ИСПОЛЬЗОВАНИЕ ИММОБИЛИЗОВАННОЙ ЦЕЛЛЮЛАЗЫ В ПРОЦЕССАХ ПЕРЕРАБОТКИ ЦЕЛЛЮЛОЗОСОДЕРЖАЩИХ ОТХОДОВ
Аннотация
Лигноцеллюлозная биомасса, источник целлюлозы, является самым распространенным возобновляемым ресурсом на Земле. Источниками целлюлозы промышленных масштабов могут служить сельскохозяйственные отходы, травянистые культуры, побочные продукты лесного хозяйства, отходы целлюлозно-бумажной и пищевой промышленности, а также твердые бытовые отходы. В данном обзоре представлены основные типы целлюлозосодержащих отходов, требующих переработки. Благодаря гидролизу целлюлозы можно получить огромное количество важнейших химических продуктов, таких как, например, биотопливо. Гидролиз целлюлозы можно легко осуществлять без применения многоступенчатых процессов и в мягких условиях с помощью целлюлаз. Целлюлаза представляет собой смесь ферментов с активностью эндоглюканазы, экзоглюканазы и β-глюкозидазы, которая катализирует многоступенчатый гидролиз целлюлозы до глюкозы. Целлюлазы обладают уникальным биотехнологическим потенциалом преобразования, поэтому они открывают возможности для разработки новых биопроцессов и продуктов. В настоящее время целлюлазы находят широкое применение в сельском хозяйстве, пивоварении и виноделии, производстве биоэтанола, текстильной промышленности, переработке пищевых продуктов, производстве бумаги и целлюлозы, экстракции оливкового масла, а также в фармацевтике и медицине. Однако, широкое использование целлюлаз ограничено их высокой стоимостью и невозможностью повторного использования. Иммобилизация ферментов на различных носителях позволяет сохранить их активность и снизить производственные затраты. Поскольку при иммобилизации ферментов важную роль играет носитель, в работе представлены различные виды наноструктурированных носителей, включая магнитоотделяемые, используемых при иммобилизации целлюлаз. Иммобилизация ферментов на наноносителях может значительно увеличить жизненные циклы биокатализаторов, тем самым снижая стоимость производства. Также в работе указываются некоторые мультиферментные системы, полученные с использованием целлюлаз.
Для цитирования:
Гребенникова О.В., Сульман А.М., Тихонов Б.Б., Молчанов В.П., Матвеева В.Г. Использование иммобилизованной целлюлазы в процессах переработки целлюлозосодержащих отходов. Мини обзор. Изв. вузов. Химия и хим. технология. 2025. Т. 68. Вып. 12. С. 23-33. DOI: 10.6060/ivkkt.20256812.7242.
Литература
Stabnikova O., Shevchenko O., Stabnikov V., Paredes-López O. Bioconversion of Wastes to Value-added Products. CRC Press. 2023. Р. 271–304. DOI: 10.1201/9781003329671.
Allwyn A., Vasudevan T. A review on cellulose and its utilization from agro-industrial waste. Drug Invent. Today. 2018. N 10. P. 89-94.
Okonko I.O., Adeola O.T., Aloysius F.E., Damilola A.O., Adewale O.A. Utilization of food wastes for sustainable development, electronic. J. Environ. Agric. Food Chem. 2007. N 8. P. 263-286.
Aziz T., Farid A., Haq F., Kiran M., Ullah A., Zhang K., Li C., Ghazanfar S., Sun H., Ullah R., Ali A., Muzammal M., Shah M., Akhtar N., Selim S., Hagagy N., Samy M., Al Jaouni S.K. A Review on the Modification of Cellulose and Its Applications. Polymers. 2022. N 15. P. 3206. DOI: 10.3390/polym14153206.
Etale A, Onyianta A.J, Turner S.R, Eichhorn S.J. Cellu-lose: A Review of Water Interactions, Applications in Com-posites, and Water Treatment. Chem Rev. 2023. V. 8. N 123. P. 2016-2048. DOI: 10.1021/acs.chemrev.2c00477.
Allwyn A., Vasudevan. T. A review on cellulose and its utilization from agro-industrial waste. Drug Invent. Today. 2018. N 10. P. 89-94.
Osipov D.O., Dotsenko G.S., Sinitsyna O.A., Kondratieva E.G., Zorov I.N., Shashkov I.A., Satrutdinov A.D., Sinitsyn A.P. Comparative Study of the Convertibility of Agricultural Residues and Other Cellulose-Containing Materials in Hydrolysis with Penicillium verruculosum Cellulase Complex. Agronomy. 2020. N 10. P. 1712. DOI: 10.3390/agronomy10111712.
Van den Born G.J., van Minnen J.G., Olivier J.G.J., Ros J.P.M. Integrated analysis of global biomass flows in search of the sustainable potential for bioenergy production. PBL. 2014. N 24. P. 1509.
Kadam K., McMillan J. Availability of corn stover as a sustainable feedstock for bioethanol production. Bioresour. Technol. 2003. N 88. P. 17–25. DOI: 10.1016/S0960-8524(02)00269-9.
Pippo W.A., Luengo C.A. Sugarcane energy use: Accounting of feedstock energy considering current agro-industrial trends and their feasibility. Int. J. Energy Environ. Eng. 2013. N 4. P. 10. DOI: 10.1186/2251-6832-4-10.
Kim S., Dale B.E. Global potential bioethanol production from wasted crops and crop residues. Biomass Bioenergy. 2004. N 26. P. 361–375. DOI: 10.1016/j.biombioe.2003.08.002.
Kuramshin A.I., Kuramshina E.A. Preparation of micro-crystalline cellulose from sugar beet pulp and its properties. Uch. Zap. Kazan. Univ. 2015. N 157. P. 18–26 (in Russian).
Riseh R.S., Vazvani M.G., Hassanisaadi M., Thakur V.K. Agricultural wastes: A practical and potential source for the isolation and preparation of cellulose and application in agriculture and different industries. Ind. Crops Prod. 2024. N 208. 117904. DOI: 10.1016/j.indcrop.2023.117904.
Searle S., Malins C. Availability of Cellulosic Residues and Wastes in the EU. White Paper [International Council on Clean Transportation]. 2013.
Mokhirev A.P., Zyryanov M.A. Logging operation technology with felling residue sorting. Syst. Methods. Technol. 2015. № 3 (27). P. 118-122.
Jeevahan J., Anderson A., Sriram V., Durairaj R.B., Britto Joseph G., Mageshwaran G. Waste into energy con-version technologies and conversion of food wastes into the potential products: a review. Int. J. Ambient Energy. 2018. N 42. P. 1083–1101. DOI: 10.1080/01430750.2018.1537939.
Prückler M., Siebenhandl-Ehn S., Apprich S., Höltinger S., Haas C., Schmid E., Kneifel W. Wheat bran-based biorefinery 1: Composition of wheat bran and strategies of functionalization. LWT-Food Sci. Technol. 2014. N 56. P. 211–221. DOI: 10.1016/j.lwt.2013.12.004.
Trivedi R.K. Biofuel from Wastes an Economic and Envi-ronmentally Feasible Resource. Energy Procedia. 2014. N 54. P. 634–641. DOI: 10.1016/j.egypro.2014.07.305.
Liu J., Guan X., Zhu D., Sun J. Optimization of the enzymatic pretreatment in oat bran protein extraction by particle swarm optimization algorithms for response surface modeling. LWT-Food Sci. Technol. 2008. N 41. P. 1913–1918. DOI: 10.1016/j.lwt.2008.02.013.
Allwyn A., Vasudevan T. A review on cellulose and its utilization from agroindustrial waste. Drug Invent. Today. 2018. N 10. P. 89-94.
Mandels M., Hontz L., Nystrom J. Enzymatic hydrolysis of waste cellulose. Biotechnol. Bioeng. 1974. N 16. P. 1471–1493. DOI: 10.1002/bit.260161105.
Maksimov A.Y. Investigation of the properties and microbiological composition of bark-wood waste from a bark dump. Vestn. Perm. Nats. Issl. Politekh. Univ. Khim. Tekhnol. Biotekhnol. 2018. V. 4. P. 98-112 (in Russian).
Maksimov A.Yu., Maksimova Yu.G., Shilova A.V., Shchetko V.A. Cultures of microorganisms producing hydrolytic enzymes, promising for processing agricultural and food industry waste. Microb. Biotekhnol.: Fund. Prikl. Asp. 2021. V. 13. P. 348-359 (in Russian). DOI: 10.47612/2226-3136-2021-13-348-359.
Sklyadnev E.V., Balabanova M.Yu., Ignatieva N.N. Complex processing of cellulose-containing waste from poultry farms and sugar production. Vestn. VGUIT. 2015. N 3. P. 136-140 (in Russian).
Haile A., Gelebo G.G., Tesfaye T. Pulp and paper mill wastes: utilizations and prospects for high value-added biomaterials. Bioresour. Bioprocess. 2021. N 8. P. 35. DOI: 10.1186/s40643-021-00385-3.
Manaenkov O.V., Kislitsa O.V., Matveeva V.G., Sulman E.M., Sulman M.G., Bronstein L.M. Cellulose Conversion Into Hexitols and Glycols in Water: Recent Advances in Catalyst Development. Front. Chem. 2019. V. 7. N 834. P. 8. DOI: 10.3389/fchem.2019.00834.
Shatrova A.S. Technology of pro-cessing pulp and paper industry waste into soils using natural processes. Izv. Tomsk. Politekh. Univ. Inzhiniring Georesur-sov. 2022. V. 333. N 8. P. 153-162 (in Russian). DOI: 10.18799/ 24131830/2022/8/3658.
Malykhin V.V. Fundamental research and practical developments in the field of technical chemistry. B.: Izd-vo Altay. gos. tekhn. univ. 2021. 375 p. (in Russian).
Koksharov S.A., Aleeva S.V., Kalinin E.N. Comparison of the structure of lignin in the bast and woody parts of flax stem and its transformations in the presence of sulfur-containing reducing agents. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 9. P. 90-102 (in Russian). DOI: 10.6060/ivkkt.20246709.7037.
Østby H., Hansen L.D., Horn S.J. Enzymatic processing of lignocellulosic biomass: principles, recent advances and perspectives. J. Ind. Microbiol. Biotechnol. 2020. N 47. P. 623–657. DOI: 10.1007/s10295-020-02301-8.
Houfani A.A., Anders N., Loogen J. Lignocellulosic biomass degradation enzymes and characterization of cellulase and xylanase from Bosea sp. FBZP-16. Biomass. Conv. Bio-ref. 2023. V. 13. P. 12085–12103. DOI: 10.1007/s13399-021-02044-1.
Gaurav N., Sivasankari S., Kiran G.S., Ninawe A., Selvin J. Utilization of bioresources for sustainable biofuels: A Review. Renew. Sustain. Energy Rev. 2017. V. 73. P. 205-214. DOI: 10.1016/j.rser.2017.01.070.
Rabinovich M.L., Melnik M.S. Progress in the study of cellulolytic enzymes and the mechanism of biodegradation of highly concentrated forms of cellulose. Usp. Biolog. Khim. 2000. V. 40. P. 205-266 (in Russian).
Fomenko I.A., Tuchkova S.N. Utilization of cellulose-containing waste using mushrooms. Novye Tekhnol. 2021. V. 17. P. 123-133 (in Russian). DOI: 10.47370/2072-0920-2021-17-5-123-133.
Khoshnevisan K., Poorakbar E., Baharifar H., Barkhi M. Recent Advances of Cellulase Immobilization onto Magnetic Nanoparticles: An Update Review. Magnetochemistry. 2019. N 5. P. 36. DOI: 10.3390/magnetochemistry5020036.
Califano V., Costantini A. Immobilization of Cellulolytic Enzymes in Mesostructured Silica Materials. Catalysts. 2020. N 10. P. 706. DOI: 10.3390/catal10060706.
Sulman A.M., Matveeva V.G., Bronstein L.M. Cellulase Immobilization on Nanostructured Supports for Biomass Waste Processing Nanomaterials. 2022. N 12. P. 3796. DOI: 10.3390/nano12213796.
Sulman A., Grebennikova O., Tikhonov B., Molchanov V., Matveeva V. Immobilized cellulase: interactions between cellulase and nanostructured supports. BIO Web Conferences. 2023. N 64. P. 01016. DOI: 10.1051/bioconf/20236401016.
Cavalcante F.T.T., de A. Falcao I.R., da S. Souza J.E., Rocha T.G., de Sousa I.G., Cavalcante A.L.G., de Oliveira A.L.B., de Sousa M.C.M., dos Santos J.C.S. De-signing of Nanomaterials-Based Enzymatic Biosensors: Synthesis, Properties, and Applications. Electrochem. 2021. N 2. P. 149–184. DOI: 10.3390/electrochem2010012.
Zarei A., Alihosseini F., Parida D., Nazir R., Gaan S. Fabrication of Cellulase Catalysts Immobilized on a Nanoscale Hybrid Polyaniline/Cationic Hydrogel Support for the Highly Efficient Catalytic Conversion of Cellulose. ACS Appl. Mater. Interfaces. 2021. N 13. P. 49816–49827. DOI: 10.1021/acsami.1c12263.
Ahmed I.N., Chang R., Tsai W.-B. Poly(acrylic acid) nanogel as a substrate for cellulase immobilization for hydrolysis of cellulose. Colloids Surf. B. 2017. N 152. P. 339–343. DOI: 10.1016/j.colsurfb.2017.01.040.
Pota G., Sapienza Salerno A., Costantini A., Silvestri B., Passaro J., Califano V. Co-immobilization of Cellulase and β-Glucosidase into Mesoporous Silica Nanoparticles for the Hydrolysis of Cellulose Extracted from Eriobotrya japonica Leaves. Langmuir. 2022. N 38. P. 5481–5493. DOI: 10.1021/acs.langmuir.2c00053.
Chen B., Qiu J., Mo H., Yu Y., Ito K., Sakai E., Feng H. Synthesis of mesoporous silica with different pore sizes for cellulase immobilization: Pure physical adsorption. New J. Chem. 2017. N 41. P. 9338–9345. DOI: 10.1039/C7NJ00441A.
Grebennikova O.V., Mikhailova A.N., Molchanov V.P., Sulman A.M., Doluda V.Yu., Matveeva V.G. Polymeric supports for enzymes immobilization in synthesis of biologically active compounds. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2021. V. 64. N 1. P. 67-72. (in Rus-sian). DOI: 10.6060/ivkkt.20216401.6223.
Wang Y., Chen D., Wang G., Zhao C., Ma Y., Yang W. Immobilization of cellulase on styrene/maleic anhydride copolymer nanoparticles with improved stability against pH changes. Chem. Eng. J. 2018. N 336. P. 152–159. DOI: 10.1016/j.cej.2017.11.030.
Saha K., Verma P., Sikder J., Chakraborty S., Curcio S. Synthesis of chitosan-cellulase nanohybrid and immobilization on alginate beads for hydrolysis of ionic liquid pretreated sug-arcane bagasse. Renew. Energy. 2019. N 133. P. 66–76. DOI: 10.1016/j.renene.2018.10.014.
Hamzah A., Sitompul L.L., Putri I.N.F., Soeprijanto Widjaja A. Synergistic effect of two type cellulase immobi-lized on chitosan microparticle as biocatalyst for coconut husk hydrolysis. Indones. J. Chem. 2019. V. 19. N 2. P. 495-502. DOI: 10.22146/ijc.39714.
Egwim E.C., Agboola А.О., Saidu A.N. Immobilization of cellulase and yeast for the hydrolysis and fermentation of pretreated bagasse for ethanol production. Niger. J. Biotechnol. 2019. V. 36. N 1. Р. 113-121. DOI: 10.4314/njb.v36i1.15.
Li L.J., Xia W.J., Ma G.P. A study on the enzymatic properties and reuse of cellulase immobilized with carbon nanotubes and sodium alginate. AMB Expr. 2019. N 9. P. 112. DOI: 10.1186/s13568-019-0835-0.
Manikant T., Rajeev S., Subhash C., Neha S. Bioderived nanostructure and their functional contribution in immobilization of cellulolytic enzymes for improving biosensing application. J. Molec. Struct. 2025. V. 1321. N 2. P. 139811. DOI: 10.1016/j.molstruc.2024.139811.
Papadopoulou A., Zarafeta D., Galanopoulou A.P., Stamatis H. Enhanced Catalytic Performance of Trichoderma reesei Cellulase Immobilized on Magnetic Hierarchical Porous Carbon Nanoparticles. Protein J. 2019. N 38. P. 640–648. DOI: 10.1007/s10930-019-09869-w.
Pei J., Huang Y., Yang Y., Yuan H., Liu X., Ni C. A Novel Layered Anchoring Structure Immobilized Cellulase via Covalent Binding of Cellulase on MNPs Anchored by LDHs. J. Inorg. Organomet. Polym. Mater. 2018. N 28. P. 1624–1635. DOI: 10.1007/s10904-018-0838-3.
Khorshidi J., Lenjannezhadian K., Jamalan H., Zeinali M. Preparation and characterization of nanomagnetic crosslinked cellulase aggregates for cellulose bioconversion. J. Chem. Technol. Biotechnol. 2015. N 91. P. 539-546. DOI: 10.1002/jctb.4615.
Raza S., Yong X., Deng J. Immobilizing cellulase on multilayered magnetic hollow particles: Preparation, bio-catalysis and adsorption performances. Micropor. Mesopor. Mater. 2019. N 285. P. 112–119. DOI: 10.1016/j.micromeso.2019.05.011.
Tan L., Tan Z., Feng H., Qiu J. Cellulose as a template to fabricate a cellulase-immobilized composite with high bioactivity and reusability. New J. Chem. 2018. N 42. P. 1665–1672. DOI: 10.1039/C7NJ03271D.
Xiaoxiao Y., Jianzhen L., Yan S., Yubing X., Yingjie S., Shanshan T., Sijia B., Liying L., Fei H., Qing H., Guang C. Co-immobilized multi-enzyme biocatalytic system on reversible and soluble carrier for saccharification of corn straw cellulose. Biores. Technol. 2024. V. 395. P. 130325. DOI: 10.1016/j.biortech.2024.130325.
Wu D., Zhuang M., Su G., Gao P., Jin Y., Fu H. Ptimization of Co-immobilization of Cellulase and β-glucosidase. IOP Conf. Ser.: Earth Environ. Sci. 2020. N 435. P. 012006. DOI: 10.1088/1755-1315/435/1/012006.
Gao J., Bai S., Wang F., Yang L., Hu Y., Yang Y., Bai B., Zhang Z. Compartmentalized co-immobilization of cellulase and cellobiose phosphorylase within zeolitic imidazolate framework efficiently synthesizes 1-p-Glc: Glycosylation of 18FDG. Int. J. Biolog. Macromol. 2025. V. 288. P. 138653. DOI: 10.1016/j.ijbiomac.2024.138653.
Chavan S., Gaikwad A. Extraction and recovery of lignin derived phenolic inhibitors to enhance enzymatic glucose production. Biomass Bioenergy. 2021. N 144. P. 105897. DOI: 10.1016/j.biombioe.2020.105897.
Kumar V., Patel S.K.S., Gupta R.K., Otari S.V., Gao H., Lee J.-K., Zhang L. Enhanced Saccharification and Fermentation of Rice Straw by Reducing the Concentration of Phenolic Compounds Using an Immobilized Enzyme Cocktail. Biotechnol. J. 2019. N 14. P. 1800468. DOI: 10.1002/biot.201800468.
Yi J., Qiu M., Zhu Z., Dong X., Decker E.A., McClements D.J. Robust and recyclable magnetic nanobiocatalysts for ex-traction of anthocyanin from black rice. Food Chem. 2021. N 364. P. 130447. DOI: 10.1016/j.foodchem.2021.130447.
Zhang H., Hua S.‐F., Zhang L. Co-immobilization of cellu-lase and glucose oxidase on graphene oxide by covalent bonds: a biocatalytic system for onepot conversion of gluconic acid from carboxymethyl cellulose. J. Chem. Technol. Biotechnol. 2019. N 95. Iss. 4. P. 1116-1125. DOI: 10.1002/jctb.6296.
Shen N., Hua S. Co-immobilization of Cellulase and Glucose Oxidase Layerby-Layer and Chain Catalytic Reaction. Catal. Lett. 2024. N 154. P. 5698–5708. DOI: 10.1007/s10562-024-04750-7.
