ISSN 0253-2778

CN 34-1054/N

Open AccessOpen Access JUSTC Chemistry 15 July 2024

Temperature-feedback two-photon-responsive metal-organic frameworks for efficient photothermal therapy

Cite this:
https://doi.org/10.52396/JUSTC-2024-0005
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  • Author Bio:

    Xianshun Sun is currently a lecturer in the School of Chemistry and Chemical Engineering, Anhui University. He received his Ph.D. degree from the University of Science and Technology of China in 2020. His research primarily revolves around the development of two-dimensional materials for biological applications

    Xin Lu is currently a post-doctoral researcher in the Institutes of Physical Science and Information Technology, Anhui University. She received her Ph.D. degree from Anhui University in 2022. Her research mainly focuses on the study and development of multiphoton absorption materials

    Wenyao Duan received his master’s degree from Anhui University in 2023, under the supervision of Dr. Dandan Li. His research mainly focuses on the investigation of multiphoton responsive metal-organic frameworks

    Dandan Li is currently an Associate Professor in the Institutes of Physical Science and Information Technology, Anhui University. She received her Ph.D. degree from Anhui University in 2016. Her research primarily revolves around the fabrication of multiphoton absorption materials for biological applications

    Hongping Zhou is currently a Professor in the School of Chemistry and Chemical Engineering, Anhui University. She received her Ph.D. degree from the University of Science and Technology of China in 2006. Her research primarily centers around the fabrication of fluorescent organic probes for biological applications

  • Corresponding author: E-mail: chemlidd@163.com; E-mail: zhpzhp@263.net
  • Received Date: 24 January 2024
  • Accepted Date: 28 March 2024
  • Available Online: 15 July 2024
  • The realization of real-time thermal feedback for monitoring photothermal therapy (PTT) under near-infrared (NIR) light irradiation is of great interest and challenge for antitumor therapy. Herein, by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe ((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium, PyS) within MOF-199, an intelligent nanoplatform (AMPP) was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT. The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge. Moreover, the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H2O2 into •OH, resulting in tumor ablation through a Fenton-like reaction, and this process can be accelerated by increasing the temperature. This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.
    Schematic illustration of temperature-sensitive photothermal therapy and promoted chemodynamic therapy.
    The realization of real-time thermal feedback for monitoring photothermal therapy (PTT) under near-infrared (NIR) light irradiation is of great interest and challenge for antitumor therapy. Herein, by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe ((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium, PyS) within MOF-199, an intelligent nanoplatform (AMPP) was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT. The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge. Moreover, the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H2O2 into •OH, resulting in tumor ablation through a Fenton-like reaction, and this process can be accelerated by increasing the temperature. This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.
    • AMPP demonstrated near-infrared light induced two-photon responsive temperature-feedback for efficient photothermal therapy.
    • AMPP displayed excellent photothermal therapy efficiency under 900 nm laser irradiation.
    • The Fenton-like reaction generated from the degradation of MOF-199 can be accelerated by increasing the temperature during the photothermal therapy process.

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  • [1]
    Chen J J, Zhu Y F, Wu C T, et al. Nanoplatform-based cascade engineering for cancer therapy. Chemical Society Reviews, 2020, 49 (24): 9057–9094. doi: 10.1039/D0CS00607F
    [2]
    Yin N, Wang Y H, Huang Y, et al. Modulating nanozyme-based nanomachines via microenvironmental feedback for differential photothermal therapy of orthotopic gliomas. Advanced Science, 2023, 10 (3): 2204937. doi: 10.1002/advs.202204937
    [3]
    Wang Z, Sun Q Q, Liu B, et al. Recent advances in porphyrin-based MOFs for cancer therapy and diagnosis therapy. Coordination Chemistry Reviews, 2021, 439: 213945. doi: 10.1016/j.ccr.2021.213945
    [4]
    Yang K, Zhao S J, Li B L, et al. Low temperature photothermal therapy: Advances and perspectives. Coordination Chemistry Reviews, 2022, 454: 214330. doi: 10.1016/j.ccr.2021.214330
    [5]
    Meng X F, Zhang B Y, Yi Y, et al. Accurate and real-time temperature monitoring during MR imaging guided PTT. Nano Letters, 2020, 20 (4): 2522–2529. doi: 10.1021/acs.nanolett.9b05267
    [6]
    Xu M Z, Xue B, Wang Y, et al. Temperature-feedback nanoplatform for NIR-II penta-modal imaging-guided synergistic photothermal therapy and CAR-NK immunotherapy of lung cancer. Small, 2021, 17 (43): 2101397. doi: 10.1002/smll.202101397
    [7]
    Yoo D, Jeong H, Noh S H, et al. Magnetically triggered dual functional nanoparticles for resistance-free apoptotic hyperthermia. Angewandte Chemie International Edition, 2013, 52 (49): 13047–13051. doi: 10.1002/anie.201306557
    [8]
    Feng T T, Ye Y X, Liu X, et al. A robust mixed-lanthanide polyMOF membrane for ratiometric temperature sensing. Angewandte Chemie International Edition, 2020, 59 (48): 21752–21757. doi: 10.1002/anie.202009765
    [9]
    Shen F F, Chen Y, Xu X F, et al. Supramolecular assembly with near-infrared emission for two-photon mitochondrial targeted imaging. Small, 2021, 17 (30): 2101185. doi: 10.1002/smll.202101185
    [10]
    Wen L L, Sun K, Liu X S, et al. Electronic state and microenvironment modulation of metal nanoparticles stabilized by MOFs for boosting electrocatalytic nitrogen reduction. Advanced Materials, 2023, 35 (15): 2210669. doi: 10.1002/adma.202210669
    [11]
    Gutiérrez M, Zhang Y, Tan J C. Confinement of luminescent guests in metal–organic frameworks: understanding pathways from synthesis and multimodal characterization to potential applications of LG@MOF systems. Chemical Reviews, 2022, 122 (11): 10438–10483. doi: 10.1021/acs.chemrev.1c00980
    [12]
    Li B, Lu X, Tian Y P, et al. Embedding multiphoton active units within metal–organic frameworks for turning on high-order multiphoton excited fluorescence for bioimaging. Angewandte Chemie International Edition, 2022, 61 (31): e202206755. doi: 10.1002/anie.202206755
    [13]
    Cui Y J, Li B, He H J, et al. Metal–organic frameworks as platforms for functional materials. Accounts of Chemical Research, 2016, 49 (3): 483–493. doi: 10.1021/acs.accounts.5b00530
    [14]
    Li J Q, Li B, Yao X, et al. In situ coordination and confinement of two-photon active unit within metal–organic frameworks for high-order multiphoton-excited fluorescent performance. Inorganic Chemistry, 2022, 61 (48): 19282–19288. doi: 10.1021/acs.inorgchem.2c03045
    [15]
    Wu Q, Du Q J, Sun X H, et al. MnMOF-based microwave-glutathione dual-responsive nano-missile for enhanced microwave Thermo-dynamic chemotherapy of drug-resistant tumors. Chemical Engineering Journal, 2022, 439: 135582. doi: 10.1016/j.cej.2022.135582
    [16]
    Yan X Y, Pan Y X, Ji L, et al. Multifunctional metal–organic framework as a versatile nanoplatform for Aβ oligomer imaging and chemo-photothermal treatment in living cells. Analytical Chemistry, 2021, 93 (41): 13823–13834. doi: 10.1021/acs.analchem.1c02459
    [17]
    Zhang X J, Chen Z K, Loh K P. Coordination-assisted assembly of 1-D nanostructured light-harvesting antenna. Journal of the American Chemical Society, 2009, 131 (21): 7210–7211. doi: 10.1021/ja901041d
    [18]
    Guo X Y, Zhang M M, Qin J, et al. Revealing the effect of photothermal therapy on human breast cancer cells: a combined study from mechanical properties to membrane HSP70. ACS Applied Materials & Interfaces, 2023, 15 (18): 21965–21973. doi: 10.1021/acsami.3c02964
    [19]
    Yao X, Pei X X, Li B, et al. Rational fabrication of a two-photon responsive metal–organic framework for enhanced photodynamic therapy. Inorganic Chemistry Frontiers, 2021, 8 (24): 5234–5239. doi: 10.1039/D1QI01056E
    [20]
    Zheng Y, Meana Y, Mazza M M A, et al. Fluorescence switching for temperature sensing in water. Journal of the American Chemical Society, 2022, 144 (11): 4759–4763. doi: 10.1021/jacs.2c00820
    [21]
    Tian Q W, Hu J Q, Zhu Y H, et al. Sub-10 nm Fe3O4@Cu2– xS core–shell nanoparticles for dual-modal imaging and photothermal therapy. Journal of the American Chemical Society, 2013, 135 (23): 8571–8577. doi: 10.1021/ja4013497
  • JUSTC-2024-0005 Supporting information.docx
  • 加载中

Catalog

    1.  Schematic illustration showing the preparation of AMPP, highlighting the process of temperature-sensitive photothermal therapy and promoted chemodynamic therapy.

    Figure  1.  (a) SEM image of MOF-199. (b) TEM image of the Au NRs. (c) TEM image of AMPP. (d) TEM image and elemental mapping of AMPP. (e) Powder XRD patterns of simulated MOF-199, synthesized MOF-199 and AMPP. (f) BET results of MOF-199 and AMPP. (g) TGA curves of MOF-199 and AMPP. (h) UV‒vis absorption spectra of PyS, the Au NRs, MOF-199 and AMPP. Concentration: 100 μg·mL−1; solvent: deionized water.

    Figure  2.  (a) Illustration of the changes in the fluorescence intensity of PyS with temperature. (b) Two-photon excited fluorescence performance of PyS upon 900 nm laser excitation at different temperatures (concentration: 1 mmol·L−1; solvent: PBS; temperature: 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C). (c) Two-photon excited fluorescence spectrum of AMPP (concentration: 150 μg·mL−1; solvent: PBS; wavelength: 780–900 nm). (d) Two-photon excited fluorescence spectrum of AMPP upon 900 nm laser excitation with different input powers (concentration: 150 μg·mL−1; solvent: PBS; power: 300–900 mW). (e) Two-photon excited fluorescence spectrum of AMPP upon 900 nm laser excitation at different temperatures (concentration: 150 μg·mL−1; solvent: PBS; temperature: 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C). (f) The linear relationship between temperature and two-photon fluorescence intensity for AMPP.

    Figure  3.  (a) The temperature variation of AMPP with different concentrations under NIR light (900 nm, 1.0 W·cm−2) for 10 min. (b) The temperature variation of AMPP with different input power densities under 900 nm (1.0 W·cm−2) laser irradiation for 10 min. (c) Photothermal conversion performance of AMPP (150 μg·mL−1) obtained from linear time data vs. −In(θ) from the cooling period. (d) Infrared thermal images of MOF-199 (150 μg·mL−1) and AMPP (150 μg·mL−1) under 900 nm laser irradiation (1.0 W·cm−2). (e) Schematic illustration showing the temperature feedback and therapeutic process of AMPP.

    Figure  4.  (a) Fluorescence intensity of AMPP within HepG2 cells under 513 nm and 900 nm laser irradiation. Right: the fluorescence intensity and corresponding temperature under different irradiation times. (b) CLSM images of HepG2 cells treated with AMPP (150 μg·mL−1), and APF was used to detect the generation of •OH (AMPP: 150 μg·mL−1; H2O2: 100 μmol·L−1; scale bar: 25 μm). (c) CLSM images of AMPP-treated HepG2 cells stained with calcein-AM/PI (laser: 900 nm, 0.1 W·cm−2; AMPP: 150 μg·mL−1; H2O2: 100 μmol·L−1; scale bar: 100 μm). (d) AMPP-incubated HepG2 cells were stained with Annexin V-FITC/PI after irradiation (laser: 900 nm, 0.1 W·cm−2; AMPP: 150 μg·mL−1; scale bar: 25 μm). (e) 3D fluorescence images of MCTs subjected to different treatments (laser: 900 nm, 0.1 W·cm−2; AMPP: 150 μg·mL−1; H2O2: 100 μmol·L−1).

    [1]
    Chen J J, Zhu Y F, Wu C T, et al. Nanoplatform-based cascade engineering for cancer therapy. Chemical Society Reviews, 2020, 49 (24): 9057–9094. doi: 10.1039/D0CS00607F
    [2]
    Yin N, Wang Y H, Huang Y, et al. Modulating nanozyme-based nanomachines via microenvironmental feedback for differential photothermal therapy of orthotopic gliomas. Advanced Science, 2023, 10 (3): 2204937. doi: 10.1002/advs.202204937
    [3]
    Wang Z, Sun Q Q, Liu B, et al. Recent advances in porphyrin-based MOFs for cancer therapy and diagnosis therapy. Coordination Chemistry Reviews, 2021, 439: 213945. doi: 10.1016/j.ccr.2021.213945
    [4]
    Yang K, Zhao S J, Li B L, et al. Low temperature photothermal therapy: Advances and perspectives. Coordination Chemistry Reviews, 2022, 454: 214330. doi: 10.1016/j.ccr.2021.214330
    [5]
    Meng X F, Zhang B Y, Yi Y, et al. Accurate and real-time temperature monitoring during MR imaging guided PTT. Nano Letters, 2020, 20 (4): 2522–2529. doi: 10.1021/acs.nanolett.9b05267
    [6]
    Xu M Z, Xue B, Wang Y, et al. Temperature-feedback nanoplatform for NIR-II penta-modal imaging-guided synergistic photothermal therapy and CAR-NK immunotherapy of lung cancer. Small, 2021, 17 (43): 2101397. doi: 10.1002/smll.202101397
    [7]
    Yoo D, Jeong H, Noh S H, et al. Magnetically triggered dual functional nanoparticles for resistance-free apoptotic hyperthermia. Angewandte Chemie International Edition, 2013, 52 (49): 13047–13051. doi: 10.1002/anie.201306557
    [8]
    Feng T T, Ye Y X, Liu X, et al. A robust mixed-lanthanide polyMOF membrane for ratiometric temperature sensing. Angewandte Chemie International Edition, 2020, 59 (48): 21752–21757. doi: 10.1002/anie.202009765
    [9]
    Shen F F, Chen Y, Xu X F, et al. Supramolecular assembly with near-infrared emission for two-photon mitochondrial targeted imaging. Small, 2021, 17 (30): 2101185. doi: 10.1002/smll.202101185
    [10]
    Wen L L, Sun K, Liu X S, et al. Electronic state and microenvironment modulation of metal nanoparticles stabilized by MOFs for boosting electrocatalytic nitrogen reduction. Advanced Materials, 2023, 35 (15): 2210669. doi: 10.1002/adma.202210669
    [11]
    Gutiérrez M, Zhang Y, Tan J C. Confinement of luminescent guests in metal–organic frameworks: understanding pathways from synthesis and multimodal characterization to potential applications of LG@MOF systems. Chemical Reviews, 2022, 122 (11): 10438–10483. doi: 10.1021/acs.chemrev.1c00980
    [12]
    Li B, Lu X, Tian Y P, et al. Embedding multiphoton active units within metal–organic frameworks for turning on high-order multiphoton excited fluorescence for bioimaging. Angewandte Chemie International Edition, 2022, 61 (31): e202206755. doi: 10.1002/anie.202206755
    [13]
    Cui Y J, Li B, He H J, et al. Metal–organic frameworks as platforms for functional materials. Accounts of Chemical Research, 2016, 49 (3): 483–493. doi: 10.1021/acs.accounts.5b00530
    [14]
    Li J Q, Li B, Yao X, et al. In situ coordination and confinement of two-photon active unit within metal–organic frameworks for high-order multiphoton-excited fluorescent performance. Inorganic Chemistry, 2022, 61 (48): 19282–19288. doi: 10.1021/acs.inorgchem.2c03045
    [15]
    Wu Q, Du Q J, Sun X H, et al. MnMOF-based microwave-glutathione dual-responsive nano-missile for enhanced microwave Thermo-dynamic chemotherapy of drug-resistant tumors. Chemical Engineering Journal, 2022, 439: 135582. doi: 10.1016/j.cej.2022.135582
    [16]
    Yan X Y, Pan Y X, Ji L, et al. Multifunctional metal–organic framework as a versatile nanoplatform for Aβ oligomer imaging and chemo-photothermal treatment in living cells. Analytical Chemistry, 2021, 93 (41): 13823–13834. doi: 10.1021/acs.analchem.1c02459
    [17]
    Zhang X J, Chen Z K, Loh K P. Coordination-assisted assembly of 1-D nanostructured light-harvesting antenna. Journal of the American Chemical Society, 2009, 131 (21): 7210–7211. doi: 10.1021/ja901041d
    [18]
    Guo X Y, Zhang M M, Qin J, et al. Revealing the effect of photothermal therapy on human breast cancer cells: a combined study from mechanical properties to membrane HSP70. ACS Applied Materials & Interfaces, 2023, 15 (18): 21965–21973. doi: 10.1021/acsami.3c02964
    [19]
    Yao X, Pei X X, Li B, et al. Rational fabrication of a two-photon responsive metal–organic framework for enhanced photodynamic therapy. Inorganic Chemistry Frontiers, 2021, 8 (24): 5234–5239. doi: 10.1039/D1QI01056E
    [20]
    Zheng Y, Meana Y, Mazza M M A, et al. Fluorescence switching for temperature sensing in water. Journal of the American Chemical Society, 2022, 144 (11): 4759–4763. doi: 10.1021/jacs.2c00820
    [21]
    Tian Q W, Hu J Q, Zhu Y H, et al. Sub-10 nm Fe3O4@Cu2– xS core–shell nanoparticles for dual-modal imaging and photothermal therapy. Journal of the American Chemical Society, 2013, 135 (23): 8571–8577. doi: 10.1021/ja4013497

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