花菁染料的J-聚集体因其独特的红移吸收和优异的光热转换效率(PCE)而在肿瘤光热治疗(PTT)中显示出巨大的优势。然而,由于分子间相互作用的复杂性,探索新的策略来调控有机材料的聚集模式仍然具有挑战性。
近日,山东大学宋锋玲教授、周潘旺研究员和刘大鹏副教授等人在Science China Materials发表研究论文,设计了两个金属Pt配位的花菁二聚体CyRPt(R = Me, Et),并在水溶液中自发自组装成聚集体。
1) CyEt-Pt聚集体为疏松和无定形堆积。通过用甲基取代乙基以减少空间位阻,这一微小的变化导致在CyMe-Pt自组装中出现了紧密有序的J-聚集体。2) 这种意外的“蝴蝶效应”使CyMe-Pt J-聚集体表现出NIR-II吸收、优异的光稳定性以及突出的光热性能(PCE = 37%)。3) 在980 nm激光以安全功率(0.5 W cm−2)照射下,CyMe-Pt J-聚集体显著抑制肿瘤生长,证明了其在肿瘤PTT中的巨大潜力。Figure 1. Schematic illustration of steric hindrance-regulated tightly stacked J-aggregates based on Pt-coordinated cyanine dimers for enhanced tumor PTT.Figure 2. Photophysical properties of CyR-Pt (R = Me and Et) aggregates. Absorption spectra (a, b) and fluorescence spectra (c) of CyR (4 μM) and CyR-Pt (R = Me and Et) NSs (2 μM) in water. Ex = 800 nm. Inset: photographs of CyR (left) and CyR-Pt NSs (right) under laser pointer irradiation. (d) TEM images of CyR-Pt (R = Me and Et) NSs. (e) AFM images of CyR-Pt (R = Me and Et) NSs. Nitrogen isothermal adsorption and desorption curves of CyMe-Pt NSs (f), and CyEt-Pt NSs (g). (h) Powder XRD patterns of CyR-Pt (R = Me and Et) NSs. (i) EDS element maps of CyMe-Pt NSs (C, N, O, S, and Pt).Figure 3. Photothermal conversion experiments. (a) Temperature changes of CyR (20 μM), CyR-Pt (R = Me and Et) NSs (10 μM), and ICG (20 μM) in water under laser irradiation (808 nm, 0.3 W cm−2). (b) Photothermal stability analysis of CyR (40 μM), CyR-Pt NSs (20 μM), and ICG (40 μM) in water under laser irradiation (808 nm, 0.3 W cm−2). (c) Absorption intensity changes of CyR (10 μM), CyR-Pt NSs (5 μM), and ICG (10 μM) under laser irradiation (808 nm, 0.3 W cm−2). A0, A: the maximum absorption intensity of samples before/after irradiation. (d) PCEs of CyR, CyR-Pt NSs, and ICG. (e) Photothermal images of CyMe-Pt NSs (20 μM) and water (as control) under laser irradiation (808 nm, 0.5 W cm−2). (f) Schematic diagrams of the calculated oscillator strength of CyMe and CyMe-Pt.Figure 4. PTT in vivo. (a) Schematic illustration of the establishment of 4T1 tumor-bearing mice model and tumor PTT. (b) Thermal images of 4T1 tumor-bearing mice in different groups under laser irradiation. (c) Tumor temperature changes in different irradiation groups. (d) Tumor volume changes of mice in different groups. (e) Images of dissected tumors after different treatments. (f) Tumor weight changes in different treatment groups. (g) Weight curves of 4T1 tumor-bearing mice in different groups over time. (h) H&E staining of tumors from the tumor-bearing mice in different groups after treatment. Scale bar: 100 μm. Data were presented as the mean ± SD. **p < 0.01; ***p < 0.001.Erting Feng, Fangyuan Lv, Shanliang Tang, Jianjun Du, Shibo Lv, Yingnan Wu, Dapeng Liu, Panwang Zhou, Fengling Song, Xiaojun Peng. The unexpected “butterfly effect” of Pt-coordinated cyanine self-assembly for enhanced tumor photothermal therapy. Sci. China Mater. (2024).https://doi.org/10.1007/s40843-024-2976-8
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