vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/achb.938QJGTNQvuzbiochemi-1274Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESСинтез привитых сополимеров трескового коллагена и акриламидов в присутствии системы алкилборан – п-хинонSynthesis of grafted copolymers of cod collagen and acrylamides in the presence of alkylborane – p-quinone systemhttps://orcid.org/0000-0003-4151-9266КузнецоваЮ. Л.KuznetsovaYu. L.

Кузнецова Юлия Леонидовна - к.х.н., доцент, доцент.

603022, Нижний Новгород, пр. Гагарина, 23

Yulia L. Kuznetsova - Cand. Sci. (Chemistry), Associate Professor, Associate Professor.

23, Gagarin Ave., Nizhny Novgorod, 603022

kyul@yandex.ruhttps://orcid.org/0000-0003-2745-251XГущинаК. С.GushchinaK. S.

Гущина Ксения Сергеевна - аспирант, младший научный сотрудник.

603022, Нижний Новгород, пр. Гагарина, 23

Ksenya S. Gushchina - Postgraduate Student, Junior Researcher.

23, Gagarin Ave., Nizhny Novgorod, 603022

ksesha.gushchina@gmail.comhttps://orcid.org/0000-0003-1132-7212ЛобановаК. С.LobanovaK. S.

Лобанова Карина Сергеевна - аспирант, младший научный сотрудник.

603022, г. Нижний Новгород, пр. Гагарина, 23

Karina S. Lobanova - Postgraduate Student, Junior Researcher.

23, Gagarin Ave., Nizhny Novgorod, 603022

kariandrs2101@yandex.ruhttps://orcid.org/0000-0002-8038-8441РумянцеваВ. О.RumyantsevaV. O.

Румянцева Виктория Олеговна - младший научный сотрудник.

603022, г. Нижний Новгород, пр. Гагарина, 23

Victoria O. Rumyantseva - Junior Researcher.

23, Gagarin Ave., Nizhny Novgorod, 603022

11.04.96@mail.ruhttps://orcid.org/0000-0002-8815-9651ЕгорихинаМ. Н.EgorikhinaM. N.

Егорихина Марфа Николаевна - к.б.н., заведующий научной лабораторией.

603005, г. Нижний Новгород, пл. Минина и Пожарского, 10/1

Marfa N. Egorikhina - Cand. Sci. (Biology), Head of the Scientific Laboratory.

10/1, Minin i Pozharsky Sq., Nizhny Novgorod, 603005

egorihina.marfa@yandex.ruhttps://orcid.org/0000-0001-7940-0880ФарафонтоваЕ. А.FarafontovaE. A.

Фарафонтова Екатерина Александровна - лаборант, Научно-исследовательский институт экспериментальной онкологии и биомедицинских технологий.

603005, Нижний Новгород, пл. Минина и Пожарского, 10/1

Ekaterina A. Farafontova - Laboratory Assistant.

10/1, Minin i Pozharsky Sq., Nizhny Novgorod, 603005

ekaterina_farafontova@mail.ruhttps://orcid.org/0000-0002-2781-6419РубцоваЮ. П.RubtsovaYu. P.

Рубцова Юлия Павловна - к.б.н., научный сотрудник, Научно-исследовательский институт экспериментальной онкологии и биомедицинских технологий.

603005, Нижний Новгород, пл. Минина и Пожарского, 10/1

Yulia P. Rubtsova - Cand. Sci. (Biology), Researcher.

10/1, Minin i Pozharsky Sq., Nizhny Novgorod, 603005

rubincherry@yandex.ruhttps://orcid.org/0000-0003-3413-2899СеменычеваЛ. Л.SemenychevaL. L.

Семенычева Людмила Леонидовна - д.х.н., доцент, заведующий лабораторией.

603022, Нижний Новгород, пр. Гагарина, 23

Luydmila L. Semenycheva - Dr. Sci. (Chemistry), Associate Professor, Head of the Laboratory.

23, Gagarin Ave., Nizhny Novgorod, 603022

llsem@yandex.ruНижегородский государственный университет им. Н.И. ЛобачевскогоРоссияNational Research Lobachevsky State University of Nizhny NovgorodRussian FederationПриволжский исследовательский медицинский университет Министерства здравоохранения Российской ФедерацииРоссияPrivolzhsky Research Medical UniversityRussian Federation202430092024143305321Copyright © Кузнецова Ю.Л., Гущина К.С., Лобанова К.С., Румянцева В.О., Егорихина М.Н., Фарафонтова Е.А., Рубцова Ю.П., Семенычева Л.Л., 20242024Кузнецова Ю.Л., Гущина К.С., Лобанова К.С., Румянцева В.О., Егорихина М.Н., Фарафонтова Е.А., Рубцова Ю.П., Семенычева Л.Л.Kuznetsova Y.L., Gushchina K.S., Lobanova K.S., Rumyantseva V.O., Egorikhina M.N., Farafontova E.A., Rubtsova Y.P., Semenycheva L.L.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/1274

Была исследована привитая полимеризация акриламида и N-изопропилакриламида на коллаген в присутствии комплекса триэтилбор–гексаметилендиамин и ряда п-хинонов: бензохинона, нафтохинона, 2,5-ди-трет-бутил-п-бензохинона и дурохинона. Во всех случаях п-хиноны ведут себя как замедлители полимеризации и снижают конверсию мономера. Исключением является привитая полимеризация акриламида на коллаген в присутствии бензохинона, который проявляет себя ингибитором полимеризации. Доля синтетического фрагмента в полученных сополимерах определяется строением мономера и п-хинона. Кривые молекулярно-массового распределения содержат моды, относящиеся к непрореагировавшему коллагену, значительно отличающиеся по интенсивности от исходного коллагена. Это обусловлено образованием привитого сополимера сшитой структуры, который нельзя проанализировать методом гель-проникающей хроматографии. Разрушение сополимеров под действием ферментов контролировали методом гель-проникающей хроматографии. Ферментативный гидролиз сополимеров протекает медленнее, чем коллагена, что подтверждает образование сополимера. Через 3 часа после начала гидролиза кривые молекулярно-массового распределения содержат низкомолекулярные моды коллагена и моды низкой интенсивности, относящиеся к полиакриламидам. Морфология сополимеров отличается от морфологии коллагена и полиакриламидов. Оценка цитотоксичности – важный этап исследований сополимеров, позволяющий рассматривать их как основу материалов для регенеративной медицины. Анализ экстрактов, полученных из сополимеров при помощи культуральной среды, методом МТТ-теста показал высокий ранг токсичности. Разведение экстрактов сополимеров коллагена и N-изопропилакриламида водными растворами приводит к ее снижению. Для сополимеров коллагена и акриламида токсичность сохраняется, что обусловлено высокой токсичностью мономера. Снижение токсичности сополимеров возможно после экстракции непрореагировавшего акриламида хлороформом.

The graft polymerization of acrylamide and N-isopropylacrylamide onto collagen in the presence of triethylborohexamethylenediamine complex and a number of p-quinones, including benzoquinone, naphthoquinone, 2,5-di-tretbutyl-p-benzoquinone, and duroquinone, was studied. In all cases, p-quinones act as polymerization retarders, reducing monomer conversion. An exception is the graft polymerization of acrylamide onto collagen in the presence of benzoquinone, which acts as a polymerization inhibitor. The proportion of the synthetic fragment in the obtained copolymers is determined by the structure of the monomer and p-quinone. The molecular weight distribution curves contain modes related to unreacted collagen, which differ significantly from those of the initial collagen in terms of intensity. This is related to the formation of a grafted copolymer of cross-linked structure, which cannot be analyzed by gel permeation chromatography. The degradation of copolymers under the action of enzymes was controlled by gel permeation chromatography. Enzymatic hydrolysis of copolymers proceeds slower than that of collagen, which confirms the formation of a copolymer. Following three hours after the onset of hydrolysis, the molecular weight distribution curves contain low-molecular weight modes of collagen and low-intensity modes related to polyacrylamide. The morphology of copolymers differs from that of collagen and polyacrylamides. Cytotoxicity evaluation of copolymers is an important research stage, determining their prospects as the basis of materials for regenerative medicine. An analysis of extracts obtained from the copolymers using culture medium by MTT assay showed a high rank of their toxicity, which can be reduced by dilution of collagen and N-isopropylacrylamide copolymer extracts with aqueous solutions. For the copolymers of collagen and acrylamide, the toxicity is maintained due to the high toxicity of the monomer. Their toxicity can be reduced by extraction of unreacted acrylamide with chloroform.

коллагенакриламидN-изопропилакриламидалкилборанп-хинонпривитой сополимерcollagenacrylamideN-isopropylacrylamidealkylboranep-quinonegrafted copolymerРабота выполнена при финансовой поддержке гранта Российского научного фонда № 22-23-20091The Russian Science Foundation financially supported this work (project no. 22-23-20091)ReferencesJagtap J.S., Labhade S.D., Chitlange S.S., Mahadevan S. Biopolymer conjugated protein based hydrogel scaffolds for tissue engineering application // International Journal of Pharmacy & Pharmaceutical Research. 2020. Vol. 17, no. 2. P. 284–316.Jagtap J.S., Labhade S.D., Chitlange S.S., Mahadevan S. Biopolymer conjugated protein based hydrogel scaffolds for tissue engineering application. International Journal of Pharmacy & Pharmaceutical Research. 2020;17(2):284-316.Kirillova A., Yeazel T.R., Asheghali D., Petersen S.R., Dort S., Gall K., et al. Fabrication of biomedical scaffolds using biodegradable polymers // Chemical Reviews. 2021. Vol. 121, no. 18. P. 11238–11304. DOI: 10.1021/acs.chemrev.0c01200.Kirillova A., Yeazel T.R., Asheghali D., Petersen S.R., Dort S., Gall K., et al. Fabrication of biomedical scaffolds using biodegradable polymers. Chemical Reviews. 2021;121(18):11238-11304. DOI: 10.1021/acs.chemrev.0c01200.Wang Y., Wang Z., Dong Y. Collagen-based biomaterials for tissue engineering // ACS Biomaterials Science & Engineering. 2023. Vol. 9, no. 3. P. 132–1150. DOI: 10.1021/acsbiomaterials.2c00730.Wang Y., Wang Z., Dong Y. Collagen-based biomaterials for tissue engineering. ACS Biomaterials Science & Engineering. 2023;9(3):1132-1150. DOI: 10.1021/acsbiomaterials.2c00730.Dewle A., Pathak N., Rakshasmare P., Srivastava A. Multifarious fabrication approaches of producing aligned collagen scaffolds for tissue engineering applications // ACS Biomaterials Science & Engineering. 2020. Vol. 6, no. 2. P. 779–797. DOI: 10.1021/acsbiomaterials.9b01225.Dewle A., Pathak N., Rakshasmare P., Srivastava A. Multifarious fabrication approaches of producing aligned collagen scaffolds for tissue engineering applications. ACS Biomaterials Science & Engineering. 2020;6(2):779-797. DOI: 10.1021/acsbiomaterials.9b01225.Sundar G., Joseph J., Prabhakumari C., John A., Abraham A. Natural collagen bioscaffolds for skin tissue engineering strategies in burns: a critical review // International Journal of Polymeric Materials and Polymeric Biomaterials. 2021. Vol. 70, no. 9. P. 593–604. DOI: 10.1080/00914037.2020.1740991.Sundar G., Joseph J., Prabhakumari C., John A., Abraham A. Natural collagen bioscaffolds for skin tissue engineering strategies in burns: a critical review. International Journal of Polymeric Materials and Polymeric Biomaterials. 2021;70(9):593-604. DOI: 10.1080/00914037.2020.1740991.Subhan F., Hussain Z., Tauseef I., Shehzad A., Wahid F. A review on recent advances and applications of fish collagen // Critical Reviews in Food Science and Nutrition. 2021. Vol. 61, no. 6. P. 1027–1037. DOI: 10.1080/10408398.2020.1751585.Subhan F., Hussain Z., Tauseef I., Shehzad A., Wahid F. A review on recent advances and applications of fish collagen. Critical Reviews in Food Science and Nutrition. 2021;61(6):1027-1037. DOI: 10.1080/10408398.2020.1751585.Lin K., Zhang D., Macedo M.H., Cui W., Sarmento B., Shen G. Advanced collagen-based biomaterials for regenerative biomedicine // Advanced Functional Materials. 2019. Vol. 29, no. 3. P. 1804943. DOI: 10.1002/adfm.201804943.Lin K., Zhang D., Macedo M.H., Cui W., Sarmento B., Shen G. Advanced collagen-based biomaterials for regenerative biomedicine. Advanced Functional Materials. 2019;29(3):1804943. DOI: 10.1002/adfm.201804943.Zheng M., Wang X., Chen Y., Yue O., Bai Z., Cui B., et al. A review of recent progress on collagen-based biomaterials // Advanced Healthcare Materials. 2023. Vol. 12, no. 16. P. 2202042. DOI: 10.1002/adhm.202202042.Zheng M., Wang X., Chen Y., Yue O., Bai Z., Cui B., et al. A review of recent progress on collagen-based biomaterials. Advanced Healthcare Materials. 2023;12(16):2202042. DOI: 10.1002/adhm.202202042.Rico-Llanos G.A., Borrego-González S., Moncayo-Donoso M., Becerra J., Visser R. Collagen type I biomaterials as scaffolds for bone tissue engineering // Polymers. 2021. Vol. 13, no. 4. P. 599. DOI: 10.3390/polym13040599.Rico-Llanos G.A., Borrego-González S., MoncayoDonoso M., Becerra J., Visser R. Collagen type I biomaterials as scaffolds for bone tissue engineering. Polymers. 2021;13(4):599. DOI: 10.3390/polym13040599.Vijayalekha A., Anandasadagopan S.K., Pandurangan A.K. An overview of collagen‑based composite scaffold for bone tissue engineering // Applied Biochemistry and Biotechnology. 2023. Vol. 195. P. 4617–4636. DOI: 10.1007/s12010-023-04318-y.Vijayalekha A., Anandasadagopan S.K., Pandurangan A.K. An overview of collagen-based composite scaffold for bone tissue engineering. Applied Biochemistry and Biotechnology. 2023;195:4617-4636. DOI: 10.1007/s12010-023-04318-y.Shekhter A.B., Fayzullin A.L., Vukolova M.N., Rudenko T.G., Osipycheva V.D., Litvitsky P.F. Medical applications of collagen and collagen-based materials // Current Medicinal Chemistry. 2019. Vol. 26, no. 3. P. 506–516. DOI: 10.2174/0929867325666171205170339.Shekhter A.B., Fayzullin A.L., Vukolova M.N., Rudenko T.G., Osipycheva V.D., Litvitsky P.F. Medical applications of collagen and collagen-based materials. Current Medicinal Chemistry. 2019;26(3):506-516. DOI: 10.2174/0929867325666171205170339.Fassini D., Wilkie I.C., Pozzolini M., Ferrario C., Sugni M., Rocha M.S., et al. Diverse and productive source of biopolymer inspiration: marine collagens // Biomacromolecules. 2021. Vol. 22, no. 5. P. 1815–1834. DOI: 10.1021/acs.biomac.1c00013.Fassini D., Wilkie I.C., Pozzolini M., Ferrario C., Sugni M., Rocha M.S., et al. Diverse and productive source of biopolymer inspiration: marine collagens. Biomacromolecules. 2021;22(5):1815-1834. DOI: 10.1021/ acs.biomac.1c00013.Rahman M.A. Collagen of extracellular matrix from marine invertebrates and its medical applications // Marine Drugs. 2019. Vol. 17, no. 2. P. 118. DOI: 10.3390/md17020118.Rahman M.A. Collagen of extracellular matrix from marine invertebrates and its medical applications. Marine Drugs. 2019;17(2):118. DOI: 10.3390/md17020118.Coppola D., Oliviero M., Vitale G.A., Lauritano C., D’Ambra I., Iannace S., et al. Marine collagen from alternative and sustainable sources: extraction, processing and applications // Marine Drugs. 2020. Vol. 18, no. 4. P. 214. DOI: 10.3390/md18040214.Coppola D., Oliviero M., Vitale G.A., Lauritano C., D’Ambra I., Iannace S., et al. Marine collagen from alternative and sustainable sources: extraction, processing and applications. Marine Drugs. 2020;18(4):214. DOI: 10.3390/md18040214.Jafari H., Lista A., Siekapen M.M., Ghaffari-Bohlouli P., Nie L., Alimoradi H., et al. Fish collagen: extraction, characterization, and applications for biomaterials engineering // Polymers. 2020. Vol. 12, no. 10. P. 2230. DOI: 10.3390/polym12102230.Jafari H., Lista A., Siekapen M.M., Ghaffari-Bohlouli P., Nie L., Alimoradi H., et al. Fish collagen: extraction, characterization, and applications for biomaterials engineering. Polymers. 2020;12(10):2230. DOI: 10.3390/polym12102230.Rajabimashhadi Z., Gallo N., Salvatore L., Lionetto F. Collagen derived from fish industry waste: progresses and challenges // Polymers. 2023. Vol. 15, no. 3. P. 544. DOI: 10.3390/polym15030544.Rajabimashhadi Z., Gallo N., Salvatore L., Lionetto F. Collagen derived from fish industry waste: progresses and challenges. Polymers. 2023;15(3):544. DOI: 10.3390/polym15030544.Salvatore L., Gallo N., Natali M.L., Campa L., Lunetti P., Madaghiele M., et al. Marine collagen and its derivatives: versatile and sustainable bio-resources for healthcare // Materials Science & Engineering C. 2020. Vol. 113. P. 110963. DOI: 10.1016/j.msec.2020.110963.Salvatore L., Gallo N., Natali M.L., Campa L., Lunetti P., Madaghiele M., et al. Marine collagen and its derivatives: versatile and sustainable bio-resources for healthcare. Materials Science & Engineering C. 2020;113:110963. DOI: 10.1016/j.msec.2020.110963.Hu Y., Liu L., Gu Z., Dan W., Dan N., Yu X. Modification of collagen with a natural derived cross-linker, alginate dialdehyde // Carbohydrate Polymers. 2014. Vol. 102. P. 324–332. DOI: 10.1016/j.carbpol.2013.11.050.Hu Y., Liu L., Gu Z., Dan W., Dan N., Yu X. Modification of collagen with a natural derived cross-linker, alginate dialdehyde. Carbohydrate Polymers. 2014;102:324-332. DOI: 10.1016/j.carbpol.2013.11.050.Fathima N.N., Rao J.R., Nair B.U. Effect of UV irradiation on the physico-chemical properties of iron crosslinked collagen // Journal of Photochemistry and Photobiology B: Biology. 2011. Vol. 105, no. 3. P. 203–206. DOI: 10.1016/j.jphotobiol.2011.09.003.Fathima N.N., Rao J.R., Nair B.U. Effect of UV irradiation on the physico-chemical properties of iron crosslinked collagen. Journal of Photochemistry and Photobiology B: Biology. 2011;105(3):203-206. DOI: 10.1016/j.jphotobiol.2011.09.003.Cao S., Li H., Li K., Lu J., Zhang L. A dense and strong bonding collagen film for carbon/carbon composites // Applied Surface Science. 2015. Vol. 347. P. 307–314. DOI: 10.1016/j.apsusc.2015.04.081.Cao S., Li H., Li K., Lu J., Zhang L. A dense and strong bonding collagen film for carbon/carbon composites. Applied Surface Science. 2015;347:307-314. DOI: 10.1016/j. apsusc.2015.04.081.Zeugolis D.I., Paul G.R., Attenburrow G. Crosslinking of extruded collagen fibers – a biomimetic three-dimensional scaffold for tissue engineering applications // Journal of Biomedical Materials Research Part A. 2009. Vol. 89A, no. 4. P. 895–908. DOI: 10.1002/jbm.a.32031.Zeugolis D.I., Paul G.R., Attenburrow G. Cross-linking of extruded collagen fibers – a biomimetic three-dimensional scaffold for tissue engineering applications. Journal of Biomedical Materials Research Part A. 2009;89A(4):895-908. DOI: 10.1002/jbm.a.32031.Zhou X., Wang J., Fang W., Tao Y., Zhao T., Xia K., et al. Genipin cross-linked type II collagen/chondroitin sulfate composite hydrogel-like cell delivery system induces differentiation of adipose-derived stem cells and regenerates degenerated nucleus pulposus // Acta Biomaterialia. 2018. Vol. 71. P. 496–509. DOI: 10.1016/j.actbio.2018.03.019.Zhou X., Wang J., Fang W., Tao Y., Zhao T., Xia K., et al. Genipin cross-linked type II collagen/chondroitin sulfate composite hydrogel-like cell delivery system induces differentiation of adipose-derived stem cells and regenerates degenerated nucleus pulposus. Acta Biomaterialia. 2018;71:496-509. DOI: 10.1016/j.actbio.2018.03.019.Goodarzi H., Jadidi K., Pourmotabed S., Sharifi E., Aghamollaei H. Preparation and in vitro characterization of cross-linked collagen–gelatin hydrogel using EDC/NHS for corneal tissue engineering applications // International Journal of Biological Macromolecules. 2019. Vol. 126. P. 620–632. DOI: 10.1016/j.ijbiomac.2018.12.125.Goodarzi H., Jadidi K., Pourmotabed S., Sharifi E., Aghamollaei H. Preparation and in vitro characterization of cross-linked collagen–gelatin hydrogel using EDC/NHS for corneal tissue engineering applications. International Journal of Biological Macromolecules. 2019;126:620-632. DOI: 10.1016/j.ijbiomac.2018.12.125.Mu C., Liu F., Cheng Q., Li H., Wu B., Zhang G., et al. Collagen cryogel cross-linked by dialdehyde starch // Macromolecular Materials and Engineering. 2010. Vol. 295, no. 2. P. 100–107. DOI: 10.1002/mame.200900292.Mu C., Liu F., Cheng Q., Li H., Wu B., Zhang G., et al. Collagen cryogel cross-linked by dialdehyde starch. Macromolecular Materials and Engineering. 2010;295(2):100-107. DOI: 10.1002/mame.200900292.Chen Z.G., Wang P.W., Wei B., Mo X.M., Cui F.Z. Electrospun collagen–chitosan nanofiber: a biomimetic extracellular matrix for endothelial cell and smooth muscle cell // Acta Biomaterialia. 2010. Vol. 6, no. 2. P. 372–382. DOI: 10.1016/j.actbio.2009.07.024.Chen Z.G., Wang P.W., Wei B., Mo X.M., Cui F.Z. Electrospun collagen–chitosan nanofiber: a biomimetic extracellular matrix for endothelial cell and smooth muscle cell. Acta Biomaterialia. 2010;6(2):372-382. DOI: 10.1016/j.actbio.2009.07.024.Kaur S., Jindal R. Synthesis of interpenetrating network hydrogel from (gum copal alcohols-collagen)-co-poly(acrylamide) and acrylic acid: Isotherms and kinetics study for removal of methylene blue dye from aqueous solution // Materials Chemistry and Physics. 2018. Vol. 220. P. 75–86. DOI: 10.1016/j.matchemphys.2018.08.008.Kaur S., Jindal R. Synthesis of interpenetrating network hydrogel from (gum copal alcohols-collagen)-copoly(acrylamide) and acrylic acid: Isotherms and kinetics study for removal of methylene blue dye from aqueous solution. Materials Chemistry and Physics. 2018;220:75-86. DOI: 10.1016/j.matchemphys.2018.08.008.Ding C., Zhang M., Ma M., Zheng J., Yang Q., Feng R. Thermal and pH dual-responsive hydrogels based on semi-interpenetrating network of poly(N-isopropylacryl-amide) and collagen nanofibrils // Polymer International. 2019. Vol. 68, no. 8. P. 1468–1477. DOI: 10.1002/pi.5852.Ding C., Zhang M., Ma M., Zheng J., Yang Q., Feng R. Thermal and pH dual-responsive hydrogels based on semiinterpenetrating network of poly(N-isopropylacrylamide) and collagen nanofibrils. Polymer International. 2019;68(8):1468-1477. DOI: 10.1002/pi.5852.Luneva O.V., Fateev A.D., Kashurin A.I., Uspenskaya M.V. Study of the properties of semi-interpenetrating networks based on acrylic hydrogel and collagen // Журнал Сибирского федерального университета. Серия: Химия. 2022. Т. 15. N 3. С. 318–328. DOI: 10.17516/1998-2836-0295. EDN: DQGEBR.Luneva O.V., Fateev A.D., Kashurin A.I., Uspenskaya M.V. Study of the properties of semi-interpenetrating networks based on acrylic hydrogel and collagen. Journal of Siberian Federal University. Chemistry. 2022;15(3):318-328. DOI: 10.17516/1998-2836-0295. EDN: DQGEBR.Zhang M., Deng F., Tang L., Wu H., Ni Y., Chen L., et al. Super-ductile, injectable, fast self-healing collagen-based hydrogels with multi-responsive and accelerated woundrepair properties // Chemical Engineering Journal. 2021. Vol. 405. P. 126756. DOI: 10.1016/j.cej.2020.126756.Zhang M., Deng F., Tang L., Wu H., Ni Y., Chen L., et al. Super-ductile, injectable, fast self-healing collagenbased hydrogels with multi-responsive and accelerated wound-repair properties. Chemical Engineering Journal. 2021;405:126756. DOI: 10.1016/j.cej.2020.126756.Ullah K., Khan S.A., Murtaza G., Sohail M., Azizullah, Manan A., et al. Gelatin-based hydrogels as potential biomaterials for colonic delivery of oxaliplatin // International Journal of Pharmaceutics. 2019. Vol. 556. P. 236–245. DOI: 10.1016/j.ijpharm.2018.12.020.Ullah K., Khan S.A., Murtaza G., Sohail M., Azizullah, Manan A., et al. Gelatin-based hydrogels as potential biomaterials for colonic delivery of oxaliplatin. International Journal of Pharmaceutics. 2019;556:236-245. DOI: 10.1016/j.ijpharm.2018.12.020.Baek K., Clay N.E., Qin E.C., Sullivan K.M., Kim D.H., Kong H. In situ assembly of the collagen–polyacrylamide interpenetrating network hydrogel: Enabling decoupled control of stiffness and degree of swelling // European Polymer Journal. 2015. Vol. 72. P. 413–422. DOI: 10.1016/j.eurpolymj.2015.07.044.Baek K., Clay N.E., Qin E.C., Sullivan K.M., Kim D.H., Kong H. In situ assembly of the collagen–polyacrylamide interpenetrating network hydrogel: Enabling decoupled control of stiffness and degree of swelling. European Polymer Journal. 2015;72:413-422. DOI: 10.1016/j. eurpolymj.2015.07.044.Khanna N.D., Kaur I., Bhalla T.C., Gautam N. Effect of biodegradation on thermal and crystalline behavior of polypropylene–gelatin based copolymers // Journal of Applied Polymer Science. 2010. Vol. 118, no. 3. P. 1476–1488. DOI: 10.1002/app.32434.Khanna N.D., Kaur I., Bhalla T.C., Gautam N. Effect of biodegradation on thermal and crystalline behavior of polypropylene–gelatin based copolymers. Journal of Applied Polymer Science. 2010;118(3):1476-1488. DOI: 10.1002/app.32434.Bas O., De-Juan-Pardo E.M., Chhaya M.P., Wunner F.M., Jeon J.E., Klein T.J., et al. Enhancing structural integrity of hydrogels by using highly organised melt electrospun fibre constructs // European Polymer Journal. 2015. Vol. 72. P. 451–463. DOI: 10.1016/j.eurpolymj.2015.07.034.Bas O., De-Juan-Pardo E.M., Chhaya M.P., Wunner F.M., Jeon J.E., Klein T.J., et al. Enhancing structural integrity of hydrogels by using highly organised melt electrospun fibre constructs. European Polymer Journal. 2015;72:451-463. DOI: 10.1016/j.eurpolymj.2015.07.034.Fujisawa S., Kadoma Y. Tri-n-butylborane/watercomplex-mediated copolymerization of methyl methacrylate with proteinaceous materials and proteins: a review // Polymers. 2010. Vol. 2, no. 4. P. 575–595. DOI: 10.3390/polym2040575.Fujisawa S., Kadoma Y. Tri-n-butylborane/watercomplex-mediated copolymerization of methyl methacrylate with proteinaceous materials and proteins: a review. Polymers. 2010;2(4):575-595. DOI: 10.3390/polym2040575.Okamura H., Sudo A., Endo T. Generation of radical species on polypropylene by alkylborane-oxygen system and its application to graft polymerization // Journal of Polymer Science: Part A: Polymer Chemistry. 2009. Vol. 47, no. 22. P. 6163–6167. DOI: 10.1002/pola.23659.Okamura H., Sudo A., Endo T. Generation of radical species on polypropylene by alkylborane-oxygen system and its application to graft polymerization. Journal of Polymer Science: Part A: Polymer Chemistry. 2009;47(22):6163-6167. DOI: 10.1002/pola.23659.Liu S., Zheng Z., Li M., Wang X. Effect of oxidation progress of tributylborane on the grafting of polyolefins // Journal of Applied Polymer Science. 2012. Vol. 125, no. 5. P. 3335–3344. DOI: 10.1002/app.34232.Liu S., Zheng Z., Li M., Wang X. Effect of oxidation progress of tributylborane on the grafting of polyolefins. Journal of Applied Polymer Science. 2012;125(5):3335-3344. DOI: 10.1002/app.34232.Komabayashi T., Zhu Q., Eberhart R., Imai Y. Current status of direct pulp-capping materials for permanent teeth // Dental Materials Journal. 2016. Vol. 35, no. 1. P. 1–12. DOI: 10.4012/dmj.2015-013.Komabayashi T., Zhu Q., Eberhart R., Imai Y. Current status of direct pulp-capping materials for permanent teeth. Dental Materials Journal. 2016;35(1):1-12. DOI: 10.4012/dmj.2015-013.Sonnenschein M.F., Redwine O.D., Wendt B.L., Kastl P.E. Colloidal encapsulation of hydrolytically and oxidatively unstable organoborane catalysts and their use in waterborne acrylic polymerization // Langmuir. 2009. Vol. 25, no. 21. P. 12488–12494. DOI: 10.1021/la9017079.Sonnenschein M.F., Redwine O.D., Wendt B.L., Kastl P.E. Colloidal encapsulation of hydrolytically and oxidatively unstable organoborane catalysts and their use in waterborne acrylic polymerization. Langmuir. 2009;25(21):12488-12494. DOI: 10.1021/la9017079.Dodonov V.A., Starostina T.I. Radical bonding thermoplastics and materials with low surface energy using acrylate compositions // Polymer Science, Series D. 2018. Vol. 11. P. 60–66. DOI: 10.1134/S1995421218010069.Dodonov V.A., Starostina T.I. Radical bonding thermoplastics and materials with low surface energy using acrylate compositions. Polymer Science, Series D. 2018;11:60-66. DOI: 10.1134/S1995421218010069.Wilson O.R., Borrelli D.J., Magenau A.J.D. Simple and rapid adhesion of commodity polymer substrates under ambient conditions using complexed alkylboranes. ACS Omega. 2022. Vol. 7, no. 32. P. 28636–28645. DOI: 10.1021/acsomega.2c03740.Wilson O.R., Borrelli D.J., Magenau A.J.D. Simple and rapid adhesion of commodity polymer substrates under ambient conditions using complexed alkylboranes. ACS Omega. 2022;7(32):28636-28645. DOI: 10.1021/acsomega.2c03740.Kuznetsova Yu.L., Morozova E.A., Sustaeva K.S., Markin A.V., Mitin A.V., Baten’kin M.A., et al. Tributylborane in the synthesis of graft copolymers of collagen and polymethyl methacrylate // Russian Chemical Bulletin. 2022. Vol. 71. P. 389–398. DOI: 10.1007/s11172-022-3424-3.Kuznetsova Yu.L., Morozova E.A., Sustaeva K.S., Markin A.V., Mitin A.V., Baten’kin M.A., et al. Tributylborane in the synthesis of graft copolymers of collagen and polymethyl methacrylate. Russian Chemical Bulletin. 2022;71:389-398. DOI: 10.1007/s11172-022-3424-3.Kuznetsova Yu.L., Sustaeva K.S., Mitin A.V., Zakharychev E.A., Egorikhina M.N., Chasova V.O., et al. Graft polymerization of acrylamide in an aqueous dispersion of collagen in the presence of tributylborane // Polymers. 2022. Vol. 14, no. 22. P. 4900. DOI: 10.3390/polym14224900.Kuznetsova Yu.L., Sustaeva K.S., Mitin A.V., Zakharychev E.A., Egorikhina M.N., Chasova V.O., et al. Graft polymerization of acrylamide in an aqueous dispersion of collagen in the presence of tributylborane. Polymers. 2022;14(22):4900. DOI: 10.3390/polym14224900.Uromicheva M.A., Kuznetsova Y.L., Valetova N.B., Mitin A.V., Semenycheva L.L., Smirnova O.N. Synthesis of grafted polybutyl acrylate copolymer on fish collagen // Известия вузов. Прикладная химия и биотехнология. 2021. Т. 11. N 1. С. 16–25. DOI: 10.21285/2227-2925-2021-11-1-16-25. EDN: IJBJHH.Uromicheva M.A., Kuznetsova Y.L., Valetova N.B., Mitin A.V., Semenycheva L.L., Smirnova O.N. Synthesis of grafted polybutyl acrylate copolymer on fish collagen. Proceedings of Universities. Applied Chemistry and Biotechnology. 2021;11(1):16-25. DOI: 10.21285/2227-2925-2021-11-1-16-25. EDN: IJBJHH.Semenycheva L., Chasova V.O., Pegeev N.L., Uromicheva M.A., Mitin A.V., Kuznetsova Yu.L., et al. Production of graft copolymers of cod collagen with butyl acrylate and vinyl butyl ether in the presence of triethylborane – prospects for use in regenerative medicine // Polymers. 2023. Vol. 15, no. 15. P. 3159. DOI: 10.3390/polym15153159.Semenycheva L., Chasova V.O., Pegeev N.L., Uromicheva M.A., Mitin A.V., Kuznetsova Yu.L., et al. Production of graft copolymers of cod collagen with butyl acrylate and vinyl butyl ether in the presence of triethylborane – prospects for use in regenerative medicine. Polymers. 2023;15(15):3159. DOI: 10.3390/polym15153159.Kuznetsova Yu.L., Gushchina K.S., Lobanova K.S., Chasova V.O., Egorikhina M.N., Grigoryeva A.O., et al. Scaffold chemical model based on collagen–methyl methacrylate graft copolymers // Polymers. 2023. Vol. 15, no. 12. P. 2618. DOI: 10.3390/polym15122618.Kuznetsova Yu.L., Gushchina K.S., Lobanova K.S., Chasova V.O., Egorikhina M.N., Grigoryeva A.O., et al. Scaffold chemical model based on collagen–methyl methacrylate graft copolymers. Polymers. 2023;15(12):2618. DOI: 10.3390/polym15122618.Kuznetsova Yu., Gushchina K., Sustaeva K., Mitin A., Egorikhina M., Chasova V., et al. Grafting of methyl methacrylate onto gelatin initiated by tri-butylborane–2,5-di-tert-butyl-p-benzoquinone system // Polymers. 2022. Vol. 14, no. 16. P. 3290. DOI: 10.3390/polym14163290.Kuznetsova Yu., Gushchina K., Sustaeva K., Mitin A., Egorikhina M., Chasova V., et al. Grafting of methyl methacrylate onto gelatin initiated by tri-butylborane–2,5-di-tert-butyl-p-benzoquinone system. Polymers. 2022;14(16):3290. DOI: 10.3390/polym14163290.Kuznetsova Yu.L., Morozova E.A., Vavilova A.S., Markin A.V., Smirnova O.N., Zakharycheva N.S., et al. Synthesis of biodegradable grafted copolymers of gelatin and polymethyl methacrylate // Polymer Science, Series D. 2020. Vol. 13. P. 453–459. DOI: 10.1134/S1995421220040115.Kuznetsova Yu.L., Morozova E.A., Vavilova A.S., Markin A.V., Smirnova O.N., Zakharycheva N.S., et al. Synthesis of biodegradable grafted copolymers of gelatin and polymethyl methacrylate. Polymer Science, Series D. 2020;13:453-459. DOI: 10.1134/S1995421220040115.Kuznetsova Yu.L., Sustaeva K.S., Vavilova A.S., Markin A.V., Lyakaev D.V., Mitin A.V., et al. Tributylborane in the synthesis of graft-copolymers of gelatin and acrylamide // Journal of Organometallic Chemistry. 2020. Vol. 924. P. 121431. DOI: 10.1016/j.jorganchem.2020.121431.Kuznetsova Yu.L., Sustaeva K.S., Vavilova A.S., Markin A.V., Lyakaev D.V., Mitin A.V., et al. Tributylborane in the synthesis of graft-copolymers of gelatin and acrylamide. Journal of Organometallic Chemistry. 2020;924:121431. DOI: 10.1016/j.jorganchem.2020.121431.Пат. № 2567171, Российская Федерация, МПК C08H 1/06, A23J 1/04. Способ получения уксусной дисперсии высокомолекулярного рыбного коллагена / Л.Л. Семенычева, М.В. Астанина, Ю.Л. Кузнецова, Н.Б. Валетова, Е.В. Гераськина, О.А. Таранкова. Заявл. 06.10.2014; опубл. 10.11.2015. Бюл. № 31.Semenycheva L.L., Astanina M.V., Kuznetsova Yu.L., Valetova N.B., Geras’kina E.V., Tarankova O.A. Method for production of acetic dispersion of high molecular fish collagen. Patent RF, no. 2567171; 2015.Simándi T.L., Tüdös F. Kinetics of radical polymerization–XLV. Steric effects in the radical reactivity of quinones // European Polymer Journal. 1985. Vol. 21, no. 10. P. 865–869. DOI: 10.1016/0014-3057(85)90165-X.Simándi T.L., Tüdös F. Kinetics of radical polymerization–XLV. Steric effects in the radical reactivity of quinones. European Polymer Journal. 1985;21(10):865-869. DOI: 10.1016/0014-3057(85)90165-X.Nistor M.-T., Pamfil D., Schick C., Vasile C. Study of the heat-induced denaturation and water state of hybrid hydrogels based on collagen and poly (N-isopropyl acrylamide) in hydrated conditions // Thermochimica Acta. 2014. Vol. 589. P. 114–122. DOI: 10.1016/j.tca.2014.05.020.Nistor M.-T., Pamfil D., Schick C., Vasile C. Study of the heat-induced denaturation and water state of hybrid hydrogels based on collagen and poly (N-isopropyl acrylamide) in hydrated conditions. Thermochimica Acta. 2014;589:114-122. DOI: 10.1016/j.tca.2014.05.020.Kalinina E.A., Vavilova A.S., Sustaeva K.S., Kuznetsova Yu.L. Polymerization of alkyl (meth)acrylates in the presence of p-quinones // Russian Chemical Bulletin. 2021. Vol. 70. P. 1775–1783. DOI: 10.1007/s11172-021-3282-4.Kalinina E.A., Vavilova A.S., Sustaeva K.S., Kuznetsova Yu.L. Polymerization of alkyl (meth)acrylates in the presence of p-quinones. Russian Chemical Bulletin. 2021;70:1775-1783. DOI: 10.1007/s11172-021-3282-4.Dodonov V.A., Kuznetsova Yu.L., Vilkova A.I., Skuchilina A.S., Nevodchikov V.I., Beloded L.N. Uncontrolled pseudoliving free-radical polymerization of methyl methacrylate in the presence of butyl-p-benzoquinones // Russian Chemical Bulletin. 2007. Vol. 56. P. 1162–1165. DOI: 10.1007/s11172-007-0176-z.Dodonov V.A., Kuznetsova Yu.L., Vilkova A.I., Skuchilina A.S., Nevodchikov V.I., Beloded L.N. Uncontrolled pseudoliving free-radical polymerization of methyl methacrylate in the presence of butyl-p-benzoquinones. Russian Chemical Bulletin. 2007;56:1162-1165. DOI: 10.1007/s11172-007-0176-z.Semenycheva L.L., Egorikhina M.N., Chasova V.O., Valetova N.B., Podguzkova M.V., Astanina M.V., et al. Enzymatic hydrolysis of collagen by pancreatin and thrombin as a step in the formation of scaffolds // Russian Chemical Bulletin. 2020. Vol. 69. P. 164–168. DOI: 10.1007/s11172-020-2738-2.Semenycheva L.L., Egorikhina M.N., Chasova V.O., Valetova N.B., Podguzkova M.V., Astanina M.V., et al. Enzymatic hydrolysis of collagen by pancreatin and thrombin as a step in the formation of scaffolds. Russian Chemical Bulletin. 2020;69:164-168. DOI: 10.1007/s11172-020-2738-2.Bender M.L., Bergeron R.J., Komiyama M. The bioorganic chemistry of enzymatic catalysis. New York. Wiley-Interscience, 1984. 312 p.Bender M.L., Bergeron R.J., Komiyama M. The bioorganic chemistry of enzymatic catalysis. New York. Wiley-Interscience; 1984, 312 p.

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