{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T15:23:55Z","timestamp":1767885835540,"version":"3.49.0"},"reference-count":36,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T00:00:00Z","timestamp":1767830400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Shandong Provincial Laboratory Project","award":["SYS202209"],"award-info":[{"award-number":["SYS202209"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>This study addresses the issues of poor stability and difficulty in recovery of free horseradish peroxidase (HRP) by developing a multi-level composite immobilized carrier that combines high loading capacity with long-term stability. The SiO2@MnO2@MAF-7 core\u2013shell structured carrier was prepared via a solvothermal self-assembly method. Three immobilization strategies\u2014adsorption, covalent cross-linking, and encapsulation\u2014were systematically compared for their immobilization efficacy on HRP. The material structure was analyzed using techniques such as specific surface area analysis (BET), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) to characterize the material structure. Enzyme kinetic parameter determination experiments were conducted to systematically evaluate the performance advantages of the immobilized enzyme. BET analysis showed that SiO2@MnO2@MAF-7 had a specific surface area of 251.99 m2\/g and a mesoporous area of 12.47 nm, and its HRP loading was 50.37 U\/mg (immobilization efficiency 85.03%). Compared with free HRP, the Km value of the immobilized enzyme was decreased by 42%, the activity retention rate was increased by 35\u201350% at 80 \u00b0C and pH 4\u20139, and the activity was maintained by 65% after five repeated uses. In this study, MAF-7 was combined with MnO2\/SiO2 for HRP immobilization for the first time, and the triple effect of rigid support-catalytic synergy-confined protection synergistically improved the stability of the enzyme, providing a new strategy for the industrial application of oxidoreductases.<\/jats:p>","DOI":"10.3390\/ma19020254","type":"journal-article","created":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T10:10:50Z","timestamp":1767867050000},"page":"254","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Study on the Immobilization of Horseradish Peroxidase on a Multi-Level Composite Carrier SiO2@MnO2@MAF-7"],"prefix":"10.3390","volume":"19","author":[{"given":"Mengjie","family":"Huang","sequence":"first","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Baihui","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-2842-6256","authenticated-orcid":false,"given":"Xiangyu","family":"Jiang","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Maojie","family":"Jiang","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7152-9882","authenticated-orcid":false,"given":"Peng","family":"Yin","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xuan","family":"Fang","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yanna","family":"Lin","sequence":"additional","affiliation":[{"name":"Shandong Laboratory of Advanced Biomaterials and Medical Devices in Weihai, Weihai 264200, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fuqiang","family":"Ma","sequence":"additional","affiliation":[{"name":"Medical Enzyme Engineering Center, CAS Key Laboratory of Bio-Medical Diagnostics, Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou 215163, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2026,1,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"105654","DOI":"10.1016\/j.microc.2020.105654","article-title":"Comparison of the performance analytical of two glyphosate electrochemical screening methods based on peroxidase enzyme inhibition","volume":"160","author":"Kergaravat","year":"2021","journal-title":"Microchem. J."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"115264","DOI":"10.1016\/j.bios.2023.115264","article-title":"Antibiotic-enzyme-inorganic nanoflowers based immunoassay for the ultrasensitive detection of Staphylococcus aureus","volume":"230","author":"Zhao","year":"2023","journal-title":"Biosens. Bioelectron."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"940","DOI":"10.1038\/s41467-019-08731-y","article-title":"Modified carbon nitride nanozyme as bifunctional glucose oxidase-peroxidase for metal-free bioinspired cascade photocatalysis","volume":"10","author":"Zhang","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2307815","DOI":"10.1002\/smll.202307815","article-title":"Nanozyme-enhanced electrochemical biosensors, mechanisms and applications","volume":"20","author":"Yang","year":"2023","journal-title":"Small"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1249","DOI":"10.1002\/jctb.5877","article-title":"Design and preparation of stable CPO\/HRP@H-MOF(Zr) composites for efficient bio-catalytic degradation of organic toxicants in wastewater","volume":"94","author":"Gao","year":"2018","journal-title":"J. Chem. Technol. Biotechnol."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"142360","DOI":"10.1016\/j.scitotenv.2020.142360","article-title":"Nanostructured materials for harnessing the power of horseradish peroxidase for tailored environmental applications","volume":"749","author":"Bilal","year":"2020","journal-title":"Sci. Total Environ."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"13363","DOI":"10.1038\/s41598-023-39687-1","article-title":"Inactivation kinetics of horseradish peroxidase (HRP) by hydrogen peroxide","volume":"13","author":"Contreras","year":"2023","journal-title":"Sci. Rep."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"793","DOI":"10.1016\/j.rser.2018.04.103","article-title":"Progress & prospect of metal-organic frameworks (MOFs) for enzyme immobilization (enzyme\/MOFs)","volume":"91","author":"Hu","year":"2018","journal-title":"Renew. Sustain. Energy Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"8786","DOI":"10.1002\/anie.201916474","article-title":"\u201cArmor-plating\u201d enzymes with metal-organic frameworks (MOFs)","volume":"59","author":"Huang","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"120476","DOI":"10.1016\/j.carbpol.2022.120476","article-title":"Construction of porous chitosan macrospheres via dual pore-forming strategy as host for alkaline protease immobilization with high activity and stability","volume":"305","author":"Tang","year":"2023","journal-title":"Carbohydr. Polym."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"4659","DOI":"10.1021\/jacs.2c12590","article-title":"Locking effect in metal@MOF with superior stability for highly chemoselective catalysis","volume":"145","author":"Zhong","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"6466","DOI":"10.1021\/acssuschemeng.0c00987","article-title":"Rapidly and precisely cross-linked enzymes using bio-orthogonal chemistry from cell lysate for the synthesis of (S)-1-(2,6-dichloro-3-fluorophenyl) ethanol","volume":"8","author":"Li","year":"2020","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"13980","DOI":"10.1007\/s10853-020-04904-z","article-title":"A sandwich-type electrochemical immunosensor for ultrasensitive detection of CEA based on core-shell Cu2O@Cu-MOF@Au NPs nanostructure attached with HRP for triple signal amplification","volume":"55","author":"Li","year":"2020","journal-title":"J. Mater. Sci."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Mohidem, N.A., Mohamad, M., Rashid, M.U., Norizan, M.N., Hamzah, F., and Mat, H.b. (2023). Recent advances in enzyme immobilisation strategies, An overview of techniques and composite Carriers. J. Compos. Sci., 7.","DOI":"10.3390\/jcs7120488"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"6581","DOI":"10.1021\/acsanm.3c00168","article-title":"Fe3O4@ZIF-8@SiO2 core-Shell nanoparticles for the removal of pyrethroid insecticides from water","volume":"6","author":"Meng","year":"2023","journal-title":"ACS Appl. Nano Mater."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"24802","DOI":"10.1016\/j.ceramint.2019.08.222","article-title":"MnO2 nanoneedles loaded on silicon oxycarbide-derived hierarchically porous carbon for supercapacitor electrodes with enhanced electrochemical performance","volume":"45","author":"Sun","year":"2019","journal-title":"Ceram. Int."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Zheng, G., Zhou, Z., Yang, J., Zhou, L., Zaremba, O., Wuttke, S., and Zhu, W. (2024). Robust immobilization and activity preservation of enzymes in porous frameworks by silica-based \u201cinorganic glue\u201d. Adv. Mater., e2407831.","DOI":"10.1002\/adma.202407831"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"69","DOI":"10.1016\/j.bios.2016.11.046","article-title":"MnO2 nanosheets as an artificial enzyme to mimic oxidase for rapid and sensitive detection of glutathione","volume":"90","author":"Liu","year":"2017","journal-title":"Biosens. Bioelectron."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"123518","DOI":"10.1016\/j.seppur.2023.123518","article-title":"Synergetic effect of photocatalysis and peroxymonosulfate activated by Co\/Mn-MOF-74@g-C3N4 Z-scheme photocatalyst for removal of tetracycline hydrochloride","volume":"313","author":"Wen","year":"2023","journal-title":"Sep. Purif. Technol."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"e202423741","DOI":"10.1002\/ange.202423741","article-title":"Enzyme surface residues direct encapsulation into metal-organic frameworks for performance regulation","volume":"137","author":"Wu","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Xia, H., Li, N., Zhong, X., and Jiang, Y. (2020). Metal-organic frameworks, A potential platform for enzyme immobilization and related applications. Front. Bioeng. Biotechnol., 8.","DOI":"10.3389\/fbioe.2020.00695"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"108299","DOI":"10.1016\/j.biotechadv.2023.108299","article-title":"Metal-organic frameworks for enzyme immobilization and nanozymes, A laccase-focused review","volume":"70","author":"Blanco","year":"2024","journal-title":"Biotechnol. Adv."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"603","DOI":"10.1351\/pac198557040603","article-title":"Reporting physisorption data for gas\/solid systems with special reference to the determination of surface area and porosity","volume":"57","author":"Sing","year":"1985","journal-title":"Pure Appl. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"8.14.1","DOI":"10.1002\/0471250953.bi0814s24","article-title":"Using AutoDock for ligand-receptor docking","volume":"24","author":"Morris","year":"2008","journal-title":"Curr. Protoc. Bioinform."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3689","DOI":"10.1016\/j.apsusc.2011.12.006","article-title":"Synthesis and characterization of core-shell structured SiO2@YVO4, Yb3+, Er3+ microspheres","volume":"258","author":"Liang","year":"2012","journal-title":"Appl. Surf. Sci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2964","DOI":"10.1007\/s10562-021-03541-8","article-title":"Insight into N2O formation over different crystal phases of MnO2 during low-temperature NH3-SCR of NO","volume":"151","author":"Yang","year":"2021","journal-title":"Catal. Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"115303","DOI":"10.1063\/5.0223464","article-title":"Antibacterial activity of Ag+\/MAF-7 nanocomposites against enterococcus faecalis","volume":"14","author":"Liu","year":"2024","journal-title":"AIP Adv."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"144178","DOI":"10.1016\/j.jclepro.2024.144178","article-title":"Construction of hierarchical porous MIL-100(Fe) for horseradish peroxidase immobilization and its degradation performance of bisphenol A","volume":"481","author":"Chen","year":"2024","journal-title":"J. Clean. Prod."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"109670","DOI":"10.1016\/j.ecoenv.2019.109670","article-title":"Immobilization of laccase onto meso-MIL-53(Al) via physical adsorption for the catalytic conversion of triclosan","volume":"184","author":"Jia","year":"2019","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"e202201378","DOI":"10.1002\/ange.202201378","article-title":"Enhancing enzyme activity by the modulation of covalent interactions in the confined channels of covalent organic frameworks","volume":"134","author":"Xing","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"e2411196","DOI":"10.1002\/advs.202411196","article-title":"Combining hard shell with soft core to enhance enzyme activity and resist external disturbances","volume":"12","author":"Wang","year":"2025","journal-title":"Adv. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Ma, M., Lu, L., Li, H., Xiong, Y., and Dong, F. (2019). Functional metal organic framework\/SiO2 nanocomposites, from versatile synthesis to advanced applications. Polymers, 11.","DOI":"10.3390\/polym11111823"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"e202406110","DOI":"10.1002\/anie.202406110","article-title":"Multivariate silicification-assisted single enzyme structure augmentation for improved enzymatic activity-stability trade-off","volume":"63","author":"Zheng","year":"2024","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"e2415477","DOI":"10.1002\/advs.202415477","article-title":"High-spin states of manganese(III) enable robust cold-adapted activity of MnO2 nanozymes","volume":"12","author":"Tian","year":"2025","journal-title":"Adv. Sci."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"14847","DOI":"10.1021\/acscatal.0c03233","article-title":"Enzyme hydration determines resistance in organic cosolvents","volume":"10","author":"Cui","year":"2020","journal-title":"ACS Catal."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2280","DOI":"10.1021\/acs.accounts.2c00304","article-title":"How do metalloproteins tame the fenton reaction and utilize \u2022OH radicals in constructive manners?","volume":"55","author":"Wang","year":"2022","journal-title":"Acc. Chem. Res."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/19\/2\/254\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,1,8]],"date-time":"2026-01-08T10:14:14Z","timestamp":1767867254000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/19\/2\/254"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,1,8]]},"references-count":36,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2026,1]]}},"alternative-id":["ma19020254"],"URL":"https:\/\/doi.org\/10.3390\/ma19020254","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,1,8]]}}}