{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T19:46:09Z","timestamp":1792784769419,"version":"4.5.0"},"reference-count":68,"publisher":"American Chemical Society (ACS)","issue":"36","license":[{"start":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T00:00:00Z","timestamp":1788220800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T00:00:00Z","timestamp":1788220800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T00:00:00Z","timestamp":1788220800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"name":"National Natural Science Foundation of China (NSFC)","award":["22205019"],"award-info":[{"award-number":["22205019"]}],"id":[{"id":"https:\/\/ror.org\/01h0zpd94","id-type":"ROR","asserted-by":"crossref"}]},{"name":"National Natural Science Foundation of China (NSFC)","award":["22521101"],"award-info":[{"award-number":["22521101"]}],"id":[{"id":"https:\/\/ror.org\/01h0zpd94","id-type":"ROR","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,16]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Small interfering RNA (siRNA) offers a promising modality for tumor immunotherapy through a precise gene-silencing mechanism, whereas its efficient loading and in vivo delivery rely on specialized carriers because of its polyanionic nature. Porous nanomaterials represent attractive platforms for designing such carriers. However, constructing biocompatible porous organic materials for efficient siRNA loading and in vivo delivery is challenging because structurally stable organic nanoparticles (NPs) with abundant, ordered, and large mesopores have rarely been reported. Herein, a linker-design strategy that balances rigidity and flexibility was used to synthesize covalent organic frameworks (COFs), resolving the dilemma of simultaneously producing organic NPs and preserving ordered large mesopores. Specifically, grafting flexible allyloxy chains onto rigid, poorly soluble linkers enhanced linker solubility and interlayer interactions, enabling the synthesis of a series of mesoporous COF nanoparticles. Thereinto, 4,4\u2032-(1,2-ethynediyl)bis(2-allyloxybenzaldehyde) and 1,3,5-tris(4-aminophenyl)benzene-derived COF (TECOF) NPs exhibited a mesopore aperture of 4.5 nm, which, to the best of our knowledge, is the largest reported for COF nanoparticles to date. Subsequently, TECOF NPs were applied as platforms to covalently graft a cisplatin-COOH complex (Pt(IV)) and encapsulate a model siRNA (siPDL1) to generate siPDL1@TECOF-Pt. After tumor-cell uptake, grafted Pt(IV) was proven to induce pyroptosis, while channel-loaded siPDL1 was released to silence PD-L1 expression. Such a nanoscale-mesoporous-COF-assisted immunotherapy strategy demonstrated significant tumor growth inhibition and prolonged survival in 4T1 tumor-bearing mice. This study provides a proof-of-concept for the construction of large-mesopore COF NPs for efficient siRNA loading and in vivo delivery.<\/jats:p>","DOI":"10.1021\/jacs.6c10067","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T09:57:11Z","timestamp":1788429431000},"page":"38878-38890","source":"Crossref","is-referenced-by-count":0,"title":["Large-Mesopore Covalent\nOrganic Framework Nanoparticles\nfor Small Interfering RNA Delivery toward Cancer Immunotherapy"],"prefix":"10.1021","volume":"148","author":[{"given":"Renzeng","family":"Chen","sequence":"first","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haiyin","family":"Yang","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huiping","family":"Zhu","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lihua","family":"Wu","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhitong","family":"Guo","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xi","family":"Yu","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-2490-6117","authenticated-orcid":true,"given":"Yuanbo","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3935-7245","authenticated-orcid":true,"given":"Yuanyu","family":"Huang","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9092-3252","authenticated-orcid":true,"given":"Bo","family":"Wang","sequence":"additional","affiliation":[{"name":"Beijing Institute of Technology , , ,","place":["Beijing, P. R. China, 100081"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,1]]},"reference":[{"key":"2026091609121290600_cit1","doi-asserted-by":"publisher","first-page":"341","DOI":"10.1038\/s41573-024-00912-9","article-title":"RNAi-based Drug Design: Considerations and Future Directions","volume":"23","author":"Tang","year":"2024","journal-title":"Nat. Rev. Drug Discovery"},{"key":"2026091609121290600_cit2","doi-asserted-by":"publisher","first-page":"1283","DOI":"10.1038\/s12276-023-00998-y","article-title":"Where Should\nsiRNAs Go: Applicable\nOrgans for siRNA Drugs","volume":"55","author":"Ahn","year":"2023","journal-title":"Exp. Mol. Med."},{"key":"2026091609121290600_cit3","doi-asserted-by":"publisher","first-page":"421","DOI":"10.1038\/s41573-019-0017-4","article-title":"The Current\nState and Future Directions\nof RNAi-Based Therapeutics","volume":"18","author":"Setten","year":"2019","journal-title":"Nat. Rev. Drug Discovery"},{"key":"2026091609121290600_cit4","doi-asserted-by":"publisher","first-page":"2285","DOI":"10.1016\/j.matt.2022.04.032","article-title":"Transforming \u201cCold\u201d Tumors into\n\u201cHot\u201d\nOnes via Tumor-Microenvironment-Responsive siRNA Micelleplexes for\nEnhanced Immunotherapy","volume":"5","author":"Yi","year":"2022","journal-title":"Matter"},{"key":"2026091609121290600_cit5","doi-asserted-by":"publisher","first-page":"327","DOI":"10.1038\/s41596-020-00418-9","article-title":"Synthesis and Use of an Amphiphilic Dendrimer\nfor siRNA Delivery into Primary Immune Cells","volume":"16","author":"Chen","year":"2021","journal-title":"Nat. Protoc."},{"key":"2026091609121290600_cit6","doi-asserted-by":"publisher","first-page":"1496","DOI":"10.1038\/s41587-024-02448-0","article-title":"Gold-siRNA Supraclusters Enhance the Anti-Tumor Immune\nResponse of Stereotactic Ablative Radiotherapy at Primary and Metastatic\nTumors","volume":"43","author":"Jiang","year":"2025","journal-title":"Nat. Biotechnol."},{"key":"2026091609121290600_cit7","doi-asserted-by":"publisher","first-page":"455","DOI":"10.1038\/s12276-022-00757-5","article-title":"RNA Therapy:\nRich History, Various Applications and Unlimited Future Prospects","volume":"54","author":"Kim","year":"2022","journal-title":"Exp. Mol. Med."},{"key":"2026091609121290600_cit8","doi-asserted-by":"publisher","first-page":"2000416","DOI":"10.1002\/adma.202000416","article-title":"Single siRNA\nNanocapsules for Effective siRNA Brain Delivery and Glioblastoma Treatment","volume":"32","author":"Zou","year":"2020","journal-title":"Adv. Mater."},{"key":"2026091609121290600_cit9","doi-asserted-by":"publisher","first-page":"224","DOI":"10.1021\/acs.accounts.2c00464","article-title":"Overcoming\nPharmaceutical Bottlenecks for Nucleic Acid Drug Development","volume":"56","author":"Lu","year":"2023","journal-title":"Acc. Chem. Res."},{"key":"2026091609121290600_cit10","doi-asserted-by":"publisher","first-page":"1090237","DOI":"10.3389\/fphar.2022.1090237","article-title":"The Therapeutic Prospects\nof N-Acetylgalactosamine-siRNA\nConjugates","volume":"13","author":"Zhang","year":"2022","journal-title":"Front. Pharmacol."},{"key":"2026091609121290600_cit11","doi-asserted-by":"publisher","first-page":"805","DOI":"10.1016\/j.xphs.2024.12.013","article-title":"Recent advances in\ndrying and development of solid formulations for\nstable mRNA and siRNA lipid nanoparticles","volume":"114","author":"Arte","year":"2025","journal-title":"J.\nPharm. 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Ed."},{"key":"2026091609121290600_cit30","doi-asserted-by":"publisher","first-page":"e202509183","DOI":"10.1002\/anie.202509183","article-title":"MitoSiege-Driven Catalase Collapse: A GSH-Responsive,\nMitochondria-Targeted COF Prodrug for Amplified Chemodynamic Therapy","volume":"64","author":"Ding","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026091609121290600_cit31","doi-asserted-by":"publisher","first-page":"33472","DOI":"10.1021\/jacs.5c07787","article-title":"Mixed-Length Multivariate Covalent Organic Framework\nfor Combined Near-Infrared Photodynamic Therapy and Drug Delivery","volume":"147","author":"Rodri\u0301guez-Camargo","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026091609121290600_cit32","doi-asserted-by":"publisher","first-page":"13469","DOI":"10.1021\/jacs.3c04183","article-title":"Harnessing Self-Repairing and Crystallization\nProcesses for Effective Enzyme Encapsulation in Covalent Organic Frameworks","volume":"145","author":"Zhang","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026091609121290600_cit33","doi-asserted-by":"publisher","first-page":"136624","DOI":"10.1016\/j.cej.2022.136624","article-title":"Covalent Organic Frameworks\nas Crystalline Sponges for Enzyme Extraction and Production from Natural\nBiosystems","volume":"444","author":"Chen","year":"2022","journal-title":"Chem. Eng. J."},{"key":"2026091609121290600_cit34","doi-asserted-by":"publisher","first-page":"21926","DOI":"10.1021\/jacs.5c05406","article-title":"Tuning Covalent Organic Frameworks\nfor Nucleic Acid Loading: Toward\nCreating a Hierarchical Artificial Cell","volume":"147","author":"Wang","year":"2025","journal-title":"J.\nAm. Chem. Soc."},{"key":"2026091609121290600_cit35","doi-asserted-by":"publisher","first-page":"101","DOI":"10.1038\/s41392-020-0207-x","article-title":"Therapeutic siRNA: State of the Art","volume":"5","author":"Hu","year":"2020","journal-title":"Signal Transduction Targeted Ther."},{"key":"2026091609121290600_cit36","doi-asserted-by":"publisher","first-page":"2468","DOI":"10.1021\/jacs.1c12020","article-title":"Supramolecular\nReinforcement\nof a Large-Pore 2D Covalent Organic Framework","volume":"144","author":"Diwakara","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"2026091609121290600_cit37","doi-asserted-by":"publisher","first-page":"8315","DOI":"10.1021\/acs.iecr.0c00304","article-title":"Construction of Large-Pore\nCrystalline Covalent Organic Framework as High-Performance Adsorbent\nfor Rhodamine B Dye Removal","volume":"59","author":"Xu","year":"2020","journal-title":"Ind. Eng. Chem.\nRes."},{"key":"2026091609121290600_cit38","doi-asserted-by":"publisher","first-page":"57","DOI":"10.31635\/ccschem.023.202303261","article-title":"Design,\nSynthesis, and Applications of Mesoporous Covalent Organic Frameworks","volume":"6","author":"Arora","year":"2024","journal-title":"CCS Chem."},{"key":"2026091609121290600_cit39","doi-asserted-by":"publisher","first-page":"58","DOI":"10.1021\/acscentsci.6b00331","article-title":"Colloidal Covalent Organic Frameworks","volume":"3","author":"Smith","year":"2017","journal-title":"ACS\nCent. Sci."},{"key":"2026091609121290600_cit40","doi-asserted-by":"publisher","first-page":"18271","DOI":"10.1021\/jacs.9b09189","article-title":"Size-Controllable\nSynthesis of Uniform Spherical Covalent\nOrganic Frameworks at Room Temperature for Highly Efficient and Selective\nEnrichment of Hydrophobic Peptides","volume":"141","author":"Ma","year":"2019","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026091609121290600_cit41","doi-asserted-by":"publisher","first-page":"3796","DOI":"10.1039\/C9SC00289H","article-title":"Controlled Growth\nof Imine-Linked Two-Dimensional Covalent Organic Framework Nanoparticles","volume":"10","author":"Li","year":"2019","journal-title":"Chem. Sci."},{"key":"2026091609121290600_cit42","doi-asserted-by":"publisher","first-page":"15711","DOI":"10.1021\/jacs.1c06518","article-title":"Interlayer Interactions as Design\nTool for Large-Pore COFs","volume":"143","author":"Emmerling","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026091609121290600_cit43","doi-asserted-by":"publisher","first-page":"2002366","DOI":"10.1002\/adma.202002366","article-title":"Structural Approaches to Control Interlayer Interactions\nin 2D Covalent Organic Frameworks","volume":"32","author":"Marti\u0301nez-Abadi\u0301a","year":"2020","journal-title":"Adv. Mater."},{"key":"2026091609121290600_cit44","doi-asserted-by":"publisher","first-page":"121","DOI":"10.1039\/D1MH00809A","article-title":"Design strategies for\nimproving the crystallinity of covalent organic frameworks and conjugated\npolymers: a review","volume":"9","author":"Yang","year":"2022","journal-title":"Mater. Horiz."},{"key":"2026091609121290600_cit45","doi-asserted-by":"publisher","first-page":"905","DOI":"10.1038\/nchem.2352","article-title":"Stable, Crystalline,\nPorous, Covalent Organic Frameworks\nas A Platform for Chiral Organocatalysts","volume":"7","author":"Xu","year":"2015","journal-title":"Nat.\nChem."},{"key":"2026091609121290600_cit46","doi-asserted-by":"publisher","first-page":"2388","DOI":"10.1002\/chem.201001290","article-title":"The Structure\nof Layered Covalent-Organic Frameworks","volume":"17","author":"Lukose","year":"2011","journal-title":"Chem.\u2500Eur.\nJ."},{"key":"2026091609121290600_cit47","doi-asserted-by":"publisher","first-page":"8438","DOI":"10.1021\/ja073231f","article-title":"Soluble Single-Walled\nCarbon Nanotubes as Longboat Delivery Systems for Platinum(IV) Anticancer\nDrug Design","volume":"129","author":"Feazell","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"2026091609121290600_cit48","doi-asserted-by":"publisher","first-page":"1051","DOI":"10.1515\/pac-2014-1117","article-title":"Physisorption of Gases, with Special\nReference to the Evaluation of Surface Area and Pore Size Distribution\n(IUPAC Technical Report)","volume":"87","author":"Thommes","year":"2015","journal-title":"Pure Appl. Chem."},{"key":"2026091609121290600_cit49","doi-asserted-by":"publisher","first-page":"13304","DOI":"10.1021\/acsnano.9b06467","article-title":"Nanoscale\nCovalent Organic Framework\nfor Combinatorial Antitumor Photodynamic and Photothermal Therapy","volume":"13","author":"Guan","year":"2019","journal-title":"ACS Nano"},{"key":"2026091609121290600_cit50","doi-asserted-by":"publisher","first-page":"1293","DOI":"10.1038\/s41467-018-03650-w","article-title":"Metal-Organic Frameworks\nfor Precise Inclusion of Single-Stranded DNA and Transfection in Immune\nCells","volume":"9","author":"Peng","year":"2018","journal-title":"Nat. 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