vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/achb.915OKCVTRvuzbiochemi-1237Research ArticleФИЗИКО-ХИМИЧЕСКАЯ БИОЛОГИЯPHYSICOCHEMICAL BIOLOGYСвойства нитратов целлюлозы, полученных нитрованием бактериальной целлюлозы с использованием смеси азотной и серной кислотProperties of cellulose nitrates produced by nitration of bacterial cellulose using mixed sulfuric-nitric acidshttps://orcid.org/0009-0009-6599-1582ГорбатоваП. А.GorbatovaP. A.

Полина Алексеевна Горбатова, лаборант, студент

659322; ул. Социалистическая, 1; 659305; ул. Трофимова, 27; Бийск

Polina A. Gorbatova, Laboratory Assistant, Student

659322; 1, Sotsialisticheskaya St.;  659305; 27, Trofimov St.; Biysk

1402plngorbatova@mail.ruhttps://orcid.org/0000-0003-3633-2392КорчагинаА. А.KorchaginaA. A.

Анна Александровна Корчагина, к. т. н., старший научный сотрудник

659322; ул. Социалистическая, 1; Бийск

Anna A. Korchagina, Cand. Sci. (Engineering), Senior Research Scientist

659322; 1, Sotsialisticheskaya St.; Biysk

yakusheva89_21.ru@mail.ruhttps://orcid.org/0000-0001-5480-7449ГисматулинаЮ. А.GismatulinaYu. A.

Юлия Александровна Гисматулина, к. т. н., старший научный сотрудник

659322; ул. Социалистическая, 1; Бийск

Yulia A. Gismatulina, Cand. Sci. (Engineering), Senior Research Scientist

659322; 1, Sotsialisticheskaya St.; Biysk

julja.gismatulina@rambler.ruhttps://orcid.org/0000-0002-5572-1476ШавыркинаН. А.ShavyrkinaN. A.

Надежда Александровна Шавыркина, к. т. н., старший научный сотрудник, доцент

659322; ул. Социалистическая, 1; 659305; ул. Трофимова, 27; Бийск

Nadezhda A. Shavyrkina, Cand. Sci. (Engineering), Senior Research Scientist, Associate Professor

659322; 1, Sotsialisticheskaya St.; 659305; 27, Trofimov St.; Biysk

32nadina@mail.ruhttps://orcid.org/0000-0002-1628-0815БудаеваВ. В.BudaevaV. V.

Вера Владимировна Будаева, к. х. н., доцент, заведующий лабораторией, ведущий научный сотрудник

659322; ул. Социалистическая, 1; Бийск

Vera V. Budaeva, Cand. Sci. (Chemistry), Associate Professor, Head of Laboratory, Lead Research Scientist

659322; 1, Sotsialisticheskaya St.; Biysk

budaeva@ipcet.ruИнститут проблем химико-энергетических технологий СО РАН; Бийский технологический институт – филиал Алтайского государственного технического университета им. И.И. ПолзуноваРоссияInstitute for Problems of Chemical and Energetic Technologies SB RAS; Biysk Technological Institute, Polzunov Altai State Technical UniversityRussian FederationИнститут проблем химико-энергетических технологий СО РАНРоссияInstitute for Problems of Chemical and Energetic Technologies SB RASRussian Federation202407072024142236244Copyright © Горбатова П.А., Корчагина А.А., Гисматулина Ю.А., Шавыркина Н.А., Будаева В.В., 20242024Горбатова П.А., Корчагина А.А., Гисматулина Ю.А., Шавыркина Н.А., Будаева В.В.Gorbatova P.A., Korchagina A.A., Gismatulina Y.A., Shavyrkina N.A., Budaeva V.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/1237

   Целью проведенного исследования являлось изучение химической функционализации бактериальной целлюлозы как альтернативного источника целлюлозы в связи с высокой востребованностью наноразмерных нитратов целлюлозы.

   Бактериальная целлюлоза со степенью полимеризации 3950 была получена с использованием в качестве продуцента симбиотической культуры Medusomyces gisevii Sa-12 на синтетической глюкозной среде. Нитрование проводилось смесью азотной и серной кислот с различным содержанием воды с последующей стабилизацией синтезированных нитратов бактериальной целлюлозы. Нитраты бактериальной целлюлозы характеризовались массовой долей азота в диапазоне от 8,68 до 11,56 %, растворимостью в спиртоэфирной смеси 16,5–91,0 %, вязкостью 32–255 мПа×с в зависимости от содержания воды (14, 16 и 20 %) в нитрующей смеси. Наноразмерный характер волокон нитратов бактериальной целлюлозы сохранился. Методами совместного термогравиметрического и дифференциально-термического анализа установлены высокая химическая чистота и энергоемкость нитратов бактериальной целлюлозы. Методом инфракрасной спектроскопии с преобразованием Фурье установлено высокое качество бактериальной целлюлозы в связи с наличием основных функциональных групп, характерных для целлюлозы классического происхождения: 3371, 2943, 1633, 1428, 1371, 1163, 1112 см-1. В инфракрасных спектрах образцов нитратов бактериальной целлюлозы зарегистрированы основные функциональные группы, подтверждающие, что синтезированные продукты являются низкозамещенными азотнокислыми эфирами целлюлозы: 1660–1643, 1282–1276, 847–837, 752–749, 691–690 см-1. Установлено, что зависимость свойств синтезированных нитратов бактериальной целлюлозы от массовой доли воды в серно-азотной смеси имеет сложный характер.

   The study set out to investigate the chemical functionalization of bacterial cellulose as an alternative means of satisfying the high demand for nano-sized cellulose nitrates.

   Using a Medusomyces gisevii Sa-12 symbiotic culture as a microbial producer, bacterial cellulose having a polymerization degree of 3950 was obtained on a synthetic glucose medium. Nitration was carried out using mixed sulfuric-nitric acids differing in their water content, followed by stabilization of the synthesized bacterial cellulose nitrates. Subject to a varying water content (14, 16 and 20 %) in the nitrating mixture, the obtained bacterial cellulose nitrates exhibited a nitrogen mass content of 8.68–11.56 %, a solubility in alcohol-ether mixture of 16.5–91.0 % and a viscosity of 32–255 mPa×s. The bacterial cellulose nitrate fibers were shown to have a nanoscale nature. Coupled thermogravimetric and differential thermal analyses revealed the bacterial cellulose nitrates to have a high chemical purity and energy content. FTIR spectroscopy confirmed the high quality of the bacterial cellulose based on the presence of basic functional groups characteristic of conventional cellulose: 3371, 2943, 1633, 1428, 1371, 1163, and 1112 cm-1. According to their infrared spectra, the detected basic functional groups corroborate that the synthesized products are low-substituted cellulose nitrate esters: 1660–1643, 1282-1276, 847–837, 752–749, and 691–690 cm-1. The relationship between the properties of the synthesized bacterial cellulose nitrates and the water mass content in mixed sulfuric-nitric acids is shown to have a complex nature.

бактериальная целлюлозанитрованиесерно-азотная смесьнитраты бактериальной целлюлозыbacterial cellulosenitrationsulfuric-nitric acid mixturebacterial cellulose nitratesИсследование выполнено при поддержке проекта Минобрнауки в рамках госзадания ИПХЭТ СО РАН (код научной темы FUFE-2024-0008, регистрационный номер 124021200031-4)This study was supported by the Ministry of Science and Higher Education of the Russian Federation under government assignment (Registration ID: 124021200031-4, Research Theme Code: FUFE-2024-0008)ReferencesAndriani D., Apriyana A.Y., Karina M. The optimization of bacterial cellulose production and its applications : a review // Cellulose. 2020. Vol. 27. P. 6747–6766. DOI: 10.1007/s10570-020-03273-9.Andriani D., Apriyana A.Y., Karina M. The optimization of bacterial cellulose production and its applications : a review. Cellulose. 2020;27:6747-6766. DOI: 10.1007/s10570-020-03273-9.Рогожин В.В., Рогожин Ю.В. Medusomyces gisevii: строение, функционирование и использование // Известия вузов. Прикладная химия и биотехнология. 2017. Т. 7. N 4. С. 24–35. DOI: 10.21285/2227-2925-2017-7-4-24-35. EDN: YMQFOA.Rogozhin V.V., Rogozhin U.V. Medusomyces gisevii: structure, function, and use. Proceedings of Universities. Applied Chemistry and Biotechnology. 2017;7(4):24-35. (In Russian). DOI: 10.21285/2227-2925-2017-7-4-24-35. EDN: YMQFOA.Hu W., Chen S., Yang J., Li Z., Wang H. Functionalized bacterial cellulose derivatives and nanocomposites // Carbohydrate Polymers. 2014. Vol. 101. P. 1043–1060. DOI: 10.1016/j.carbpol.2013.09.102.Hu W., Chen S., Yang J., Li Z., Wang H. Functionalized bacterial cellulose derivatives and nanocomposites. Carbohydrate Polymers. 2014;101:1043-1060. DOI: 10.1016/j.carbpol.2013.09.102.Rahman M.S., Hasan M.S., Nitai A.S., Nam S., Karmakar A.K., Ahsan M.S., et al. Recent developments of carboxymethyl cellulose // Polymers. 2021. Vol. 13, no. 8. P. 1345. DOI: 10.3390/polym13081345.Rahman M.S., Hasan M.S., Nitai A.S., Nam S., Karmakar A.K., Ahsan M.S., et al. Recent developments of carboxymethyl cellulose. Polymers. 2021;13(8):1345. DOI: 10.3390/polym13081345.Alharbi N.D., Guirguis O.W. Macrostructure and optical studies of hydroxypropyl cellulose in pure and Nano-composites forms // Results in Physics. 2019. Vol. 15. P. 102637. DOI: 10.1016/j.rinp.2019.102637.Alharbi N.D., Guirguis O.W. Macrostructure and optical studies of hydroxypropyl cellulose in pure and Nano-composites forms. Results in Physics. 2019;15:102637. DOI: 10.1016/j.rinp.2019.102637.Tan W., Zhang J., Zhao X., Li Q., Dong F., Guo Z. Preparation and physicochemical properties of antioxidant chitosan ascorbate/methylcellulose composite films // International Journal of Biological Macromolecules. 2020. Vol. 146. P. 53–61. DOI: 10.1016/j.ijbiomac.2019.12.044.Tan W., Zhang J., Zhao X., Li Q., Dong F., Guo Z. Preparation and physicochemical properties of antioxidant chitosan ascorbate/methylcellulose composite films. International Journal of Biological Macromolecules. 2020;146:53-61. DOI: 10.1016/j.ijbiomac.2019.12.044.Nursyafiqah J.R., Siti Hasnawati J., Jahwarhar Izuan A.R., Mohd Nor Faiz N., Ong K.K., Wan Md Zin W.Y. Response surface methodology for optimization of nitrocellulose preparation from nata de coco bacterial cellulose for propellant formulation // Heliyon. 2024. Vol. 10, no. 4. P. e25993. DOI: 10.1016/j.heliyon.2024.e25993.Nursyafiqah J.R., Siti Hasnawati J., Jahwarhar Izuan A.R., Mohd Nor Faiz N., Ong K.K., Wan Md Zin W.Y. Response surface methodology for optimization of nitrocellulose preparation from nata de coco bacterial cellulose for propellant formulation. Heliyon. 2024;10(4):e25993. DOI: 10.1016/j.heliyon.2024.e25993.Siti Hasnawati J., Nursyafiqah J.R., Noor Aisyah A.S., Siti Aminah M.N., Ong K.K., Wan Md Zin W.Y. Conversion of bacterial cellulose to cellulose nitrate with high nitrogen content as propellant ingredient // Solid State Phenomena. 2021. Vol. 317. P. 305–311. DOI: 10.4028/www.scientific.net/SSP.317.305.Siti Hasnawati J., Nursyafiqah J.R., Noor Aisyah A.S., Siti Aminah M.N., Ong K.K., Wan Md Zin W.Y. Conversion of bacterial cellulose to cellulose nitrate with high nitrogen content as propellant ingredient. Solid State Phenomena. 2021;317:305-311. DOI: 10.4028/www.scientific.net/SSP.317.305.Nursyafiqah J.R., Siti Hasnawati J., Ong K.K., Wan Md Zin W.Y. Preliminary study on the effect of sulphuric acid to nitric acid mixture composition, temperature and time on nitrocellulose synthesis based Nata de Coco // Solid State Phenomena. 2021. Vol. 317. P. 312–319. DOI: 10.4028/www.scientific.net/SSP.317.312.Nursyafiqah J.R., Siti Hasnawati J., Ong K.K., Wan Md Zin W.Y. Preliminary study on the effect of sulphuric acid to nitric acid mixture composition, temperature and time on nitrocellulose synthesis based Nata de Coco. Solid State Phenomena. 2021;317:312-319. DOI: 10.4028/www.scientific.net/SSP.317.312.Huang J., Zhao M., Hao Y., Wei Q. Recent advances in functional bacterial cellulose for wearable physical sensing applications // Advanced Materials Technologies. 2022. Vol. 7, no. 1. P. 2100617. DOI: 10.1002/admt.202100617.Huang J., Zhao M., Hao Y., Wei Q. Recent advances in functional bacterial cellulose for wearable physical sensing applications. Advanced Materials Technologies. 2022;7(1):2100617. DOI: 10.1002/admt.202100617.Chandel N., Jain K., Jain A., Raj T., Patel A.K., Yang Y.-H., et al. The versatile world of cellulose-based materials in healthcare: from production to applications // Industrial Crops and Products. 2023. Vol. 201. P. 116929. DOI: 10.1016/j.indcrop.2023.116929.Chandel N., Jain K., Jain A., Raj T., Patel A.K., Yang Y.-H., et al. The versatile world of cellulose-based materials in healthcare: from production to applications. Industrial Crops and Products. 2023;201:116929. DOI: 10.1016/j.indcrop.2023.116929.Cao X., Nan F., Zheng Y., Chen L., He W. Hygroscopicity of nitrocellulose with different nitrogen content // Propellants, Explosives, Pyrotechnics. 2024. Vol. 49, no. 3. P. e202300035. DOI: 10.1002/prep.202300035.Cao X., Nan F., Zheng Y., Chen L., He W. Hygroscopicity of nitrocellulose with different nitrogen content. Propellants, Explosives, Pyrotechnics. 2024;49(3):e202300035. DOI: 10.1002/prep.202300035.Chen L., Cao X., Gao J., Wang Y., Zhang Y., Liu J., et al. Synthesis of 3D porous network nanostructure of nitrated bacterial cellulose gel with eminent heat-release, thermal decomposition behaviour and mechanism // Propellants, Explosives, Pyrotechnics. 2021. Vol. 46, no. 8. P. 1292–1303. DOI: 10.1002/prep.202100010.Chen L., Cao X., Gao J., Wang Y., Zhang Y., Liu J., et al. Synthesis of 3D porous network nanostructure of nitrated bacterial cellulose gel with eminent heat-release, thermal decomposition behaviour and mechanism. Propellants, Explosives, Pyrotechnics. 2021;46(8):1292-1303. DOI: 10.1002/prep.202100010.Shavyrkina N.A., Skiba E.A., Kazantseva A.E., Gladysheva E.K., Budaeva V.V., Bychin N.V., et al. Static culture combined with aeration in biosynthesis of bacterial cellulose // Polymers. 2021. Vol. 13, no. 23. P. 4241. DOI: 10.3390/polym13234241.Shavyrkina N.A., Skiba E.A., Kazantseva A.E., Gladysheva E.K., Budaeva V.V., Bychin N.V., et al. Static culture combined with aeration in biosynthesis of bacterial cellulose. Polymers. 2021;13(23):4241. DOI: 10.3390/polym13234241.Корчагина А.А., Будаева В.В., Алешина Л.А., Люханова И.В., Бычин Н.В., Сакович Г.В. Модификация растительной целлюлозы и ее синтетического аналога в низкозамещенные продукты этерификации // Известия высших учебных заведений. Серия Химия и химическая технология. 2022. Т. 65. N 6. С. 64–74. DOI: 10.6060/ivkkt.20226506.6598. EDN: QGXUCZ.Korchagina A.А., Budaeva V.V., Aleshina L.A., Lyukhanova I.V., Bychin N.V., Sakovich G.V. Modification of plant cellulose and its synthetic analogue into low-substituted esterification products. ChemChemTech. 2022;65(6):64-74. (In Russian). DOI: 10.6060/ivkkt.20226506.6598. EDN: QGXUCZ.Budaeva V.V., Gismatulina Y.A., Mironova G.F., Skiba E.A., Gladysheva E.K., Kashcheyeva E.I., et al. Bacterial nanocellulose nitrates // Nanomaterials. 2019. Vol. 9, no. 12. P. 1694. DOI: 10.3390/nano9121694.Budaeva V.V., Gismatulina Y.A., Mironova G.F., Skiba E.A., Gladysheva E.K., Kashcheyeva E.I., et al. Bacterial nanocellulose nitrates. Nanomaterials. 2019;9(12):1694. DOI: 10.3390/nano9121694.Sun D.-P., Ma B., Zhu C.-L., Liu C.-S., Yang J.-Z. Novel nitrocellulose made from bacterial cellulose // Journal of Energetic Materials. 2010. Vol. 28, no. 2. P. 85–97. DOI: 10.1080/07370650903222551.Sun D.-P., Ma B., Zhu C.-L., Liu C.-S., Yang J.-Z. Novel nitrocellulose made from bacterial cellulose. Journal of Energetic Materials. 2010;28(2):85-97. DOI: 10.1080/07370650903222551.Liu J. Nitrate esters chemistry and technology. Singapore: Springer, 2019. 684 p. DOI: 10.1007/978-981-13-6647-5.Liu J. Nitrate esters chemistry and technology. Singapore: Springer; 2019, 684 p. DOI: 10.1007/978-981-13-6647-5.Gismatulina Yu.A. Promising energetic polymers from nanostructured bacterial cellulose // Polymers. 2023. Vol. 15, no. 9. P. 2213. DOI: 10.3390/polym15092213.Gismatulina Yu.A. Promising energetic polymers from nanostructured bacterial cellulose. Polymers. 2023;15(9):2213. DOI: 10.3390/polym15092213.Singhania R.R., Patel A.K., Tseng Y.-S., Kumar V., Chen C.-W., Haldar D., et al. Developments in bioprocess for bacterial cellulose production // Bioresource Technology. 2022. Vol. 344. P. 126343. DOI: 10.1016/j.biortech.2021.126343.Singhania R.R., Patel A.K., Tseng Y.-S., Kumar V., Chen C.-W., Haldar D., et al. Developments in bioprocess for bacterial cellulose production. Bioresource Technology. 2022;344:126343. DOI: 10.1016/j.biortech.2021.126343.Wahid F., Huang L.-H., Zhao X.-Q., Li W.-C., Wang Y.-Y. Bacterial cellulose and its potential for biomedical applications // Biotechnology Advances. 2021. Vol. 53. P. 107856. DOI: 10.1016/j.biotechadv.2021.107856.Wahid F., Huang L.-H., Zhao X.-Q., Li W.-C., Wang Y.-Y. Bacterial cellulose and its potential for biomedical applications. Biotechnology Advances. 2021;53:107856. DOI: 10.1016/j.biotechadv.2021.107856.Trache D., Khimeche K., Mezroua A., Benziane M. Physicochemical properties of microcrystalline nitrocellulose from Alfa grass fibres and its thermal stability // Journal of Thermal Analysis and Calorimetry. 2016. Vol. 124. P. 1485–1496. DOI: 10.1007/s10973-016-5293-1.Trache D., Khimeche K., Mezroua A., Benziane M. Physicochemical properties of microcrystalline nitrocellulose from Alfa grass fibres and its thermal stability. Journal of Thermal Analysis and Calorimetry. 2016;124:1485-1496. DOI: 10.1007/s10973-016-5293-1.Tarchoun A.F., Trache D., Klapötke T.M., Selmani A., Saada M., Chelouche S., et al. New insensitive high-energy dense biopolymers from giant reed cellulosic fibers: their synthesis, characterization, and non-isothermal decomposition kinetics // New Journal of Chemistry. 2021. Vol. 45, no. 11. P. 5099–5113. DOI: 10.1039/d0nj05484d.Tarchoun A.F., Trache D., Klapötke T.M., Selmani A., Saada M., Chelouche S., et al. New insensitive high-energy dense biopolymers from giant reed cellulosic fibers: their synthesis, characterization, and non-isothermal decomposition kinetics. New Journal of Chemistry. 2021;45(11):5099-5113. DOI: 10.1039/d0nj05484d.Duan X., Li Z., Shi X., Pei C. Giant panda feces: potential raw material in preparation of nitrocellulose for propellants // Cellulose. 2023. Vol. 30. P. 3127–3140. DOI: 10.1007/s10570-023-05054-6.Duan X., Li Z., Shi X., Pei C. Giant panda feces: potential raw material in preparation of nitrocellulose for propellants. Cellulose. 2023;30:3127-3140. DOI: 10.1007/s10570-023-05054-6.Tarchoun A.F., Trache D., Klapötke T.M., Chelouche S., Derradji M., Bessa W., et al. A promising energetic polymer from Posidonia oceanica brown algae: synthesis, characterization, and kinetic modeling // Macromolecular Chemistry and Physics. 2019. Vol. 220, no. 22. P. 1900358. DOI: 10.1002/macp.201900358.Tarchoun A.F., Trache D., Klapötke T.M., Chelouche S., Derradji M., Bessa W., et al. A promising energetic polymer from Posidonia oceanica brown algae: synthesis, characterization, and kinetic modeling. Macromolecular Chemistry and Physics. 2019;220(22):1900358. DOI: 10.1002/macp.201900358.Gao X., Jiang L., Xu Q., Wu W.-Q., Mensah R.A. Thermal kinetics and reactive mechanism of cellulose nitrate decomposition by traditional multi kinetics and modeling calculation under isothermal and non-isothermal conditions // Industrial Crops and Products. 2020. Vol. 145. P. 112085. DOI: 10.1016/j.indcrop.2020.112085.Gao X., Jiang L., Xu Q., Wu W.-Q., Mensah R.A. Thermal kinetics and reactive mechanism of cellulose nitrate decomposition by traditional multi kinetics and modeling calculation under isothermal and non-isothermal conditions. Industrial Crops and Products. 2020;145:112085. DOI: 10.1016/j.indcrop.2020.112085.Duan X., Li Z., Wu B., Shen J., Pei C. Preparation of nitrocellulose by homogeneous esterification of cellulose based on ionic liquids // Propellants, Explosives, Pyrotechnics. 2023. Vol. 48, no. 2. P. e202200186. DOI: 10.1002/prep.202200186.Duan X., Li Z., Wu B., Shen J., Pei C. Preparation of nitrocellulose by homogeneous esterification of cellulose based on ionic liquids. Propellants, Explosives, Pyrotechnics. 2023;48(2):e202200186. DOI: 10.1002/prep.202200186.Tarchoun A.F., Trache D., Klapötke T.M., Krumm B., Mezroua A., Derradji M., et al. Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials // Cellulose. 2021. Vol. 28. P. 6107–6123. DOI: 10.1007/s10570-021-03965-w.Tarchoun A.F., Trache D., Klapötke T.M., Krumm B., Mezroua A., Derradji M., et al. Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials. Cellulose. 2021;28:6107-6123. DOI: 10.1007/s10570-021-03965-w.

The authors declare that there are no conflicts of interest present.