Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment

Rheumatoid arthritis (RA) is a major autoimmune disease characterized by significant joint inflammation and bone destruction. Many first-line RA treatment drugs such as methotrexate (MTX) have limited solubility in major solvents and are difficult to be delivered to RA joints in a sustained manner....

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Main Authors: Hao Li, Yuanning Lyu, Ruinan Wang, Hong Yu, Mingxin Lin, Zhuo Li, Yanlin Zhong, Puyi Sheng, Kunyu Zhang, Weiming Liao, Liming Bian
Format: Article
Language:English
Published: KeAi Communications Co., Ltd. 2025-11-01
Series:Bioactive Materials
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Online Access:http://www.sciencedirect.com/science/article/pii/S2452199X25003329
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author Hao Li
Yuanning Lyu
Ruinan Wang
Hong Yu
Mingxin Lin
Zhuo Li
Yanlin Zhong
Puyi Sheng
Kunyu Zhang
Weiming Liao
Liming Bian
author_facet Hao Li
Yuanning Lyu
Ruinan Wang
Hong Yu
Mingxin Lin
Zhuo Li
Yanlin Zhong
Puyi Sheng
Kunyu Zhang
Weiming Liao
Liming Bian
author_sort Hao Li
collection DOAJ
description Rheumatoid arthritis (RA) is a major autoimmune disease characterized by significant joint inflammation and bone destruction. Many first-line RA treatment drugs such as methotrexate (MTX) have limited solubility in major solvents and are difficult to be delivered to RA joints in a sustained manner. Meanwhile, the efficient co-delivery of osteoinductive ions such as magnesium ions (Mg2+) for RA treatment is also challenging due to the uncontrolled burst release. By capitalizing on the enhanced supramolecular interactions of cyanuric acid (CYA) upon the pH-induced keto-enol tautomerization, a supramolecular hydrogel (Gel-MTX/Mg) with efficient co-delivery of MTX and Mg2+ is proposed. This hydrogel features pH-responsive on-demand release of MTX and Mg2+ in RA joints triggered by the pathological pH-induced keto-enol tautomerization of CYA. The release of MTX and Mg2+ from the Gel-MTX/Mg hydrogel induces anti-inflammatory M2 macrophage polarization, inhibits osteoclast differentiation, and enhances osteoblastic differentiation. Furthermore, RNA-seq results reveal that the Gel-MTX/Mg hydrogel promotes the enrichment of signaling pathways related to anti-inflammatory and bone-remodeling activities. One-time intra-articular administration of the Gel-MTX/Mg hydrogel significantly suppresses inflammation symptoms and protects bone and cartilage in a rat model. This supramolecular hydrogel that is capable of simultaneously delivering both therapeutic drugs and ions in response to pathological conditions has promising potential for the treatment of RA and other inflammatory and bone-degenerative diseases.
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spelling doaj-art-366d53feb2f642dd9d6a41ff21fbe4622025-08-20T02:48:10ZengKeAi Communications Co., Ltd.Bioactive Materials2452-199X2025-11-015349550610.1016/j.bioactmat.2025.07.039Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatmentHao Li0Yuanning Lyu1Ruinan Wang2Hong Yu3Mingxin Lin4Zhuo Li5Yanlin Zhong6Puyi Sheng7Kunyu Zhang8Weiming Liao9Liming Bian10Department of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China; Guangdong Provincial Key Laboratory of Orthopedics and Traumatology, The First Affiliated Hospital of Sun Yat-Sen University, Guangzhou, 510080, ChinaSchool of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, ChinaSchool of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, ChinaSchool of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, ChinaSchool of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, ChinaDepartment of Biomedical Engineering, The Chinese University of Hong Kong, Sha Tin, New Territories, Hong Kong, 999077, ChinaDepartment of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China; Guangdong Provincial Key Laboratory of Orthopedics and Traumatology, The First Affiliated Hospital of Sun Yat-Sen University, Guangzhou, 510080, ChinaDepartment of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China; Guangdong Provincial Key Laboratory of Orthopedics and Traumatology, The First Affiliated Hospital of Sun Yat-Sen University, Guangzhou, 510080, China; Corresponding authors. Department of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China.School of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, China; Guangdong Provincial Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006, China; Corresponding author. School of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China.Department of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China; Guangdong Provincial Key Laboratory of Orthopedics and Traumatology, The First Affiliated Hospital of Sun Yat-Sen University, Guangzhou, 510080, China; Corresponding authors. Department of Joint Surgery, The First Affiliated Hospital of Sun Yat-sen University, Guangzhou, 510080, China.School of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China; National Engineering Research Center for Tissue Restoration and Reconstruction, South China University of Technology, Guangzhou, 510006, China; Guangdong Provincial Key Laboratory of Biomedical Engineering, South China University of Technology, Guangzhou 510006, China; Corresponding author. School of Biomedical Sciences and Engineering, Guangzhou International Campus, South China University of Technology, Guangzhou, 511442, China.Rheumatoid arthritis (RA) is a major autoimmune disease characterized by significant joint inflammation and bone destruction. Many first-line RA treatment drugs such as methotrexate (MTX) have limited solubility in major solvents and are difficult to be delivered to RA joints in a sustained manner. Meanwhile, the efficient co-delivery of osteoinductive ions such as magnesium ions (Mg2+) for RA treatment is also challenging due to the uncontrolled burst release. By capitalizing on the enhanced supramolecular interactions of cyanuric acid (CYA) upon the pH-induced keto-enol tautomerization, a supramolecular hydrogel (Gel-MTX/Mg) with efficient co-delivery of MTX and Mg2+ is proposed. This hydrogel features pH-responsive on-demand release of MTX and Mg2+ in RA joints triggered by the pathological pH-induced keto-enol tautomerization of CYA. The release of MTX and Mg2+ from the Gel-MTX/Mg hydrogel induces anti-inflammatory M2 macrophage polarization, inhibits osteoclast differentiation, and enhances osteoblastic differentiation. Furthermore, RNA-seq results reveal that the Gel-MTX/Mg hydrogel promotes the enrichment of signaling pathways related to anti-inflammatory and bone-remodeling activities. One-time intra-articular administration of the Gel-MTX/Mg hydrogel significantly suppresses inflammation symptoms and protects bone and cartilage in a rat model. This supramolecular hydrogel that is capable of simultaneously delivering both therapeutic drugs and ions in response to pathological conditions has promising potential for the treatment of RA and other inflammatory and bone-degenerative diseases.http://www.sciencedirect.com/science/article/pii/S2452199X25003329Supramolecular hydrogelStructural tautomerizationDrug deliveryRheumatoid arthritisAnti-inflammationBone remodeling
spellingShingle Hao Li
Yuanning Lyu
Ruinan Wang
Hong Yu
Mingxin Lin
Zhuo Li
Yanlin Zhong
Puyi Sheng
Kunyu Zhang
Weiming Liao
Liming Bian
Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
Bioactive Materials
Supramolecular hydrogel
Structural tautomerization
Drug delivery
Rheumatoid arthritis
Anti-inflammation
Bone remodeling
title Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
title_full Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
title_fullStr Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
title_full_unstemmed Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
title_short Supramolecular drug-laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
title_sort supramolecular drug laden hydrogel based on structural tautomerization enhances drug delivery for rheumatoid arthritis treatment
topic Supramolecular hydrogel
Structural tautomerization
Drug delivery
Rheumatoid arthritis
Anti-inflammation
Bone remodeling
url http://www.sciencedirect.com/science/article/pii/S2452199X25003329
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