Self-assembled Near-Infrared Metallacycles and Metallacages for Cancer Theranostics

doi:10.6023/A26030068

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (7): 1175-1196.DOI: 10.6023/A26030068 Previous Articles Next Articles

Review

自组装近红外金属大环和金属笼用于癌症诊疗

董祎^a, 王伟光^b, 刘雯骞^a, 朱雪雨^a, 陈靖宇^a, 周炯^a^,^*()

^a 东北大学理学院化学系理学院化学系沈阳 110819
^b 北京大学深圳研究生院环境与能源学院环境与能源学院深圳 518055

投稿日期:2026-03-04 发布日期:2026-05-15

作者简介:

董祎, 东北大学理学院化学专业2023级本科生, 目前在周炯教授课题组进行科研创新训练, 主要研究方向为超分子大环吸附分离.

周炯, 东北大学教授、博士生导师. 从事功能导向的超分子化学及智能化学研究. 在Chem、PNAS、Nat. Commun.、J. Am. Chem. Soc.、Angew. Chem. Int. Ed.、Adv. Mater.等国际知名期刊发表SCI论文80余篇, 引用5000余次, 13篇ESI高被引论文, 4篇ESI热点论文, 封面论文11篇. 担任国家“英才计划”导师、国际先进材料学会终身会士、Vebleo协会会士等. 连续入选全球前2%顶尖科学家(2023~2025), 获得国际先进材料学会科学家奖、辽宁省化学会青年化学奖等荣誉.

基金资助:
国家自然科学基金(22101043); 中央高校基本科研业务费专项资金(N25LPY027); 以及东北大学的资助.

Self-assembled Near-Infrared Metallacycles and Metallacages for Cancer Theranostics

Yi Dong^a, Weiguang Wang^b, Wenqian Liu^a, Xueyu Zhu^a, Jingyu Chen^a, Jiong Zhou^a^,^*()

^a Department of Chemistry, College of Sciences, Northeastern University, Shenyang 110819, China
^b School of Environment and Energy, Shenzhen Graduate School, Peking University, Shenzhen 518055, China

Received:2026-03-04 Published:2026-05-15
Contact: * E-mail: zhoujiong@mail.neu.edu.cn
Supported by:
National Natural Science Foundation of China(22101043); Fundamental Research Funds for the Central Universities(N25LPY027); and Northeastern University.

As a class of supramolecular architectures, metallacycles and metallacages have demonstrated broad application prospects in the field of precision tumor therapy in recent years, owing to their highly tailorable design, precisely controllable spatial configurations, and multifunctional integration capabilities. Near-infrared (NIR) light, characterized by its excellent tissue penetration depth, low light scattering, and minimal background fluorescence interference, has become a crucial tool for bioimaging and deep-tissue therapy. NIR-luminescent metallacycles and metallacages not only combine the programmability of supramolecular structures with the functional diversity of metal coordination, but also exhibit synergistic integration of multiple therapeutic modalities — including photothermal therapy (PTT), photodynamic therapy (PDT), chemotherapy, and immunotherapy — under imaging guidance. Through precise ligand engineering and metal-center modulation, these systems can achieve efficient drug accumulation, targeted release, and real-time visualization of the therapeutic process at deep-seated tumor sites, offering innovative strategies for personalized, highly targeted, and low-side-effect comprehensive cancer treatment. This article systematically reviews the key research advances in this field in recent years, categorizing and summarizing progress in terms of structural design, imaging mechanisms, therapeutic modalities, and their synergistic mechanisms, while also discussing current challenges and future development directions.

Key words: metallacycles, metallacages, near-infrared, multimodal synergy, precision medicine

Cite this article

Yi Dong, Weiguang Wang, Wenqian Liu, Xueyu Zhu, Jingyu Chen, Jiong Zhou. Self-assembled Near-Infrared Metallacycles and Metallacages for Cancer Theranostics[J]. Acta Chimica Sinica, 2026, 84(7): 1175-1196.

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Fig. & Tab. 15

Figure 1. Schematic illustration of NIR-emissive metallacycles and metallacages for cancer theranostics

Figure 2. (a) Molecular structure of metallacycle 1; (b) Normalized absorption and emission spectra of metallacycle 1 (inset: NIR-II signal of metallacycle 1); (c) NIR-II imaging monitoring of therapeutic response in U87MG tumors using nanoparticles derived from metallacycle 1 (82 mW/cm², 100 ms)[85]; (d) Molecular structure of metallacycle 2; (e) Absorption and emission spectra of metallacycle 2; (f) Tumor growth inhibition curves of HepG2 treated with PBS, cisplatin, and nanoparticles derived from metallacycle 2[86]. Copyright © 2019 Royal Society of Chemistry and 2019 National Academy of Sciences

Figure 3. (a) Structures of metallacycles 3~5; (b) Infrared fluorescence microscopy image of A549 cells and (c) SK-HEP-1 cells after co-incubation with the near-infrared ligand (red region) and metallacycles 3~5, scale bar=100 μm (Compounds: cyanostilbene-based dipyridyl donor and metallacycles 3~5)[90]. Copyright © 2019 Elsevier

Figure 4. (a) Molecular structure of metallacycle 6; (b) Emission spectrum of metallacycle 6; (c) Representative images of A549 mouse tumors under four different treatment regimens; (d) Histological examination of tumor tissues after PDT treatment with the four regimens (scale bar: 50 μm)[91]. Copyright © 2018 National Academy of Sciences

Figure 5. (a) Molecular structure of metallacycle 7; (b) Absorption and emission spectra of metallacycle 7 and ligand DTPABT-P; (c) Generation rate of 1O2 for metallacycle 7 and ligand DTPABT-P[92]; (d) Molecular structure of metallacycle 8; (e) Emission spectra of metallacycle 8 in the solid state and in solution; (f) Emission spectra of nanoparticles (8 NPs) prepared from metallacycle 8 (inset shows the PLQY of 8 NPs)[93]. Copyright © 2020 and 2023 Royal Society of Chemistry

Figure 6. (a) Molecular structures of metallacycles 9~11; (b) Absorption and emission spectra of metallacycles 9~11 and their constituent aza-BODIPY chromophores (1~3); (c) Schematic illustration of the energy levels and PDT/PTT synergistic effects of nanoparticles derived from metallacycle 11 in tumor tissues; (d) Fluorescence imaging of HeLa cells incubated with nanoparticles derived from metallacycle 11 and stained with AM/PI, after irradiation with an 808 nm laser (0.5 W/cm²) for 5 min or less. Images were collected 30 min post-irradiation (red: dead cells, green: live cells, scale bar=200 μm)[94]. Copyright © 2020 American Chemical Society

Figure 7. (a) Structural formula of metallacage 12; (b) PET images of U87MG tumor-bearing nude mice at 2, 4, 6, 12, 24, and 48 h post-injection of 64Cu@12NPs; (c) PET/CT images of mice under different treatment regimens, with red dashed circles indicating orthotopic hepatocellular carcinoma tumors; (d) Tumor growth curves for the mice after different formulations (n = 9)[95]. Copyright © 2018 Springer Nature

Figure 8. (a) Structural formula of metallacycle 13; (b) Absorption/emission spectra of nanoparticles derived from metallacycle 13 (inset: NIR emission signal of metallacycle 13); (c) Representative tumor morphology images of mice treated with different formulations[96]. Copyright © 2019 National Academy of Sciences

Figure 9. (a) Molecular structures of metallacycles 14; (b) UV-vis absorption spectra of P@CY and P@14 in PBS, and of CY and metallacycle 14 in DMF; (c) Photographs of excised tumors from 4T1 tumor-bearing mice after 14 days of treatment[97]; (d) Molecular structures of metallacycles 15; (e) Photographs of metallacycle 15 with different water fractions under visible and fluorescence light; (f) CLSM images of γ-H2AX-stained A2780 cells after different treatments (scale bar=20 μm)[98]. Copyright © 2020 American Chemical Society Publications and 2021 Wiley

Figure 10. (a) Structural formula of metallacycle 16; (b) Absorption and normalized emission spectra of metallacycle 16 in dichloromethane (DCM) (λex=808 nm); (c) Cell cycle analysis under different treatments[99]; (d) Structural formula of metallacage 17; (e) Absorption and fluorescence emission of metallacage 17 (inset: NIR-II signal of metallacage 17, λex=808 nm); (f) NIR-II fluorescence images of A549 tumor-bearing mice at different time points after intratumoral injection of metallacage 17 (5 µL, 4 mg/mL) followed by 808 nm laser irradiation (28 mW/cm2)[100]. Copyright © 2020 American Chemical Society Publications and 2021 Wiley

Figure 11. (a) Schematic structure of metallacycle 18; (b) fluorescence emission spectrum of metallacycle 18 in CH2Cl2 (inset: NIR-II fluorescence image of metallacycle 18 in CH2Cl2 under 808 nm excitation using a 1000 nm long-pass filter); (c) NIR-II images showing therapeutic responses of A549 tumors in mice after treatment with nanoparticles derived from metallacycle 18 (28 mW/cm2)[101]; (d) schematic structure of metallacage 19; (e) emission spectra of metallacage 19 in DMSO/toluene mixed solvents with different toluene fractions (fT); (f) photographs of excised tumors collected 15 days after different treatments (note: 19-1 refers to nanoparticles prepared from ligand 19)[102]. Copyright © 2022 Springer Nature and 2022 Wiley

Figure 12. (a) Structural formulas of metallacycles 20~23; (b) normalized absorption spectra of metallacycles 20~23 (20 μmol/L) in DMF and their corresponding emission spectra; (c) tumor volume changes during 16 days of treatment[103]. Copyright © 2023 Wiley

Figure 13. (a) Structural formulas of metallacage 24; (b) absorption/emission spectra of M24NPs; (c) infrared thermal images of U87 tumor-bearing mice after injection with PBS, BNPs, CNPs, or M24NPs (20 μg/mL) followed by 808 nm laser irradiation (1.0 W/cm2, 10 min) (BNPs refer to nanoparticles prepared from BTTP)[104]. Copyright © 2024 American Chemical Society

Figure 14. (a) Molecular structure of metallacycle 25; (b) Normalized absorption and corresponding emission spectra of metallacycle 25 (20 μmol/L) and ligand L (40 μmol/L) in DMF (λex=808 nm); (c) Quantitative analysis of the proportion of Foxp3+ T-cell subpopulations in total cells isolated from mouse tumor tissues, data presented as mean ± SEM[105]; (d) Molecular structure of metallacycle 26; (e) DCF fluorescence images of metallacycle 26 (5 μmol/L) and aza-BODIPY ligand (15 μmol/L) under 808 nm laser excitation (1 W/cm²) at different depths of tissue phantom occlusion layers; (f) TUNEL staining of tumor sections under different treatment conditions, scale bar=50 μm[106]. Copyright © 2024 American Chemical Society and 2024 Wiley

Figure 15. (a) Chemical structure of metallacycle 27. (b) Normalized absorption and emission spectra of metallacycle 27 in DMF (λex=808 nm). (c) Percentage changes in wound area after different treatments. Scale bar=5 mm[107]. Copyright © 2022 National Academy of Sciences

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自组装近红外金属大环和金属笼用于癌症诊疗

Self-assembled Near-Infrared Metallacycles and Metallacages for Cancer Theranostics

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