Polyaspartic acid grafted dopamine polymer chelated Fe<sup>3+</sup> for magnetic resonance imaging visual photothermal therapy agent_Journal of Biomedical Engineering

Authors：

DU Liang , LU Fulin ,  WU Changqiang

Medical Imaging Key Laboratory of Sichuan Province, North Sichuan Medical College, Nanchong, Sichuan 637000, P. R. China;

Corresponding author：

WU Changqiang, Email: wucq1984@nsmc.edu.cn

Keywords：

Magnetic resonance imaging; Photothermal conversion; Visual therapy

DOI：

10.7507/1001-5515.202109033

Video：

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This study aims to explore the potential of polyaspartic acid grafted dopamine copolymer (PAsp-g-DA) chelated Fe³⁺ for magnetic resonance imaging (MRI) visual photothermal therapy. Polyaspartic acid grafted copolymer of covalently grafted dopamine and polyethylene glycol (PAsp-g-DA/PEG) was obtained by the ammonolysis reaction of poly succinimide (PSI), and then chelated with Fe³⁺ in aqueous solution. The relaxivity in vitro, magnetic resonance imaging enhancement in vivo and photothermal conversion effect at 808 nm were investigated. The results showed that polymeric iron coordination had good near-infrared absorption and photothermal conversion properties, good magnetic resonance enhancement effect, and good longitudinal relaxation efficiency under different magnetic field intensities. In summary, this study provides a new magnetic resonance visual photothermal therapeutic agent and a new research idea for the research in related fields.

Citation： DU Liang, LU Fulin, WU Changqiang. Polyaspartic acid grafted dopamine polymer chelated Fe³⁺ for magnetic resonance imaging visual photothermal therapy agent. Journal of Biomedical Engineering, 2022, 39(2): 398-404. doi: 10.7507/1001-5515.202109033 Copy

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2.	Liu Y, Ai K, Liu J, et al. Dopamine-melanin colloidal nanospheres: an efficient near-infrared photothermal therapeutic agent for in vivo cancer therapy. Adv Mater, 2013, 25(9): 1353-1359.
3.	Kharey P, Dutta S B, Manikandan M, et al. Green synthesis of near-infrared absorbing eugenate capped iron oxide nanoparticles for photothermal application. Nanotechnology, 2020, 31(9): 95705.
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9.	Yu S, Li G, Liu R, et al. Dendritic Fe₃O₄@poly(dopamine)@PAMAM nanocomposite as controllable no-releasing material: a synergistic photothermal and no antibacterial study. Adv Funct Mater, 2018, 28(20): 1707440.
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12.	Shan X, Chen Q, Yin X, et al. Polypyrrole-based double rare earth hybrid nanoparticles for multimodal imaging and photothermal therapy. J Mater Chem B, 2020, 8(3): 426-437.
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15.	Thapa B, Diaz-Diestra D, Beltran-Huarac J, et al. Enhanced MRI T₂ relaxivity in contrast-probed anchor-free PEGylated iron oxide nanoparticles. Nanoscale Res Lett, 2017, 12(1): 312.
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17.	Boehm-Sturm P, Haeckel A, Hauptmann R, et al. Low-molecular-weight iron chelates may be an alternative to gadolinium-based contrast agents for T₁-weighted contrast-enhanced MR imaging. Radiology, 2018, 286(2): 537-546.
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19.	曹宇. 多功能光热纳米载体在肿瘤多模式成像与光学治疗中的应用. 北京: 北京科技大学, 2019.
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21.	Shang T, Yu X, Han S, et al. Nanomedicine-based tumor photothermal therapy synergized immunotherapy. Biomater Sci, 2020, 8(19): 5241-5259.
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24.	Harrington M J, Masic A, Holten-Andersen N, et al. Iron-clad fibers: a metal-based biological strategy for hard flexible coatings. Science, 2010, 328(5975): 216-220.
25.	Miao Y, Xie F, Cen J, et al. Fe³⁺@polyDOPA-b-polysarcosine, a T₁-weighted MRI contrast agent via controlled NTA polymerization. Acs Macro Lett, 2018, 7(6): 693-698.
26.	Bharti S, Kaur G, Gupta S, et al. Luminescent core@shell nanoparticles functionalized with PEG for biological applications. Colloid Polym Sci, 2019, 297(4): 603-611.

1. Liang G, Han J, Xing D. Precise tumor photothermal therapy guided and monitored by magnetic resonance/ photoacoustic imaging using a safe and ph-responsive Fe(Ⅲ) complex. Adv Healthc Mater, 2021, 10(3): e2001300.
2. Liu Y, Ai K, Liu J, et al. Dopamine-melanin colloidal nanospheres: an efficient near-infrared photothermal therapeutic agent for in vivo cancer therapy. Adv Mater, 2013, 25(9): 1353-1359.
3. Kharey P, Dutta S B, Manikandan M, et al. Green synthesis of near-infrared absorbing eugenate capped iron oxide nanoparticles for photothermal application. Nanotechnology, 2020, 31(9): 95705.
4. 杨晓露, 杨兴旺, 黄燕, 等. 一种新型磁共振成像造影剂的制备及性能. 高等学校化学学报, 2012, 33(2): 426-429.
5. Addisu K D, Hailemeskel B Z, Mekuria S L, et al. Bioinspired, manganese-chelated alginate-polydopamine nanomaterials for efficient in vivo T₁-weighted magnetic resonance imaging. Acs Appl Mater Inter, 2018, 10(6): 5147-5160.
6. Vasireddi A K, Leo M E, Squires J H. Magnetic resonance imaging of pediatric liver tumors. Pediatr Radiol, 2022, 52(2): 177-188.
7. Xiao Y D, Paudel R, Liu J, et al. MRI contrast agents: classification and application (review). Int J Mol Med, 2016, 38(5): 1319-1326.
8. Pan L L, Yang Y, Li D L, et al. Linker-free gold nanoparticle superstructure coated with poly(dopamine) by site-specific polymerization for amplifying photothermal cancer therapy. Chem Asian J, 2020, 15(17): 2742-2748.
9. Yu S, Li G, Liu R, et al. Dendritic Fe₃O₄@poly(dopamine)@PAMAM nanocomposite as controllable no-releasing material: a synergistic photothermal and no antibacterial study. Adv Funct Mater, 2018, 28(20): 1707440.
10. Marotti M, Schmiedl U, White D, et al. Metal chelates as urographic contrast agents for magnetic resonance imaging. A comparative study. Rofo, 1987, 146(1): 89-93.
11. 李胜斌, 许戴芸, 吕永辉, 等. 铁基磁共振造影剂的研究现状与临床应用展望. 中国CT和MRI杂志, 2021, 19(2): 1-6.
12. Shan X, Chen Q, Yin X, et al. Polypyrrole-based double rare earth hybrid nanoparticles for multimodal imaging and photothermal therapy. J Mater Chem B, 2020, 8(3): 426-437.
13. Lin L S, Cong Z X, Cao J B, et al. Multifunctional Fe₃O₄@polydopamine core-shell nanocomposites for intracellular mRNA detection and imaging-guided photothermal therapy. Acs Nano, 2014, 8(4): 3876-3883.
14. Gong C, Lu C, Li B, et al. Dopamine-modified poly(amino acid): an efficient near-infrared photothermal therapeutic agent for cancer therapy. J Mater Sci, 2017, 52(2): 955-967.
15. Thapa B, Diaz-Diestra D, Beltran-Huarac J, et al. Enhanced MRI T₂ relaxivity in contrast-probed anchor-free PEGylated iron oxide nanoparticles. Nanoscale Res Lett, 2017, 12(1): 312.
16. Servant A, Jacobs I, Bussy C, et al. Gadolinium-functionalised multi-walled carbon nanotubes as a T₁ contrast agent for MRI cell labelling and tracking. Carbon, 2016, 97: 126-133.
17. Boehm-Sturm P, Haeckel A, Hauptmann R, et al. Low-molecular-weight iron chelates may be an alternative to gadolinium-based contrast agents for T₁-weighted contrast-enhanced MR imaging. Radiology, 2018, 286(2): 537-546.
18. 王花. 大枣多糖铁(Ⅲ)复合物的合成研究. 西安: 西北大学, 2009.
19. 曹宇. 多功能光热纳米载体在肿瘤多模式成像与光学治疗中的应用. 北京: 北京科技大学, 2019.
20. Soenen S J, Hodenius M, De Cuyper M. Magnetoliposomes: versatile innovative nanocolloids for use in biotechnology and biomedicine. Nanomedicine, 2009, 4(2): 177-191.
21. Shang T, Yu X, Han S, et al. Nanomedicine-based tumor photothermal therapy synergized immunotherapy. Biomater Sci, 2020, 8(19): 5241-5259.
22. Huang X, Lu Y, Guo M, et al. Recent strategies for nano-based PTT combined with immunotherapy: from a biomaterial point of view. Theranostics, 2021, 11(15): 7546-7569.
23. Asik D, Abozeid S M, Turowski S G, et al. Dinuclear Fe(Ⅲ) hydroxypropyl-appended macrocyclic complexes as MRI probes. Inorg Chem, 2021, 60(12): 8651-8664.
24. Harrington M J, Masic A, Holten-Andersen N, et al. Iron-clad fibers: a metal-based biological strategy for hard flexible coatings. Science, 2010, 328(5975): 216-220.
25. Miao Y, Xie F, Cen J, et al. Fe³⁺@polyDOPA-b-polysarcosine, a T₁-weighted MRI contrast agent via controlled NTA polymerization. Acs Macro Lett, 2018, 7(6): 693-698.
26. Bharti S, Kaur G, Gupta S, et al. Luminescent core@shell nanoparticles functionalized with PEG for biological applications. Colloid Polym Sci, 2019, 297(4): 603-611.

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Polyaspartic acid grafted dopamine polymer chelated Fe³⁺ for magnetic resonance imaging visual photothermal therapy agent

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Polyaspartic acid grafted dopamine polymer chelated Fe³⁺ for magnetic resonance imaging visual photothermal therapy agent