Department of Chemistry, State Key Laboratory of Molecular Engineering of Polymers and Chem, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.
Department of Vascular Surgery Zhongshan Hospital, Fudan University, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202410118. doi: 10.1002/anie.202410118. Epub 2024 Sep 3.
Molecular phosphorescence in the second near-infrared window (NIR-II, 1000-1700 nm) holds promise for deep-tissue optical imaging with high contrast by overcoming background fluorescence interference. However, achieving bright and stable NIR-II molecular phosphorescence suitable for biological applications remains a formidable challenge. Herein, we report a new series of symmetric isocyanorhodium(I) complexes that could form oligomers and exhibit bright, long-lived (7-8 μs) phosphorescence in aqueous solution via metallophilic interaction. Ligand substituents with enhanced dispersion attraction and electron-donating properties were explored to extend excitation/emission wavelengths and enhanced stability. Further binding the oligomers with fetal bovine serum (FBS) resulted in NIR-II molecular phosphorescence with high quantum yields (up to 3.93 %) and long-term stability in biological environments, enabling in vivo tracking of single-macrophage dynamics and high-contrast time-resolved imaging. These results pave the way for the development of highly-efficient NIR-II molecular phosphorescence for biomedical applications.
分子磷光在近红外二区(NIR-II,1000-1700nm)中具有很大的应用潜力,它可以通过克服背景荧光干扰来实现高对比度的深层组织光学成像。然而,实现适合生物应用的明亮且稳定的 NIR-II 分子磷光仍然是一个巨大的挑战。在此,我们报告了一系列新的对称异氰基铑(I)配合物,它们可以通过金属配合作用形成寡聚物,并在水溶液中表现出明亮、长寿命(7-8μs)的磷光。我们探索了具有增强的色散吸引力和供电子性能的配体取代基,以扩展激发/发射波长并增强稳定性。进一步将寡聚物与胎牛血清(FBS)结合,在生物环境中得到了具有高光量子产率(高达 3.93%)和长期稳定性的 NIR-II 分子磷光,实现了对单个巨噬细胞动力学的体内跟踪和高对比度的时间分辨成像。这些结果为开发用于生物医学应用的高效 NIR-II 分子磷光铺平了道路。