Peng Pengfei, Wu Na, Ye Lixiang, Jiang Feilong, Feng Wei, Li Fuyou, Liu Yongsheng, Hong Maochun
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
ACS Nano. 2020 Dec 22;14(12):16672-16680. doi: 10.1021/acsnano.0c02601. Epub 2020 Jul 8.
Lanthanide-doped inorganic upconversion nanocrystals (UCNCs) are promising as fluorescent diagnostic and therapeutic agents for applications ranging from biological imaging to disease theranostics. However, all currently available lanthanide-doped inorganic UCNCs are not biodegradable and thus cannot be harmlessly eliminated from the body of living organism during a reasonable period of time, making their clinical translations nearly impossible. Here, we report a class of red-emitting biodegradable UCNCs based on Yb/Er-doped inorganic potassium heptafluozirconate (KZrF:Yb/Er) that features a dynamically "soft" crystal lattice containing water-soluble [ZrF] cluster and a K cation. The red-emitting KZrF:Yb/Er UCNCs exhibit a pH-dependent biodegradation capability upon exposure to water both and , and the rapid biodegradation rate, monitored using the intrinsic red upconversion luminescence, can be tuned particularly in a mild acidic tumor microenvironment (pH ∼5-6). More importantly, the final biodegradation products of KZrF:Yb/Er UCNCs can be excreted from the body of mice in a short period of time with no evidence of toxicity, in stark contrast to the nondegradable β-NaYF:Yb/Er UCNCs that primarily accumulate in the main organs of mice. These findings described here unambiguously would benefit the future biomedical applications and clinical translations of lanthanide-doped inorganic UCNCs.
镧系元素掺杂的无机上转换纳米晶体(UCNCs)有望成为从生物成像到疾病诊疗等广泛应用的荧光诊断和治疗剂。然而,目前所有可用的镧系元素掺杂的无机UCNCs都不可生物降解,因此在合理时间内无法从生物体中无害地消除,这使得它们几乎无法进行临床转化。在此,我们报道了一类基于掺Yb/Er的无机七氟锆酸钾(KZrF:Yb/Er)的发红光可生物降解UCNCs,其具有动态“软”晶格,包含水溶性[ZrF]簇和K阳离子。发红光的KZrF:Yb/Er UCNCs在暴露于水时均表现出pH依赖性生物降解能力,并且使用固有红色上转换发光监测的快速生物降解速率尤其可以在轻度酸性肿瘤微环境(pH ∼5-6)中进行调节。更重要的是,KZrF:Yb/Er UCNCs的最终生物降解产物可以在短时间内从小鼠体内排出,没有毒性迹象,这与主要积聚在小鼠主要器官中的不可降解β-NaYF:Yb/Er UCNCs形成鲜明对比。此处描述的这些发现无疑将有利于镧系元素掺杂的无机UCNCs的未来生物医学应用和临床转化。