Amorphization-induced electronic modulation of Gd(OH)3 nanocages with enhanced enzymatic activities for antitumor therapy
Amorphization-induced electronic modulation of Gd(OH)3 nanocages with enhanced enzymatic activities for antitumor therapy
In nanotechnology-based cancer therapy, modulating electronic states of nanomaterials is crucial for influencing spatiotemporal dynamic behaviors of intracellular reduction-oxidation and redox homeostasis. Although rare-earth transition metals with 4f electrons present electronic energy levels suitable for electronic modulation, its practical realization is challenging due to strong 4f electron localization. Theoretical studies indicate that amorphization can significantly alter the electronic states of the 4f-dominated nanomaterials. However, the isotropic nature of disordered structures poses challenges for morphology and dimensional regulation of amorphous nanomaterials, which is important in tumor therapy. In this study, we designed and synthesized amorphous Gd(OH)3 nanocages with regulated electronic states for antitumor therapy. The reduction of the Gd-O coordination number in the amorphous structure significantly diversifies the spatial occupancy, alters the electronic states, and enhances hole delocalization, thereby boosting the redox capability of the originally inert Gd3+ compound (half-filled 4f7 orbit). This results in unexpected peroxidase (POD)-like catalytic activity, with a Kcat of 3.49 × 104 s-1, which is an order of magnitude higher than that of the natural HRP enzyme. The amorphous Gd(OH)3 nanocages also show impressive antitumor effects both in vitro and in vivo, demonstrating that amorphization is an effective strategy for modulating the electronic states of rare earth elements and unlocking new catalytic and biomedical potential for advanced synthetic nanozymes.
26060-26068
Wang, Zezhou
3489a3ba-19a8-4aec-a92d-314e1832a32a
Hu, Qi
7898eba7-3cc3-49bb-8e8a-e74ec841cd26
Zhang, Mengmeng
8a2aa19f-6d6d-463a-b6fa-ce493d1fa5b6
Li, Chen
646b8168-e50b-456c-a3a7-66b691f72e16
Wang, Shu
7ca21a8d-2516-4c83-81e5-3da6eccca879
Li, Yanhong
666e1ce3-6faf-47a3-b810-08018cdbade8
Li, Fengshi
07e943d4-ca63-443f-8057-f3177eed3bce
Guo, Tianqi
3ab3d35a-0541-4bc4-b405-2a0d91933f3c
Hu, Pengfei
e4384705-1979-4795-be3e-420861b63261
Jiang, Kewei
05b97c43-5f7b-42e0-bb2c-b041422c011f
Teobaldi, Gilberto
32ff0851-3550-4d03-ae33-f71fc814d440
Liu, Li Min
8cf7b7f2-0284-425b-a4e8-08c68569b9dc
Guo, Lin
5f95bb9e-4f0b-4664-b24e-e01705588bd9
23 July 2025
Wang, Zezhou
3489a3ba-19a8-4aec-a92d-314e1832a32a
Hu, Qi
7898eba7-3cc3-49bb-8e8a-e74ec841cd26
Zhang, Mengmeng
8a2aa19f-6d6d-463a-b6fa-ce493d1fa5b6
Li, Chen
646b8168-e50b-456c-a3a7-66b691f72e16
Wang, Shu
7ca21a8d-2516-4c83-81e5-3da6eccca879
Li, Yanhong
666e1ce3-6faf-47a3-b810-08018cdbade8
Li, Fengshi
07e943d4-ca63-443f-8057-f3177eed3bce
Guo, Tianqi
3ab3d35a-0541-4bc4-b405-2a0d91933f3c
Hu, Pengfei
e4384705-1979-4795-be3e-420861b63261
Jiang, Kewei
05b97c43-5f7b-42e0-bb2c-b041422c011f
Teobaldi, Gilberto
32ff0851-3550-4d03-ae33-f71fc814d440
Liu, Li Min
8cf7b7f2-0284-425b-a4e8-08c68569b9dc
Guo, Lin
5f95bb9e-4f0b-4664-b24e-e01705588bd9
Wang, Zezhou, Hu, Qi, Zhang, Mengmeng, Li, Chen, Wang, Shu, Li, Yanhong, Li, Fengshi, Guo, Tianqi, Hu, Pengfei, Jiang, Kewei, Teobaldi, Gilberto, Liu, Li Min and Guo, Lin
(2025)
Amorphization-induced electronic modulation of Gd(OH)3 nanocages with enhanced enzymatic activities for antitumor therapy.
Journal of the American Chemical Society, 147 (29), .
(doi:10.1021/jacs.5c09591).
Abstract
In nanotechnology-based cancer therapy, modulating electronic states of nanomaterials is crucial for influencing spatiotemporal dynamic behaviors of intracellular reduction-oxidation and redox homeostasis. Although rare-earth transition metals with 4f electrons present electronic energy levels suitable for electronic modulation, its practical realization is challenging due to strong 4f electron localization. Theoretical studies indicate that amorphization can significantly alter the electronic states of the 4f-dominated nanomaterials. However, the isotropic nature of disordered structures poses challenges for morphology and dimensional regulation of amorphous nanomaterials, which is important in tumor therapy. In this study, we designed and synthesized amorphous Gd(OH)3 nanocages with regulated electronic states for antitumor therapy. The reduction of the Gd-O coordination number in the amorphous structure significantly diversifies the spatial occupancy, alters the electronic states, and enhances hole delocalization, thereby boosting the redox capability of the originally inert Gd3+ compound (half-filled 4f7 orbit). This results in unexpected peroxidase (POD)-like catalytic activity, with a Kcat of 3.49 × 104 s-1, which is an order of magnitude higher than that of the natural HRP enzyme. The amorphous Gd(OH)3 nanocages also show impressive antitumor effects both in vitro and in vivo, demonstrating that amorphization is an effective strategy for modulating the electronic states of rare earth elements and unlocking new catalytic and biomedical potential for advanced synthetic nanozymes.
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Manuscript Amorphous Gd(OH)3 0629
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Accepted/In Press date: 1 July 2025
e-pub ahead of print date: 9 July 2025
Published date: 23 July 2025
Identifiers
Local EPrints ID: 504858
URI: http://eprints.soton.ac.uk/id/eprint/504858
ISSN: 0002-7863
PURE UUID: 8811cbfe-9921-4a70-817a-bb27371d30a3
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Date deposited: 19 Sep 2025 16:45
Last modified: 19 Sep 2025 16:45
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Contributors
Author:
Zezhou Wang
Author:
Qi Hu
Author:
Mengmeng Zhang
Author:
Chen Li
Author:
Shu Wang
Author:
Yanhong Li
Author:
Fengshi Li
Author:
Tianqi Guo
Author:
Pengfei Hu
Author:
Kewei Jiang
Author:
Gilberto Teobaldi
Author:
Li Min Liu
Author:
Lin Guo
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