HYSCORE Spectroscopy to Resolve Electron–Nuclear Structure of Vanadyl Porphyrins in Asphaltenes from the Athabasca Oil Sands In Situ Conditions

The purpose of this work is to analyze the electron–nuclear interactions of the vanadyl-porphyrin (VP) complexes in oil asphaltenes. Asphaltenes from the Athabasca oil sands were studied by HYperfine Sublevel CORrelation Spectroscopy (HYSCORE) electron paramagnetic resonance (EPR). It makes it possible to resolve and interpret complex hyperfine spectra of intrinsic VP with strong and weak hyperfine interactions between the electron magnetic moment and various nuclear spins (1H, 14N, 51V). The main parameters of spin-Hamiltonian for the VP spin system are determined. The axially symmetric structure of the VP complexes is revealed, and the local nuclear environment of the paramagnetic center is investigated. The results can be used for the study of asphaltene electron–nuclear structure and asphaltene aggregates with the aim of elucidating asphaltenes’ transformation(s) under the influence of external treatment

Exploring the Properties of the V_B^- Defect in hBN: Optical Spin Polarization, Rabi Oscillations, and Coherent Nuclei Modulation

Optically active point defects in semiconductors have received great attention in the field of solid-state quantum technologies. Hexagonal boron nitride, with an ultra-wide band gap E_g = 6 eV, containing a negatively charged boron vacancy (V_B^-) with unique spin, optical, and coherent properties presents a new two-dimensional platform for the implementation of quantum technologies. This work establishes the value of V_B^ - spin polarization under optical pumping with {\lambda}ext = 532 nm laser using high-frequency ({\nu}mw = 94 GHz) electron paramagnetic resonance (EPR) spectroscopy. In optimal conditions polarization was found to be P = 38.4 %. Our study reveals that Rabi oscillations induced on polarized spin states persist for up to 30-40 microseconds, which is nearly two orders of magnitude longer than what was previously reported. Analysis of the coherent electron-nuclear interaction through the observed electron spin echo envelope modulation (ESEEM) made it possible to detect signals from remote nitrogen and boron nuclei, and to establish a corresponding quadrupole coupling constant Cq = 180 kHz related to nuclear quadrupole moment of 14N. These results have fundamental importance for understanding spin properties of boron vacancy

Study of Tricalcium Phosphate Ceramics Doped with Gadolinium Ions with Various EPR Techniques

Tricalcium phosphate (TCP)-based materials, such as β-Ca3(PO4)2 doped with rare earth ions (RE), have shown applications as biomaterials, lighting emitting materials, scintillating materials, in vivo imaging probes, and thermoluminescent dosimeters. Their properties are found to be dependent on the distribution of RE3+ on Ca2+ sites that can be controlled by pulsed electron paramagnetic resonance (EPR) and electron spin echo envelop modulation (ESEEM) experiments. The main spectroscopic parameters (spin Hamiltonian values) of Gd3+ and nitrogen impurity centers are quantitatively determined (g-factor, the fine structure parameters D and E, the hyperfine constants A) as well as dynamic characteristics: spin–lattice T1 and spin–spin T2 relaxation times. Based on the analysis of the EPR datasets, the interatomic distance between Gd3+ and 31P was estimated in the dipole–dipole approximation. Two structurally nonequivalent Gd3+ positions in the β-TCP structure have been identified. The obtained valuable results demonstrate applicability of modern EPR techniques to characterize Gd-TCP systems despite the powder structure of the material and high electron spin S = 7/2 of Gd3+ ions

Influence of Synthesis Conditions on Gadolinium-Substituted Tricalcium Phosphate Ceramics and Its Physicochemical, Biological, and Antibacterial Properties

Gadolinium-containing calcium phosphates are promising contrast agents for various bioimaging modalities. Gadolinium-substituted tricalcium phosphate (TCP) powders with 0.51 wt% of gadolinium (0.01Gd-TCP) and 5.06 wt% of (0.1Gd-TCP) were synthesized by two methods: precipitation from aqueous solutions of salts (1) (Gd-TCP-pc) and mechano-chemical activation (2) (Gd-TCP-ma). The phase composition of the product depends on the synthesis method. The product of synthesis (1) was composed of β-TCP (main phase, 96%), apatite/chlorapatite (2%), and calcium pyrophosphate (2%), after heat treatment at 900 °C. The product of synthesis (2) was represented by β-TCP (main phase, 73%), apatite/chlorapatite (20%), and calcium pyrophosphate (7%), after heat treatment at 900 °C. The substitution of Ca2+ ions by Gd3+ in both β-TCP (main phase) and apatite (admixture) phases was proved by the electron paramagnetic resonance technique. The thermal stability and specific surface area of the Gd-TCP powders synthesized by two methods were significantly different. The method of synthesis also influenced the size and morphology of the prepared Gd-TCP powders. In the case of synthesis route (1), powders with particle sizes of tens of nanometers were obtained, while in the case of synthesis (2), the particle size was hundreds of nanometers, as revealed by transmission electron microscopy. The Gd-TCP ceramics microstructure investigated by scanning electron microscopy was different depending on the synthesis route. In the case of (1), ceramics with grains of 1–50 μm, pore sizes of 1–10 µm, and a bending strength of about 30 MPa were obtained; in the case of (2), the ceramics grain size was 0.4–1.4 μm, the pore size was 2 µm, and a bending strength of about 39 MPa was prepared. The antimicrobial activity of powders was tested for four bacteria (S. aureus, E. coli, S. typhimurium, and E. faecalis) and one fungus (C. albicans), and there was roughly 30% of inhibition of the micro-organism’s growth. The metabolic activity of the NCTC L929 cell and viability of the human dental pulp stem cell study demonstrated the absence of toxic effects for all the prepared ceramic materials doped with Gd ions, with no difference for the synthesis route