Vol 49, No 3 (2018)

The results of the electron paramagnetic resonance (EPR) and transient EPR (TREPR) of copper complexes of coproporphyrin I in different solvents before and after the laser pulse photo-excitation have been presented. Continuous-wave EPR spectra of the CuCPP-1 complex in o-terphenyl indicate the presence of only monomer fragments, while in the solution of the chloroform and isopropanol mixture, the complexes dimerize and the amount of dimers is five times larger than that of monomer complexes. Parameters describing EPR spectra of monomer and dimer CuCPP-1 complexes have been determined. It was established that the fine structure tensor of the dimer complex is rotated with respect to the g-tensor, which coincides with the tensor of monomer complexes. TREPR spectra of CuCPP-1 complexes in o-terphenyl and in the chloroform and isopropanol mixture after the laser photo-excitation are mainly due to spin-polarized ground states of monomer and dimer complexes, respectively. The TREPR spectra of the monomer CuCPP-1 show the emissive spin-polarized signal of the ground state. For dimer fragments, the net polarization is observed in the form of absorption and there is a small contribution from the multiplet polarization, which decays fast in time. The time dependence of TREPR of CuCPP-1 complexes in the chloroform and isopropanol mixture is described with allowance for these contributions from the ground state of the dimer and the contribution from the ground state of the monomer, which is manifested at larger times. Differences in the spin polarization of ground states and their possible origin are discussed.

Pulse dipolar electron paramagnetic resonance spectroscopy provides means of distance measurements in the range of ~ 1.5–10 nm between two spin labels tethered to a biological system. However, the extraction of distance distribution between spin labels is an ill-posed mathematical problem. The most common approach for obtaining distance distribution employs Tikhonov regularization method, where a regularization parameter characterizing the smoothness of distribution is introduced. However, in case of multi-modal distance distributions with peaks of different widths, the use of a single regularization parameter might lead to certain distortions of actual distribution shapes. Recently, a multi-Gaussian Monte Carlo approach was proposed for eliminating this drawback and verified for model biradicals [1]. In the present work, we for the first time test this approach on complicated biological systems exhibiting multi-modal distance distributions. We apply multi-Gaussian analysis to pulsed electron–electron double resonance data of supramolecular ribosomal complexes, where the 11-mer oligoribonucleotide (MR) bearing two nitroxide labels at its termini is used as a reporter. Calculated distance distributions reveal the same conformations of MR as those obtained by Tikhonov regularization, but feature the peaks having different widths, which leads to a better resolution in several cases. The advantages, complications, and further perspectives of application of Monte-Carlo-based multi-Gaussian approach to real biological systems are discussed.

The spin-Hamiltonian parameters (g factors g_//, g_⊥ and zero-field splitting D) of the trigonal Cr³⁺ centers in Cr³⁺-doped ABO₃ (A = Sc, In, Lu) borate crystals are computed from both the complete diagonalization (of energy matrix) method and also the perturbation method based on the two-spin–orbit-parameter model, where the contributions to spin-Hamiltonian parameters due to both the spin–orbit parameter of central dⁿ ion and that of ligands via covalence effect are considered. The calculated results are compatible with those available in experiments. The defect structures of the trigonal (CrO₆)⁹⁻ octahedral centers are also evaluated from the calculations. It is found that the trigonal (MO₆)⁹⁻ octahedra change from the elongation in the host crystals to the compression in the impurity centers because of the large size and nature mismatch substitution in these Cr³⁺-doped ABO₃ crystals. The results are discussed.

Nuclear magnetic resonance (NMR) plays a significant role in porous media analysis and petroleum exploration, but its response is significantly influenced by the internal magnetic field gradient in fluid saturated porous medium, which obviously limits the accuracy of rock core analysis and logging interpretation. The influential factors of the internal magnetic field gradient in formation and its influences on NMR response are studied in this paper, based on NMR mechanism through one- and two-dimensional core NMR experiments. The results indicate that the internal magnetic field gradient is positively correlated with the static magnetic field strength and the magnetic susceptibility difference between pore fluid and solid grains, while it presents negative correlation with pore radius. The internal magnetic field gradient produces an additional diffusion relaxation in hydrogen relaxation system and accelerates the attenuation of magnetization vector. As a result, T₂ spectrum shifts to the left and NMR porosity and diffusion coefficient of the fluid could be inaccurate. This research sets a foundation for the NMR porosity correction and fluid distribution on T₂-G maps based on the internal magnetic field gradient correction.