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1.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Kovel E. S., Sachkova A. S., Vnukova N. G., Churilov G. N., Knyazeva E. M., Kudryasheva N. S.
Заглавие : Antioxidant Activity and Toxicity of Fullerenols via Bioluminescence Signaling: Role of Oxygen Substituents
Место публикации : Int. J. Mol. Sci. - 2019. - Vol. 20, Is. 9. - Ст.2324. - ISSN 14220067 (ISSN) , DOI 10.3390/ijms20092324
Примечания : Cited References: 74. - This work was supported by PRAN-32, Program: 'Nanostructures: physics, chemistry, biology, technological basis'; RFBR 18-29-19003; RFBR-Krasnoyarsk Regional Foundation 18-44-240004, Tomsk Polytechnic University CE Program.
Аннотация: Fullerenols are nanosized water-soluble polyhydroxylated derivatives of fullerenes, a specific allotropic form of carbon, bioactive compounds, and perspective basis for drug development. Our paper analyzes the antioxidant activity and toxicity of a series of fullerenols with different number of oxygen substituents. Two groups of fullerenols were under investigation: (1) C60Oy(OH)(x), C60,70Oy(OH)(x), where x+y = 24-28 and (2) C60,70Oy(OH)(x), Fe0,5C60Oy(OH)(x), Gd@C82Oy(OH)(x), where x+y = 40-42. Bioluminescent cellular and enzymatic assays (luminous marine bacteria and their enzymatic reactions, respectively) were applied to monitor toxicity in the model fullerenol solutions and bioluminescence was applied as a signaling physiological parameter. The inhibiting concentrations of the fullerenols were determined, revealing the fullerenols' toxic effects. Antioxidant fullerenol' ability was studied in solutions of model oxidizer, 1,4-benzoquinone, and detoxification coefficients of general and oxidative types (D-GT and D-OxT) were calculated. All fullerenols produced toxic effect at high concentrations (0.01 g L-1), while their antioxidant activity was demonstrated at low and ultralow concentrations (0.001 g L-1). Quantitative toxic and antioxidant characteristics of the fullerenols (effective concentrations, concentration ranges, D-GT, and D-OxT) were found to depend on the number of oxygen substituents. Lower toxicity and higher antioxidant activity were determined in solutions of fullerenols with fewer oxygen substituents (x+y ⋍ 24-28). The differences in fullerenol properties were attributed to their catalytic activity due to reversible electron acceptance, radical trapping, and balance of reactive oxygen species in aqueous solutions. The results provide pharmaceutical sciences with a basis for selection of carbon nanoparticles with appropriate toxic and antioxidant characteristics. Based on the results, we recommend, to reduce the toxicity of prospective endohedral gadolinium-fullerenol preparations Gd@C82Oy(OH)(x), decreasing the number of oxygen groups to x+y ⋍ 24-28. The potential of bioluminescence methods to compare toxic and antioxidant characteristics of carbon nanostructures were demonstrated.
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2.

Вид документа : Статья из сборника (однотомник)
Шифр издания :
Автор(ы) : Sushko E. S., Sachkova A. S., Внукова, Наталья Григорьевна, Чурилов, Григорий Николаевич, Stepin E. A., Kicheeva A. G., Kudryasheva N. S.
Заглавие : Biological activity of fullerenols of various structure. The role of reactive oxygen species. Bioluminescent monitoring
Коллективы : Congress of Biophysicists of Russia
Место публикации : Biophysical reviews: 7th Congress of Biophysicists of Russia : conference proceedings. - 2023. - Vol. 15, Is. 5. - Ст.S7.437. - P.1663. - DOI 10.1007/s12551-023-01150-w
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3.

Вид документа : Статья из сборника (однотомник)
Шифр издания :
Автор(ы) : Dubinina I. A., Dudnik A. I., Vnukova N. G., Churilov G. N.
Заглавие : Comparative study of antioxidant activity of fullerenols including higher and endohedral fullerenols by inhibition of adrenaline autoxidation
Коллективы : "Advanced carbon nanostructures", International conference
Место публикации : International Conference Advanced Carbon Nanostructures: abstracts of invited lectures & contributed papers. - 2015. - P.63
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4.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Stepin E. A., Sushko E. S., Vnukova N. G., Churilov G. N., Rogova A. V., Tomilin F. N., Kudryasheva N. S.
Заглавие : Effects of endohedral Gd-containing fullerenols with a different number of oxygen substituents on bacterial bioluminescence
Колич.характеристики :19 с
Место публикации : Int. J. Mol. Sci. - 2024. - Vol. 25, Is. 2. - Ст.708. - ISSN 16616596 (ISSN), DOI 10.3390/ijms25020708. - ISSN 14220067 (eISSN)
Примечания : Cited References: 102. - This research was funded by the State Assignment of the Ministry of Science and Higher Education of the Russian Federation, project No. 0287-2021-0020, and partly supported by the Russian Science Foundation No. 23-26-10018, Krasnoyarsk Regional Science Foundation
Аннотация: Gadolinium (Gd)-containing fullerenols are perspective agents for magnetic resonance imaging and cancer research. They combine the unique paramagnetic properties of Gd with solubility in water, low toxicity and antiradical activity of fullerenols. We compared the bioeffects of two Gd-containing fullerenols with a different number of oxygen groups—20 and 42: Gd@C82O20H14 and Gd@C82O42H32. The bioluminescent bacteria-based assay was applied to monitor the toxicity of fullerenols, bioluminescence was applied as a signal physiological parameter, and bacterial enzyme-based assay was used to evaluate the fullerenol effects on enzymatic intracellular processes. Chemiluminescence luminol assay was applied to monitor the content of reactive oxygen species (ROS) in bacterial and enzymatic media. It was shown that Gd@C82O42H32 and Gd@C82O20H14 inhibited bacterial bioluminescence at 10?1 and 10?2 gL?1, respectively, revealing a lower toxicity of Gd@C82O42H32. Low-concentration (10?3–10?1 gL?1) bacterial bioluminescence activation by Gd@C82O42H32 was observed, while this activation was not found under exposure to Gd@C82O20H14. Additional carboxyl groups in the structure of Gd@C82O42H32 were determined by infrared spectroscopy and confirmed by quantum chemical calculations. The groups were supposed to endow Gd@C82O42H32 with higher penetration ability through the cellular membrane, activation ability, lower toxicity, balancing of the ROS content in the bacterial suspensions, and lower aggregation in aqueous media.
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5.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Sachkova A. S., Kovel E. S., Churilov G. N., Guseynov O. A., Bondar A. A., Dubinina I. A., Kudryasheva N. S.
Заглавие : On mechanism of antioxidant effect of fullerenols
Место публикации : Biochem. Biophys. Rep.: Elsevier, 2017. - Vol. 9. - P.1-8. - ISSN 24055808 (ISSN), DOI 10.1016/j.bbrep.2016.10.011
Примечания : Cited References: 69. - The work was supported by the Russian Foundation for Basic Research, Grants No 15-03-06786 and 15–43-04377-sibir; the state budget allocated to the fundamental research at the Russian Academy of Sciences (project No 01201351504). Adaptation of the bioluminescent enzymatic technique to assess the antioxidant activity of bioactive compounds (humates and fullerenols) was partially supported by the Russian Science Foundation, Grant N 16-06-14-10115.
Ключевые слова (''Своб.индексиров.''): antioxidant activity--bacterial enzymes--fullerenol--hormesis--luminous marine bacteria--ultralow concentrations
Аннотация: Fullerenols are nanosized water-soluble polyhydroxylated derivatives of fullerenes, specific allotropic form of carbon, bioactive compounds and perspective pharmaceutical agents. Antioxidant activity of fullerenols was studied in model solutions of organic and inorganic toxicants of oxidative type – 1,4-benzoquinone and potassium ferricyanide. Two fullerenol preparations were tested: С60О2–4(ОН)20–24 and mixture of two types of fullerenols С60О2–4(ОН)20–24+С70О2–4(ОН)20–24. Bacteria-based and enzyme-based bioluminescent assays were used to evaluate a decrease in cellular and biochemical toxicities, respectively. Additionally, the enzyme-based assay was used for the direct monitoring of efficiency of the oxidative enzymatic processes. The bacteria-based and enzyme-based assays showed similar peculiarities of the detoxification processes: (1) ultralow concentrations of fullerenols were active (ca 10–17–10−4 and 10–17–10−5 g/L, respectively), (2) no monotonic dependence of detoxification efficiency on fullerenol concentrations was observed, and (3) detoxification of organic oxidizer solutions was more effective than that of the inorganic oxidizer. The antioxidant effect of highly diluted fullerenol solutions on bacterial cells was attributed to hormesis phenomenon; the detoxification was concerned with stimulation of adaptive cellular response under low-dose exposures. Sequence analysis of 16S ribosomal RNA was carried out; it did not reveal mutations in bacterial DNA. The suggestion was made that hydrophobic membrane-dependent processes are involved to the detoxifying mechanism. Catalytic activity of fullerenol (10−8 g/L) in NADH-dependent enzymatic reactions was demonstrated and supposed to contribute to adaptive bacterial response.
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6.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Tomilin F. N., Artyushenko P. V., Shchugoreva I. A., Rogova A. V., Vnukova N. G., Churilov G. N., Shestakov N. P., Tchaikovskaya O. N., Ovchinnikov S. G., Avramov P. V.
Заглавие : Structure and vibrational spectroscopy of C82 fullerenol valent isomers: An experimental and theoretical joint study
Место публикации : Molecules. - 2023. - Vol. 28, Is. 4. - Ст.1569. - ISSN 14203049 (eISSN), DOI 10.3390/molecules28041569
Примечания : Cited References: 57. - Synthesis and spectroscopic study of the Gd@C82OxHy complexes were supported by the Ministry of Science and Higher Education of the Russian Federation under project FWES-2022-0005. Molecular design of the fullerene derivatives was supported by the National Research Foundation of the Republic of Korea, grant NRF 2021R1A2C1010455. DFTB3 electronic structure calculations were supported by Project FSWM-2020-0033 of the Russian Ministry of Science and Education
Аннотация: Gd@C82OxHy endohedral complexes for advanced biomedical applications (computer tomography, cancer treatment, etc.) were synthesized using high-frequency arc plasma discharge through a mixture of graphite and Gd2O3 oxide. The Gd@C82 endohedral complex was isolated by high-efficiency liquid chromatography and consequently oxidized with the formation of a family of Gd endohedral fullerenols with gross formula Gd@C82O8(OH)20. Fourier-transformed infrared (FTIR) spectroscopy was used to study the structure and spectroscopic properties of the complexes in combination with the DFTB3 electronic structure calculations and infrared spectra simulations. It was shown that the main IR spectral features are formed by a fullerenole C82 cage that allows one to consider the force constants at the DFTB3 level of theory without consideration of gadolinium endohedral ions inside the carbon cage. Based on the comparison of experimental FTIR and theoretical DFTB3 IR spectra, it was found that oxidation of the C82 cage causes the formation of Gd@C82O28H20, with a breakdown of the integrity of the parent C82 cage with the formation of pores between neighboring carbonyl and carboxyl groups. The Gd@C82O6(OOH)2(OH)18 endohedral complex with epoxy, carbonyl and carboxyl groups was considered the most reliable fullerenole structural model.
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7.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Dubinina I. A., Kuzmina E. M., Dudnik A. I., Vnukova N. G., Churilov G. N., Samoylova N. A.
Заглавие : Study of antioxidant activity of fullerenols by inhibition of adrenaline autoxidation
Место публикации : Наносистемы: физ., хим., матем.: Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики, 2016. - Т. 7, № 1. - С.153-157. - ISSN 2220-8054, DOI 10.17586/2220-8054-2016-7-1-153-157; Nanosystems: phys., chem., mathem.
Примечания : Библиогр.: 8. - The work was supported by the Russian Foundation for Basic Research 15-03-06786.
Ключевые слова (''Своб.индексиров.''): fullerenol--antioxidant activity--endohedral fullerenol--adrenaline autoxidation
Аннотация: In this paper, we describe application of the adrenaline autoxidation reaction to determine the antioxidant activity of fullerenols C60, C70 their mixture with higher fullerenol and endohedral fullerenol Y@C82. It was shown that the adrenaline autoxidation reaction can be applied to determine the antioxidant activity of fullerenols. The antioxidant activity of C70 fullerenol was higher than that of C60 fullerenol Additionally, the antioxidant activity of Y@C82 fullerenol was higher than that of C70 fullerenol.
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8.

Вид документа : Статья из журнала
Шифр издания :
Автор(ы) : Shakirova A. A., Tomilin F. N., Pomogaev V. A., Vnukova N. G., Churilov G. N., Kudryasheva N. S., Tchaikovskaya O. N., Ovchinnikov S. G., Avramov P. V.
Заглавие : Synthesis, mass spectroscopy detection, and density functional theory investigations of the Gd endohedral complexes of C82 fullerenols
Коллективы : RFBRRussian Foundation for Basic Research (RFBR) [18-29-19003 MK]; Russian Ministry of Science and EducationMinistry of Education and Science, Russian Federation [0721-2020-0033]; Collaborative NRF-RFBR grant (Korean) [NRF-2019K2A9A1A06100125]; Collaborative NRF-RFBR grant (Russian) [19-53-51005 NIFa RFFI-Korea]; NRF [2021R1A2C1010455]
Место публикации : Computation. - 2021. - Vol. 9, Is. 5. - Ст.58. - ISSN 2079-3197(eISSN), DOI 10.3390/computation9050058
Примечания : Cited References: 41. - The experimental results were funded by RFBR project No. 18-29-19003 MK. The quantum chemical study was funded by project 0721-2020-0033 of the Russian Ministry of Science and Education. The collaboration and coordination of Russian and Korean teams was supported by Collaborative NRF-RFBR grant (Korean ID: NRF-2019K2A9A1A06100125; Russian ID: Project No. 19-53-51005 NIFa RFFI-Korea) and NRF 2021R1A2C1010455 grant
Предметные рубрики: ZETA VALENCE QUALITY
BIOLOGICAL-ACTIVITY
BASIS-SETS
TOXICITY
Аннотация: Gd endohedral complexes of C82 fullerenols were synthesized and mass spectrometry analysis of their composition was carried out. It was established that the synthesis yields a series of fullerenols Gd@C82Ox(OH)y (x = 0, 3; y = 8, 16, 24, 36, 44). The atomic and electronic structure and properties of the synthesized fullerenols were investigated using the density functional theory calculations. It was shown that the presence of endohedral gadolinium increases the reactivity of fullerenols. It is proposed that the high-spin endohedral fullerenols are promising candidates for application in magnetic resonance imaging.
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9.

Вид документа : Статья из сборника (однотомник)
Шифр издания :
Автор(ы) : Kovel E. S., Sachkova A. S., Churilov G. N., Kudryasheva N. S.
Заглавие : Использование биолюминесцентных тестовых систем для обнаружения антиоксидантной активности фуллеренолов
Коллективы : Томский государственный архитектурно-строительный университет, Томский государственный университет, Томский политехнический университет, Томский государственный университет систем управления и радиоэлектроники, "Перспективы развития фундаментальных наук", Международная конференция студентов, аспирантов и молодых ученых
Место публикации : Перспективы развития фундаментальных наук: сб. науч. трудов XIII Междун. конф. студентов, аспирантов и мол. ученых. - 2016. - Т. 2: Химия. - С. 217-219
Примечания : Библиогр.: 6
Аннотация: Антиоксидантные свойства фуллеренолов (водорастворимых наноразмерных частиц, полигидроксилированных производных фуллеренов) были исследованы в растворахмодельных окислителей органического и неорганического происхождения – 1,4-бензохинона и феррицианида калия. Изучена антиоксидантная активность двух препаратов фуллеренолов – C60Оу(OH)х и смеси C60Оу(OH)х+C70Оу(OH)х (у=2-4, х=22-24). Для оценки клеточной и биохимической токсичности растворов были использованы две биолюминесцентные тестовые системы: лиофилизированные бактерии Photobacterium phosphoreum и биферментная система NADH:FMN-оксидоредуктаза–люцифераза. Кроме того, ферментативный биотест был использован для прямого мониторинга эффективности ферментативных редокс-процессов. Обнаружены сходства процессов детоксикации растворов окислителей препаратами фуллеренолов: (1) активность низких концентраций фуллеренолов (10-17-10-4 и 10-17-10-5 г/л, соответственно для бактериальной и ферментативной систем), (2)более эффективная детоксикация растворов органического окислителя, чем неорганического. Проанализированы скорости биохимических процессов в растворах окислитель+фуллеренол; выявлено, что фуллеренолы (10-8 г/л) изменяют скорости эндогенных NADH-зависимых процессов. При этом ускорение ферментативных NADH-зависимых реакций является основой защитного отклика биотестовой системы, а ускорение автоокисления NADH уменьшает восстановительные свойства среды и, следовательно, подавляет бактериальную люминесцентную физиологическую функцию. Таким образом, выявлены антиоксидантные свойства высокоразбавленных растворов фуллеренолов; продемонстрирован высокий потенциал биолюминесцентных тестов для мониторинга и сравнения антиоксидантых свойств биологическиактивных веществ. Обсуждается роль гидрофобных свойств среды и клеточных мембран в процессах детоксикации растворов окислителей на примере фуллеренолов как физиологически-активных веществ.
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