|
|
多功能有机框架及其生物医学应用研究进展
|
Abstract:
有机框架材料(Organic framework materials, OFs)凭借其结构可调、功能多样等特性,在生物医学领域展现出重要的应用潜力。本文系统梳理了金属–有机框架(MOFs)、共价有机框架(COFs)及氢键有机框架(HOFs)三类材料的结构特点,并重点评述了它们在生物医学方面的前沿应用。研究表明,通过合理的结构孔隙设计,OFs可实现高效药物负载,例如ZIF-8在抗癌药物递送中的应用;表面功能化修饰可增强其抗菌性能,如Ag-MOFs通过促进活性氧(ROS)生成以提升抗菌效果;部分OFs还可作为高灵敏度生物传感平台,例如基于COFs的荧光探针;此外,OFs在光热治疗中也显示出良好潜力,如HOFs在近红外光照射下的肿瘤消融效果。然而,OFs在走向临床转化的过程中仍面临生物相容性、体内降解行为及大规模制备等关键挑战。未来研究应聚焦于开发智能响应型OFs系统(如pH或光触发释放机制),并探索其在多模态协同治疗中的应用,以推动该类材料从基础研究向临床实践的转化。
Organic framework materials (OFs) exhibit broad prospects in the biomedical field due to their tunable structure and multifunctionality. This review systematically summarizes the classification, formation mechanisms, and synthesis strategies (such as solvothermal method and microwave-assisted method) of MOFs, COFs, and HOFs, and focuses on their innovative applications in biomedicine. Research indicates that OFs can achieve efficient drug loading through pore engineering (such as ZIF-8 delivering anticancer drugs), enhance antibacterial performance through surface functionalization (such as the ROS generation capability of Ag-MOFs), serve as high-sensitivity biosensors (such as COFs fluorescent probes), or treat cancer through photothermal effects (the application of HOFs in photothermal therapy). However, the clinical translation of OFs still faces challenges such as biocompatibility, in vivo degradation behavior, and large-scale preparation. Future research needs to focus on the design of intelligent responsive systems (such as pH/light-triggered release) and the development of multimodal treatment platforms to facilitate their transition from laboratory research to practical applications.
| [1] | Mohan, B., Singh, G., Gupta, R.K., Sharma, P.K., Solovev, A.A., Pombeiro, A.J.L., et al. (2024) Hydrogen-Bonded Organic Frameworks (HOFs): Multifunctional Material on Analytical Monitoring. Trac-Trends in Analytical Chemistry, 170, Article 117436. https://doi.org/10.1016/j.trac.2023.117436 |
| [2] | Cao, J.P., Tang, G. and Yan, F. (2024) Applications of Emerging Metal and Covalent Organic Frameworks in Perovskite Photovoltaics: Materials and Devices. Advanced Energy Materials, 14, Article 2304027. https://doi.org/10.1002/aenm.202304027 |
| [3] | Yang, Y., Sun, Z.Y., Wu, Y.W., Liang, Z.W., Li, F.K., Zhu, M., et al. (2024) Porous Organic Framework Materials (MOF, COF, and HOF) as the Multifunctional Separator for Rechargeable Lithium Metal Batteries. Small, 20, e2401457. https://doi.org/10.1002/smll.202401457 |
| [4] | Masoomi, M.Y., Morsali, A., Dhakshinamoorthy, A. and Garcia, H. (2019) Mixed-Metal MOFs: Unique Opportunities in Metal-Organic Framework (MOF) Functionality and Design. Angewandte Chemie International Edition, 58, 15188-15205. https://doi.org/10.1002/anie.201902229 |
| [5] | Kaur, H., Siwal, S.S., Saini, R.V. and Thakur, V.K. (2024) Covalent-Organic Framework-Based Materials in Theranostic Applications: Insights into Their Advantages and Challenges. ACS Omega, 9, 6235-6252. https://doi.org/10.1021/acsomega.3c08456 |
| [6] | Jiang, M., Yan, X., Wang, Y., Pu, F., Liu, H., Li, Y., et al. (2023) One-Component Artificial Gustatory System Based on Hydrogen-Bond Organic Framework for Discrimination of Versatile Analytes. Advanced Functional Materials, 33, Article 2300091. https://doi.org/10.1002/adfm.202300091 |
| [7] | Ding, M., Liu, W. and Gref, R. (2022) Nanoscale MOFs: From Synthesis to Drug Delivery and Theranostics Applications. Advanced Drug Delivery Reviews, 190, Article 114496. https://doi.org/10.1016/j.addr.2022.114496 |
| [8] | Wang, Y., Yan, J., Wen, N., Xiong, H., Cai, S., He, Q., et al. (2020) Metal-Organic Frameworks for Stimuli-Responsive Drug Delivery. Biomaterials, 230, Article 119619. https://doi.org/10.1016/j.biomaterials.2019.119619 |
| [9] | Huang, Y., Hao, X., Ma, S., Wang, R. and Wang, Y. (2022) Covalent Organic Framework-Based Porous Materials for Harmful Gas Purification. Chemosphere, 291, Article 132795. https://doi.org/10.1016/j.chemosphere.2021.132795 |
| [10] | Zhou, C.L., Pan, M.F., Li, S.J., Sun, Y.X., et al. (2022) Metal Organic Frameworks (MOFs) as Multifunctional Nanoplatform for Anticorrosion Surfaces and Coatings. Advances in Colloid and Interface Science, 305, Article 102707. https://doi.org/10.1016/j.cis.2022.102707 |
| [11] | Ding, L., Shi, M., Xu, Y., Yu, E., Zhang, Y., Li, J., et al. (2025) Covalent Organic Framework: A Rising Star in Antibacterial Agents. Advanced Functional Materials, 35, Article 2411237. https://doi.org/10.1002/adfm.202411237 |
| [12] | Honarvar Nazari, M., Zhang, Y., Mahmoodi, A., Xu, G., Yu, J., Wu, J., et al. (2022) Nanocomposite Organic Coatings for Corrosion Protection of Metals: A Review of Recent Advances. Progress in Organic Coatings, 162, Article 106573. https://doi.org/10.1016/j.porgcoat.2021.106573 |
| [13] | Liu, W., Yan, Z., Zhang, Z., Zhang, Y., Cai, G. and Li, Z. (2019) Bioactive and Anti-Corrosive Bio-MOF-1 Coating on Magnesium Alloy for Bone Repair Application. Journal of Alloys and Compounds, 788, 705-711. https://doi.org/10.1016/j.jallcom.2019.02.281 |
| [14] | Pettinari, C., Pettinari, R., Di Nicola, C., Tombesi, A., Scuri, S. and Marchetti, F. (2021) Antimicrobial MOFs. Coordination Chemistry Reviews, 446, Article 214121. https://doi.org/10.1016/j.ccr.2021.214121 |
| [15] | Zhu, L., Huo, A., Chen, Y., Bai, X., Cao, C., Zheng, Y., et al. (2023) A ROS Reservoir Based on a Polyoxometalate and Metal-Organic Framework Hybrid for Efficient Bacteria Eradication and Wound Healing. Chemical Engineering Journal, 476, Article 146613. https://doi.org/10.1016/j.cej.2023.146613 |
| [16] | Pandya, I., Kumar, S., Aswal, V.K., El Seoud, O., Assiri, M.A. and Malek, N. (2024) Metal Organic Framework-Based Polymeric Hydrogel: A Promising Drug Delivery Vehicle for the Treatment of Breast Cancer. International Journal of Pharmaceutics, 658, Article 124206. https://doi.org/10.1016/j.ijpharm.2024.124206 |
| [17] | Diercks, C.S. and Yaghi, O.M. (2017) The Atom, the Molecule, and the Covalent Organic Framework. Science, 355, eaal1585. https://doi.org/10.1126/science.aal1585 |
| [18] | Abuzeid, H.R., EL-Mahdy, A.F.M. and Kuo, S. (2021) Covalent Organic Frameworks: Design Principles, Synthetic Strategies, and Diverse Applications. Giant, 6, Article 100054. https://doi.org/10.1016/j.giant.2021.100054 |
| [19] | He, Y.B. and Chen, B.L. (2011) A Microporous Hydrogen-Bonded Organic Framework for Highly Selective C2H2/C2H4 Separation at Ambient Temperature. Journal of the American Chemical Society, 133, 14570-14573. https://doi.org/10.1021/ja2066016 |
| [20] | Wang, B., Lin, R., Zhang, Z., Xiang, S. and Chen, B. (2020) Hydrogen-Bonded Organic Frameworks as a Tunable Platform for Functional Materials. Journal of the American Chemical Society, 142, 14399-14416. https://doi.org/10.1021/jacs.0c06473 |
| [21] | Chen, W., Liu, M., Yang, H., Nezamzadeh-Ejhieh, A., Lu, C., Pan, Y., et al. (2023) Recent Advances of Fe(III)/Fe(II)-MPNs in Biomedical Applications. Pharmaceutics, 15, Article 1323. https://doi.org/10.3390/pharmaceutics15051323 |
| [22] | Guo, X., Zhou, L., Liu, X., Tan, G., Yuan, F., Nezamzadeh-Ejhieh, A., et al. (2023) Fluorescence Detection Platform of Metal-Organic Frameworks for Biomarkers. Colloids and Surfaces B: Biointerfaces, 229, Article 113455. https://doi.org/10.1016/j.colsurfb.2023.113455 |
| [23] | Zheng, Q., Li, J., Yuan, W., Liu, X., Tan, L., Zheng, Y., et al. (2019) Metal-Organic Frameworks Incorporated Polycaprolactone Film for Enhanced Corrosion Resistance and Biocompatibility of Mg Alloy. ACS Sustainable Chemistry & Engineering, 7, 18114-18124. https://doi.org/10.1021/acssuschemeng.9b05196 |
| [24] | Rao, C., Liao, D., Pan, Y., Zhong, Y., Zhang, W., Ouyang, Q., et al. (2022) Novel Formulations of Metal-Organic Frameworks for Controlled Drug Delivery. Expert Opinion on Drug Delivery, 19, 1183-1202. https://doi.org/10.1080/17425247.2022.2064450 |
| [25] | Shao, Y., Suo, H., Wang, S., Peng, Y., Chu, X., Long, Z., et al. (2024) A Facile Method to Construct ZIF-8 MOFs on Contact Lens for High Antibiotics Loading and Self-Defensive Release. Chemical Engineering Journal, 481, Article 148576. https://doi.org/10.1016/j.cej.2024.148576 |
| [26] | Hu, W., Ouyang, Q., Jiang, C., Huang, S., Alireza, N., Guo, D., et al. (2024) Biomedical Metal-Organic Framework Materials on Antimicrobial Therapy: Perspectives and Challenges. Materials Today Chemistry, 41, Article 102300. https://doi.org/10.1016/j.mtchem.2024.102300 |
| [27] | Xie, W., Chen, J., Cheng, X., Feng, H., Zhang, X., Zhu, Z., et al. (2023) Multi-Mechanism Antibacterial Strategies Enabled by Synergistic Activity of Metal-Organic Framework-Based Nanosystem for Infected Tissue Regeneration. Small, 19, Article 2205941. https://doi.org/10.1002/smll.202205941 |
| [28] | Hynek, J., Zelenka, J., Rathouský, J., Kubát, P., Ruml, T., Demel, J., et al. (2018) Designing Porphyrinic Covalent Organic Frameworks for the Photodynamic Inactivation of Bacteria. ACS Applied Materials & Interfaces, 10, 8527-8535. https://doi.org/10.1021/acsami.7b19835 |
| [29] | Zhang, C., Guo, J., Zou, X., Guo, S., Guo, Y., Shi, R., et al. (2021) Acridine-Based Covalent Organic Framework Photosensitizer with Broad-Spectrum Light Absorption for Antibacterial Photocatalytic Therapy. Advanced Healthcare Materials, 10, Article 2100775. https://doi.org/10.1002/adhm.202100775 |
| [30] | Liu, B., Pan, X., Nie, D., Hu, X., Liu, E. and Liu, T. (2022) Ionic Hydrogen-Bonded Organic Frameworks for Ion-Responsive Antimicrobial Membranes. Advanced Materials, 34, Article 2202280. https://doi.org/10.1002/adma.202202280 |
| [31] | Wang, Y., Ma, K., Bai, J., Xu, T., Han, W., Wang, C., et al. (2022) Chemically Engineered Porous Molecular Coatings as Reactive Oxygen Species Generators and Reservoirs for Long-Lasting Self-Cleaning Textiles. Angewandte Chemie International Edition, 61, e202115956. https://doi.org/10.1002/anie.202115956 |
| [32] | Yu, J.L. and Bai, Z. (2025) Recent Advances in Zn-MOFs and Their Derivatives for Cancer Therapeutic Applications; Application and Prospect of Cu-Based Metal-Organic Frameworks in Tumor Therapy. Journal of Molecular Structure, 321, Article 139984. |
| [33] | Ghosh, A., Ghosh, A., Bhattacharyya, A., Mitra, R., Das, B.B. and Bhaumik, A. (2023) Mitochondrial Topoisomerase 1 Targeted Anticancer Therapy Using Irinotecan Encapsulated Mesoporous MIL-101(Fe) Synthesized via a Vapour Assisted Method. Dalton Transactions, 53, 3010-3019. https://doi.org/10.1039/d3dt03654e |
| [34] | Ma, J., Chen, Z., Diao, Y., Ye, M., Liu, X., Cui, S., et al. (2024) Current and Promising Applications of UiO-Based MOFs in Breast Cancer Therapy. Reactive and Functional Polymers, 200, Article 105918. https://doi.org/10.1016/j.reactfunctpolym.2024.105918 |
| [35] | Deng, Y., Guo, M., Zhou, L., Huang, Y., Srivastava, S., Kumar, A., et al. (2024) Prospects, Advances and Biological Applications of MOF-Based Platform for the Treatment of Lung Cancer. Biomaterials Science, 12, 3725-3744. https://doi.org/10.1039/d4bm00488d |
| [36] | Hassan, A., Roy, S., Das, A., Wahed, S.A., Bairagi, A., Mondal, S., et al. (2024) Covalent Organic Frameworks as Potential Drug Carriers and Chemotherapeutic Agents for Ovarian Cancers. ACS Biomaterials Science & Engineering, 10, 4227-4236. https://doi.org/10.1021/acsbiomaterials.4c00351 |
| [37] | Yang, H., Liao, D., Cai, Z., Zhang, Y., Nezamzadeh-Ejhieh, A., Zheng, M., et al. (2023) Current Status of Fe-Based MOFs in Biomedical Applications. RSC Medicinal Chemistry, 14, 2473-2495. https://doi.org/10.1039/d3md00416c |
| [38] | Skorjanc, T., Shetty, D., Kumar, S., Makuc, D., Mali, G., Volavšek, J., et al. (2023) Nitroreductase-Sensitive Fluorescent Covalent Organic Framework for Tumor Hypoxia Imaging in Cells. Chemical Communications, 59, 5753-5756. https://doi.org/10.1039/d3cc01110k |
| [39] | Ouyang, S., Chen, C., Lin, P., Wu, W., Chen, G., Li, P., et al. (2023) Hydrogen-Bonded Organic Frameworks Chelated Manganese for Precise Magnetic Resonance Imaging Diagnosis of Cancers. Nano Letters, 23, 8628-8636. https://doi.org/10.1021/acs.nanolett.3c02466 |
| [40] | Kong, X., Ji, X., He, T., Xie, L., Zhang, Y., Lv, H., et al. (2020) A Green-Emission Metal-Organic Framework-Based Nanoprobe for Imaging Dual Tumor Biomarkers in Living Cells. ACS Applied Materials & Interfaces, 12, 35375-35384. https://doi.org/10.1021/acsami.0c10038 |
| [41] | Liu, Y., Zhang, Y., Li, X., Gao, X., Niu, X., Wang, W., et al. (2019) Fluorescence-Enhanced Covalent Organic Framework Nanosystem for Tumor Imaging and Photothermal Therapy. Nanoscale, 11, 10429-10438. https://doi.org/10.1039/c9nr02140j |
| [42] | Singh, N., Won, M., An, J., Yoon, C., Kim, D., Joong Lee, S., et al. (2024) Advances in Covalent Organic Frameworks for Cancer Phototherapy. Coordination Chemistry Reviews, 506, Article 215720. https://doi.org/10.1016/j.ccr.2024.215720 |
| [43] | Zeng, Y., Liao, D., Kong, X., Huang, Q., Zhong, M., Liu, J., et al. (2023) Current Status and Prospect of ZIF-Based Materials for Breast Cancer Treatment. Colloids and Surfaces B: Biointerfaces, 232, Article 113612. https://doi.org/10.1016/j.colsurfb.2023.113612 |