the total impact of NPs on relaxation of water molecules, but also the impact on relaxation of local water molecules, directly connected to paramagnetic Gd3+ ions in NPs. Different magnetic field strengths did not alter the spin–lattice relaxivity of NPs. This suggests that Gd-based UCNPs could be developed into high-performance multimodal magnetic resonance imaging contrast agents working over a broad range of imaging field strengths used in clinical routine.

Applied Magnetic Resonance. 2019;50(4):553-561
pages 553-561 views

1H and 93Nb Solid-State NMR and IR Study of Acidity of Nanodisperse Nb2O5·nH2O

Yakovlev I., Papulovskiy E., Paukshtis E., Bondareva V., Toktarev A., Zaikovskii V., Lapina O.

Аннотация

Niobium oxide hydrate is a promising material for various heterogeneous catalytic processes due to its strong acidity and stability in aqueous medium. While different synthesis conditions may lead to various particle morphologies, the effect of morphology of Nb2O5·nH2O particles on their acidic properties is not fully understood yet. In this paper, we have successfully synthesized and characterized nanodisperse niobium oxide hydrate. Using infrared (IR) spectroscopy, we demonstrated that the sample exhibits strong Brønsted acidity close in strength to sulfuric acid. Furthermore, solid-state nuclear magnetic resonance (NMR) spectroscopy in combination with ab initio calculations gave additional insight into the nature of strong acidic sites and proved to be a useful tool for identification of acidic sites in Nb2O5·nH2O systems. Thus, we have shown that it is not necessary to follow difficult high-temperature solid-state processes or processes with ammonia, which often contaminates the material, to synthesize highly acidic nanodisperse Nb2O5·nH2O.

Applied Magnetic Resonance. 2019;50(4):589-597
pages 589-597 views

Editorial

Multeity of Magnetic Resonance and Its Applications

Chizhik V., Tagirov M.
Applied Magnetic Resonance. 2019;50(4):523-526
pages 523-526 views