Study of Organic Self-Assembled Nanosystems by Means of High-Frequency ESR/ENDOR: The Case of Oil Asphaltenes

© 2018, Pleiades Publishing, Ltd. An approach to investigate self-assembly of oil disperse systems based on high-field electron nuclear double resonance has been suggested. As exemplified by asphaltenes, the oil components most prone to self-assembly, the formation of planar rather than multilayer structures has been directly evidenced experimentally. The suggested method can be applied to elucidate the self-assembly mechanism in wide range of organic objects

Toward the Asphaltene Structure by Electron Paramagnetic Resonance Relaxation Studies at High Fields (3.4 T)

© 2016 American Chemical Society.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

Multifrequency (9 and 95 GHz) EPR study of stable radicals in asphaltenes fractions of oils and bitumen

© Published under licence by IOP Publishing Ltd. Structural characterization of asphaltenes in complex systems such as native hydrocarbons is in the focus of scientific and industrial interests since many years. Various analytical tools and approaches are used for that. We present the results of our study of asphaltene fractions A1 and A2 with the predominantly "island" type and "archipelago" type asphaltene molecules by conventional and pulsed electron paramagnetic resonance (EPR) at X-band (9 GHz) and W-band (95 GHz) with aim to expand the abilities of EPR technique for asphaltene characterization. Shift to the higher frequencies allows to separate spectrally the contributions from paramagnetic complexes of different origin, define the EPR parameters more accurately comparing to the conventional X-band EPR. Application of pulsed techniques allows (at least partially) to separate the radicals in time domain. Features of the obtained spectra are described. Electronic relaxation times are found to be different for stable "free" radical for A1 and A2 fractions. We suggest that the obtained results can be used for investigation of various petroleum systems

Study of Organic Self-Assembled Nanosystems by Means of High-Frequency ESR/ENDOR: The Case of Oil Asphaltenes

© 2018, Pleiades Publishing, Ltd. An approach to investigate self-assembly of oil disperse systems based on high-field electron nuclear double resonance has been suggested. As exemplified by asphaltenes, the oil components most prone to self-assembly, the formation of planar rather than multilayer structures has been directly evidenced experimentally. The suggested method can be applied to elucidate the self-assembly mechanism in wide range of organic objects

High-Field (3.4 T) ENDOR Investigation of Asphaltenes in Native Oil and Vanadyl Complexes by Asphaltene Adsorption on Alumina Surface

© 2019 Marat Gafurov et al. Vanadyl porphyrin complexes in asphaltenes from heavy (Karmalinskoye) oil and in asphaltene films obtained as a result of adsorption on the surface of aluminum oxide were studied by electron paramagnetic resonance (EPR) and double electron-nuclear resonance (ENDOR) in the W-band frequency range (microwave frequency of 95 GHz, magnetic field of 3.4 T). Mims ENDOR spectra from 1H and 27Al nuclei are observed. ENDOR spectra are different for native oil and asphaltenes from one side and the adsorbed samples from the other side while no significant changes in X- (microwave frequency of 9 GHz) or W-band EPR spectra are found. The results allow supposing that vanadyl porphyrin complexes (at least in the studied asphaltene films) participate in the formation of asphaltene aggregates through the functional groups rather than π-π interactions. The data show the feasibility of the commercial pulsed ENDOR approaches for the investigation of crude oils and their constituents under external influence

Toward the Asphaltene Structure by Electron Paramagnetic Resonance Relaxation Studies at High Fields (3.4 T)

© 2016 American Chemical Society.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

Multifrequency (9 and 95 GHz) EPR study of stable radicals in asphaltenes fractions of oils and bitumen

© Published under licence by IOP Publishing Ltd. Structural characterization of asphaltenes in complex systems such as native hydrocarbons is in the focus of scientific and industrial interests since many years. Various analytical tools and approaches are used for that. We present the results of our study of asphaltene fractions A1 and A2 with the predominantly "island" type and "archipelago" type asphaltene molecules by conventional and pulsed electron paramagnetic resonance (EPR) at X-band (9 GHz) and W-band (95 GHz) with aim to expand the abilities of EPR technique for asphaltene characterization. Shift to the higher frequencies allows to separate spectrally the contributions from paramagnetic complexes of different origin, define the EPR parameters more accurately comparing to the conventional X-band EPR. Application of pulsed techniques allows (at least partially) to separate the radicals in time domain. Features of the obtained spectra are described. Electronic relaxation times are found to be different for stable "free" radical for A1 and A2 fractions. We suggest that the obtained results can be used for investigation of various petroleum systems

High-Field (3.4 T) ENDOR Investigation of Asphaltenes in Native Oil and Vanadyl Complexes by Asphaltene Adsorption on Alumina Surface

© 2019 Marat Gafurov et al. Vanadyl porphyrin complexes in asphaltenes from heavy (Karmalinskoye) oil and in asphaltene films obtained as a result of adsorption on the surface of aluminum oxide were studied by electron paramagnetic resonance (EPR) and double electron-nuclear resonance (ENDOR) in the W-band frequency range (microwave frequency of 95 GHz, magnetic field of 3.4 T). Mims ENDOR spectra from 1H and 27Al nuclei are observed. ENDOR spectra are different for native oil and asphaltenes from one side and the adsorbed samples from the other side while no significant changes in X- (microwave frequency of 9 GHz) or W-band EPR spectra are found. The results allow supposing that vanadyl porphyrin complexes (at least in the studied asphaltene films) participate in the formation of asphaltene aggregates through the functional groups rather than π-π interactions. The data show the feasibility of the commercial pulsed ENDOR approaches for the investigation of crude oils and their constituents under external influence