


Vol 48, No 4 (2017)
- Year: 2017
- Articles: 6
- URL: https://journal-vniispk.ru/0937-9347/issue/view/15439
Original Paper
Influence of Pressure on the Intramolecular Spin Exchange in a Short Imidazolium-Nitroxide Biradical
Abstract
A short-chain imidazoline-type nitroxide biradical R5NO–CH=N–N=C(CH3)–R5N, B2, with nitroxide rings R5N and R5NO as 1-oxyl-2,2,5,5-tetramethyl-3-imidazoline and 1-oxyl-2,2,5,5-tetramethyl-3-N-oxide imidazoline, respectively, has been studied using X-band electron paramagnetic resonance (EPR) spectroscopy in CH3CN solutions at variable temperature T and pressure P. Changes of the solution viscosity on the intramolecular electron spin exchange in B2 is characterized by calculating the value of the exchange integral |J/a|, where a denotes the 14N hyperfine splitting (hfs) constant. It is revealed that the intramolecular dynamics in B2 do not follow the Debye–Stokes–Einstein law, while the Arrhenius dependence is fulfilled. Probable reasons of such behavior are discussed.



Accelerated 3D Coronary Vessel Wall MR Imaging Based on Compressed Sensing with a Block-Weighted Total Variation Regularization
Abstract
Coronary vessel wall magnetic resonance (MR) imaging is important for heart disease diagnosis but often suffers long scan time. Compressed sensing (CS) has been previously used to accelerate MR imaging by reconstructing an MR image from undersampled k-space data using a regularization framework. However, the widely used regularizations in the current CS methods often lead to smoothing effects and thus are unable to reconstruct the coronary vessel walls with sufficient resolution. To address this issue, a novel block-weighted total variation regularization is presented to accelerate the coronary vessel wall MR imaging. The proposed regularization divides the image into two parts: a region-of-interest (ROI) which contains the coronary vessel wall, and the other region with less concerned features. Different penalty weights are given to the two regions. As a result, the small details within ROI do not suffer from over-smoothing while the noise outside the ROI can be significantly suppressed. Results with both numerical simulations and in vivo experiments demonstrated that the proposed method can reconstruct the coronary vessel wall from undersampled k-space data with higher qualities than the conventional CS with the total variation or the edge-preserved total variation.



β-Phosphorus Hyperfine Coupling Constant in Nitroxides: Conformational Effects in 6-Membered Ring Nitroxides
Abstract
Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant aP in β-phosphorylated 6-membered ring nitroxides (∆aP = 24 G in Org. Biomol. Chem. 2015). Thus, it led us to investigate the effect of solvent for several 6-membered ring nitroxides. Although smaller than mentioned above, a change of 5–7 G in aP with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, aN increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas aP exhibits the reverse trends. The change of aP with the solvent depends a lot on a subtle interplay between the destabilizing steric hindrance due to the bulkiness of the substituents and the stabilizing hyperconjugation interactions SOMO → σ*C–P between the anti-bonding orbitals of the C–P bond and the SOMO.



Magnetic Resonance Study of Fe-Implanted TiO2 Rutile
Abstract
Single-crystal (100) and (001) TiO2 rutile substrates have been implanted with 40 keV Fe+ at room temperature with high doses in the range of (0.5–1.5) × 1017 ions/cm2. A ferromagnetic resonance (FMR) signal has been observed for all samples with the intensity and the out-of-plane anisotropy increasing with the implantation dose. The FMR signal has been related to the formation of a percolated metal layer consisting of close-packed iron nanoparticles in the implanted region of TiO2 substrate. Electron spin resonance (ESR) signal of paramagnetic Fe3+ ions substituting Ti4+ positions in the TiO2 rutile structure has been also observed. The dependences of FMR resonance fields on the DC magnetic field orientation reveal a strong in-plane anisotropy for both (100) and (001) substrate planes. An origin of the in-plane anisotropy of FMR signal is attributed to the textured growth of the iron nanoparticles. As result of the nanoparticle growth aligned with respect to the structure of the rutile host, the in-plane magnetic anisotropy of the samples reflects the symmetry of the crystal structure of the TiO2 substrates. Crystallographic directions of the preferential growth of iron nanoparticles have been determined by computer modeling of anisotropic ESR signal of substitutional Fe3+ ions.



T1–T2 Correlation and Biopolymer Diffusion Within Human Osteoarthritic Cartilage Measured with Nuclear Magnetic Resonance
Abstract
Cartilage is a load-bearing tissue that provides smooth articulation during motion of human joints like the knee and hip. Cartilage deterioration in the form of osteoarthritis (OA) causes painful joint motion in more than 100 million patients worldwide, and thus there is great interest in improving our understanding of cartilage to further clinical treatment. Previous studies have examined many aspects of cartilage mechanics, including the flow of interstitial water and repulsion of neighboring glycosaminoglycan chains. However, the contributions of specific molecules to overall tissue properties remain unclear. In this study, we use nuclear magnetic resonance (NMR) diffusometry and relaxometry to examine the molecular dynamics of water and cartilage polymers in OA human articular cartilage. To our knowledge, this is the first identification of two macromolecular populations corresponding to collagen and proteoglycan in human cartilage through their diffusive properties. Further, we performed NMR T1–T2 correlation studies on human cartilage and observed two populations of water distinguished by differing NMR relaxation corresponding to a solid-like component and a liquid-like component. These results provide fundamental insight on the water behavior and polymeric interactions that drive the functional mechanics of cartilage. This study provides a basis to both expand our understanding of basic cartilage mechanics and provide molecular dynamics data for design of novel biomaterials to improve joint health.



Influence of Defects on Photoconductivity and Photocatalytic Activity of Nitrogen-Doped Titania
Abstract
Samples of nitrogen-doped titanium dioxide (anatase, 0.2 ≤ N ≤ 1.0 wt%) prepared by the sol–gel method were investigated using X-band electron paramagnetic resonance spectroscopy, photoconductivity, and photocatalysis measurements. N· and NO· paramagnetic defects in N-TiO2 have been observed; their concentrations and spin-Hamiltonian parameters were calculated. An increase both in the rate of the generation of free charge carriers and in the rate of photocatalysis was found in N-TiO2 in contrast with non-doped titania under visible light. The correlation of the density of the observed radicals with the photoconductivity and photocatalysis data is discussed.


