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Molecular Engineering of Near‐Infrared‐II Photosensitizers with Steric‐Hindrance Effect for Image‐Guided Cancer Photodynamic Therapy,Advanced Functional Materials
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The design of photosensitizers (PSs) with fluorescence in the second near‐infrared (NIR‐II, 1000–1700 nm) window remains a challenge, as the introduction of donor or acceptor units with excessively strong electron‐withdrawing or donating ability leads to longer‐wavelength emission but insufficient production of singlet oxygen (1O2). In this study, a series of acceptor‐donor‐acceptor‐donor‐acceptor‐type PSs are designed by adjusting the steric hindrance of the molecules. Compound BNET forms a dihedral angle of 88° with a nearly vertically twisted backbone to show that the intensity of local emission in the first near‐infrared (750–900 nm) region declines in the aggregated state, while the emission peaks of twisted intramolecular charge transfer span over 1000 nm with significant enhancement. The albumin‐bound NIR‐II PS nanoparticles exhibit efficient 1O2 generation, good photostability and biocompatibility, and negligible dark toxicity. The nanoparticles demonstrate high specific NIR‐II fluorescence imaging of tumor lesions as well as effective image‐guided photodynamic therapy in mice bearing orthotopic colon cancer or pancreatic cancer. The designed NIR‐II PS nanoparticles show great potential for biomedical applications.
中文翻译：
在第二个近红外（NIR-II，1000-1700 nm）窗口中带有荧光的光敏剂（PSs）的设计仍然是一个挑战，因为引入吸电子或吸电子能力过强的供体或受体单元会导致更长的时间波长发射，但单线态氧产生不足（1 O 2）。在这项研究中，通过调节分子的空间位阻，设计了一系列受体-受体-受体-受体-受体型PS。复合BNET与几乎垂直扭曲的骨架形成88度的二面角，表明第一个近红外（750-900 nm）区域的局部发射强度以聚集态下降，而扭曲的分子内电荷的发射峰传输跨度超过1000 nm，具有显着增强。结合白蛋白的NIR-II PS纳米颗粒表现出有效的1 O 2产生，良好的光稳定性和生物相容性以及可忽略的暗毒性。纳米颗粒在患有原位结肠癌或胰腺癌的小鼠中表现出对肿瘤病变的高特异性NIR-II荧光成像以及有效的图像引导光动力疗法。设计的NIR-II PS纳米颗粒在生物医学应用中显示出巨大的潜力。 |
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