Structural modifications of VO2+ chelates in the organic matter of oils and bitumens from the EPR spectra

Gilinskaya, L. G.; Borisova, L S; Костырева, Е.А.

doi:10.1134/s0022476615030051

Cited by 6 publications

(6 citation statements)

References 8 publications

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“…Petroporphyrins are the metal-containing components of petroleum and considered as biomarkers confirming its biological origin. , In the past decade, there has been a rapid progress in the study of petroporphyrin composition by ultrahigh-resolution mass-spectrometric methods which help to discover new types of petroporphyrins − contributing to better understanding the processes of oil genesis. EPR (electron paramagnetic resonance) and ENDOR (electron–nuclear double resonance) spectroscopic methods sensitive to electronic and structural environments of paramagnetic vanadyl ions provided additional insight into the structure and properties of petroporphyrins − and revealed the applicability of the latter in the study of asphaltene aggregation processes. − New HPLC-based approaches directed to solving a problem of quantitative analysis of petroporphyrins in petroleum objects were proposed. , However, the practical aspects of petroporphyrin application still remain unstudied. At the same time, synthetic metalloporphyrins have been tested in a large number of oxidative catalytic processes having great practical importance: epoxidation of olefins, − functionalization of the C–H bond, − oxygenation of sulfides, ,, dimerization of sulfides, etc., , while their metal-free counterparts exhibited high efficacy as photoactive components of solar cells .…”

Section: Introductionmentioning

confidence: 99%

Comparative Study of Resins and Asphaltenes of Heavy Oils as Sources for Obtaining Pure Vanadyl Porphyrins by the Sulfocationite-Based Chromatographic Method

et al. 2018

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The resins and asphaltenes of three heavy oils differing in origin (Permian and Carboniferous) and vanadium content (0.025–0.165 wt %) have been studied as sources for isolation of spectrally pure vanadyl porphyrins by sulfocationite-based chromatographic method developed by us recently. This method consists of removing the low polar nonporphyrin components from the resins or DMF extract of asphaltenes on SiO2-column followed by chromatographic isolation of vanadyl porphyrins on the sulfocationite. The asphaltenes were revealed to be a more promising source of vanadyl porphyrins because they possess ≥5 times higher content of vanadium, provide better accumulation of vanadyl porphyrins during deposition extraction by N,N-dimethylformamide, and are less contaminated by low polar nonporphyrin compounds capable of coeluting with vanadyl porphyrins through the sulfocationite column. According to matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy, DPEP vanadyl porphyrins were found to be the most abundant type for all studied samples (34.1–54.5%). Rhodo vanadyl porphyrins belong to minor components (3.3–8.7% for each subtype) while Etio and Di-DPEP types take the intermediate position (9.8–28.7%). The resins and asphaltenes of the same oil showed significant difference in the group composition of purified vanadyl porphyrins. For the resins, a ∼1.3-fold decreased content of DPEP vanadyl porphyrins was found, which was compensated by a ∼1.5- and/or ∼1.8-fold increase in the content of Etio and Rhodo vanadyl porphyrins, respectively. However, this change in the composition of vanadyl porphyrins is not accompanied by a notable change of their average molecular weight despite the fact that increased concentration of more substituted (i.e., more hydrophobic) vanadyl porphyrins could be expected for less polar resins. This fact was interpreted in favor of association of vanadyl porphyrins with nonporphyrin components of the oil.

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Section: Introductionmentioning

confidence: 99%

Comparative Study of Resins and Asphaltenes of Heavy Oils as Sources for Obtaining Pure Vanadyl Porphyrins by the Sulfocationite-Based Chromatographic Method

et al. 2018

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“…Ванадий мөлшері жоғары ауыр мұнайдың дисперсті жүйесінің құрылымының пайда болу кезеңінде мұнай құрамындағы асфальтендер мөлшерінің жоғары болуы оның құрамы мен қасиеттеріне айтарлықтай әсер етіп, мұнайды өндіру, өңдеу,тасымалдау сатыларында маңызды фактор болып табылады (Гольдберг және т.б., 1986;Gilinskaya, 2015). Мұнай асфальтендері жеңіл алкандармен еріту кезінде тұнатын белгілі бір құраммен сипатталады.…”

Section: Introductionunclassified

Assessment of the Possibility of Obtaining Sorbents From Asphalt and Use as an Adhesive Additive to Road Bitumen

Kainenova,

Оrynbassar,

Kosmbayeva

et al. 2024

SCT

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doctor of chemistry, professor, academician of NAS RK, president of NAS RK, general director of JSC "Institute of fuel, catalysis and electrochemistry named after D.V. Sokolsky (Almaty, Kazakhstan) H = 4 Editorial board: ADEKENOV Sergazy Mynzhasarovich (deputy editor-in-chief) doctor of chemical sciences, professor, academician of NAS RK, director of the international Scientific and production holding «Phytochemistry» (Karaganda, Kazakhstan) H = 11 AGABEKOV Vladimir Enokovich (deputy editor-in-chief), doctor of chemistry, professor, academician of NAS of Belarus, honorary director of the Institute of Chemistry of new materials (Minsk, Belarus) H = 13 STRNAD Miroslav, head of the laboratory of the institute of Experimental Botany of the Czech academy of sciences, professor (Olomouc, Czech Republic) H = 66 BURKITBAYEV Mukhambetkali, doctor of chemistry, professor, academician of NAS RK, first vice-rector of al-Farabi KazNU (Almaty, Kazakhstan) H = 11 HOHMANN Judith, head of the department of pharmacognosy, faculty of Pharmacy, university of Szeged, director of the interdisciplinary center for Life sciences (Szeged, ungary) H = 38 ROSS Samir, Ph.D, professor, school of Pharmacy, national center for scientific research of Herbal Products, University of Mississippi (Oxford, USA) H = 35 KHUTORYANSKY Vitaly, Ph.D, pharmacist, professor at the University of Reading (Reading, England) H = 40 TELTAYEV Bagdat Burkhanbayuly, doctor of technical sciences, professor, corresponding member of NAS RK, ministry of Industry and infrastructure development of the Republic of Kazakhstan (Almaty, Kazakhstan) H = 13 PHARUK Asana Dar, professor at Hamdard al-Majid college of Oriental medicine. faculty of Oriental medicine, Hamdard university (Karachi, Pakistan) H = 21 FAZYLOV Serik Drakhmetovich, doctor of chemistry, professor, academician of NAS RK, deputy director for institute of Organic synthesis and coal chemistry (Karaganda, Kazakhstan) H = 6 ZHOROBEKOVA Sharipa Zhorobekovna, doctor of chemistry, professor, academician of NAS of Kyrgyzstan, Institute of Chemistry and chemical technology of NAS KR (Bishkek, Kyrgyzstan) H = 4 KHALIKOV Jurabay Khalikovich, doctor of chemistry, professor, academician of the academy of sciences of tajikistan, institute of Chemistry named after V.I. Nikitin AS RT (Tajikistan) H = 6 FARZALIEV Vagif Medzhid ogly, doctor of chemistry, professor, academician of NAS of Azerbaijan (Azerbaijan) H = 13 GARELIK Hemda, PhD in chemistry, president of the department of Chemistry and Environment of the International Union of Pure and Applied Chemistry (London, England) H = 15 News of the National Academy of Sciences of the Republic of Kazakhstan. Series of chemistry and technology.

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“…Different aspects of application of various electron paramagnetic resonance (EPR) and double resonance (ENDOR) techniques for the elucidation of the asphaltene architecture and the oil PC nature are covered in refs. [2,19,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

“…The effectiveness of the use of the VP as a native probe for the investigation of asphaltenes is determined by the resolved anisotropic spectral parameters (g-factor and hyperfine components, zero-field splitting, quadrupole tensors) in the EPR/ENDOR spectra, which makes VP to be orientationselective even in disordered media [40][41][42][43][44][45][46][47][48][49][50][51]. Using X-band (microwave frequency ν MW of 9 GHz, magnetic field B 0 of 0.34 T) and high-frequency (ν MW of 95 GHz, B 0 of 3.4 T, W-band) conventional and pulsed EPR/ENDOR techniques, we have shown that, on the one hand, the EPR and ENDOR spectra for VP in the initial oil samples of different genesis are similar while, on other hand, the relaxation parameters of VP (the electron longitudinal (T 1e ) and transverse (T 2e ) relaxation times) and the temperature dependences of the EPR spectra depend strongly on the nature of the sample and the method of the fractionation procedure [49][50][51][52].…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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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.

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Structural modifications of VO2+ chelates in the organic matter of oils and bitumens from the EPR spectra

Cited by 6 publications

References 8 publications

Comparative Study of Resins and Asphaltenes of Heavy Oils as Sources for Obtaining Pure Vanadyl Porphyrins by the Sulfocationite-Based Chromatographic Method

Comparative Study of Resins and Asphaltenes of Heavy Oils as Sources for Obtaining Pure Vanadyl Porphyrins by the Sulfocationite-Based Chromatographic Method

Assessment of the Possibility of Obtaining Sorbents From Asphalt and Use as an Adhesive Additive to Road Bitumen

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

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