Henan Key Laboratory of Diamond Optoelectronic Materials and Devices, Key Laboratory of Material Physics, Ministry of Education, and School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450052, China.
Department of Respiratory and Critical Care Medicine, The First Affiliated Hospital of Zhengzhou University, Zhengzhou, 450052, China.
Nat Commun. 2024 Mar 15;15(1):2365. doi: 10.1038/s41467-024-46668-z.
It remains a challenge to obtain biocompatible afterglow materials with long emission wavelengths, durable lifetimes, and good water solubility. Herein we develop a photooxidation strategy to construct near-infrared afterglow carbon nanodots with an extra-long lifetime of up to 5.9 h, comparable to that of the well-known rare-earth or organic long-persistent luminescent materials. Intriguingly, size-dependent afterglow lifetime evolution from 3.4 to 5.9 h has been observed from the carbon nanodots systems in aqueous solution. With structural/ultrafast dynamics analysis and density functional theory simulations, we reveal that the persistent luminescence in carbon nanodots is activated by a photooxidation-induced dioxetane intermediate, which can slowly release and convert energy into luminous emission via the steric hindrance effect of nanoparticles. With the persistent near-infrared luminescence, tissue penetration depth of 20 mm can be achieved. Thanks to the high signal-to-background ratio, biological safety and cancer-specific targeting ability of carbon nanodots, ultralong-afterglow guided surgery has been successfully performed on mice model to remove tumor tissues accurately, demonstrating potential clinical applications. These results may facilitate the development of long-lasting luminescent materials for precision tumor resection.
获得具有长发射波长、长寿命和良好水溶性的生物相容性余晖材料仍然是一个挑战。在此，我们开发了一种光氧化策略，构建了具有长达 5.9 小时的超长寿命的近红外余晖碳点，可与知名的稀土或有机长余辉发光材料相媲美。有趣的是，我们从水溶液中的碳点体系中观察到了尺寸依赖性余晖寿命从 3.4 小时到 5.9 小时的演变。通过结构/超快动力学分析和密度泛函理论模拟，我们揭示了碳点中的持久发光是由光氧化诱导的二氧杂环丁烷中间体激活的，该中间体可以通过纳米颗粒的空间位阻效应缓慢释放并将能量转化为发光发射。具有持久的近红外发光，组织穿透深度可达 20 毫米。由于碳点具有高信噪比、生物安全性和癌症特异性靶向能力，超长时间余晖引导手术已成功应用于小鼠模型，能够准确切除肿瘤组织，显示出潜在的临床应用前景。这些结果可能有助于开发用于精确肿瘤切除的长余辉发光材料。
