具有红色上转换发光和近红外二区发光的生物可降解镧系掺杂无机纳米颗粒用于生物成像和光动力治疗  

Biodegradable near-infrared-IIb lanthanide-doped inorganic nanoparticles with red up-conversion luminescence for bioimaging and photodynamic therapy

作　　者：柳林 史俊朋 彭珊珊 钟红芸 林芃 王瑾媛 孙霞 宋良 袁荃 张云 Lin Liu;Junpeng Shi;Shanshan Peng;Hongyun Zhong;Peng Lin;Jinyuan Wang;Xia Sun;Liang Song;Quan Yuan;Yun Zhang(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials,Xiamen Institute of Rare Earth Materials,Haixi Institute,Chinese Academy of Sciences,Xiamen 361021,China;University of Chinese Academy of Sciences,Beijing 100049,China;Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China;Molecular Science and Biomedicine Laboratory,State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China)

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials,Xiamen Institute of Rare Earth Materials,Haixi Institute,Chinese Academy of Sciences,Xiamen 361021,China [3]University of Chinese Academy of Sciences,Beijing 100049,China [4]Fujian Science and Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China [5]Molecular Science and Biomedicine Laboratory,State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China

出　　处：《Science China Materials》2023年第7期2893-2901,共9页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(61705228 and 62105333);the Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3);Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ114)。

摘　　要：近红外二区镧掺杂无机纳米颗粒由于其较低的光子散射和较弱的自身荧光特性而受到广泛关注.然而,这些纳米颗粒具有“刚性”和生理惰性的晶格结构(例如NaYF_(4):Yb,Er),无法在体内降解,限制了它们在生物医学上的进一步应用.改变化学结构,实现晶体由“刚性”向“软性”的转变,是一种促进其可降解生物应用的可行方法.在这里,我们报道了一种可生物降解的近红外二区镧掺杂无机纳米颗粒Na_(3)ZrF_(7):Yb,Er,Ce(NZF).通过Na的调控和Ce^(3+)的掺杂优化,NZF纳米粒子的近红外二区下转换发光强度比Na_(3)ZrF_(7):Yb,Er提高了约37倍.由于其“软”的晶格特征,水可以破坏其晶体结构,降解产物可以从器官和组织中排出.此外,NZF还表现出红色的上转换发光能力.在表面改性后,我们基于其近红外二区的下转换发光和红色上转换发光的特性进行了可降解生物成像应用和光动力治疗的概念验证,这些发现将有利于稀土掺杂无机纳米颗粒的未来生物医学应用.The near-infrared-II(NIR-II)lanthanide-doped inorganic nanoparticles(NPs)have received considerable attention because of their low photon scattering and autofluorescence for deep tissue penetration.These NIR-II NPs have a“rigid”and physiologically inert crystal lattice(such as NaYF_(4):Yb,Er)and cannot be degraded in vivo,limiting their biomedical applications.Changing the chemical structure to achieve the transition from“rigid”to“soft”crystals is a feasible method for realizing their biodegradable applications.Herein,we developed a type of biodegradable NIR-IIb lanthanide-doped inorganic NPs,Na_(3)ZrF_(7):Yb,Er,Ce(NZF).By optimizing the regulation of Na and doping with Ce^(3+),the NIR-IIb down-conversion luminescence(DCL)intensity of NZF NPs increased 37 times compared with Na_(3)ZrF_(7):Yb,Er.Additionally,because of their“soft”crystal lattice features,water can destroy their crystal structure,and the degradation products can be excreted from the organs and tissues.Furthermore,NZF NPs exhibit red-emitting up-conversion luminescence(UCL).After surface modifications,we performed the proof of concept in biodegradable bioimaging applications and photodynamic therapy based on their NIR-IIb DCL and red-emitting UCL.These findings will benefit the future biomedical applications of lanthanide-doped inorganic NPs.

关 键 词：BIODEGRADABLE NIR-IIb lanthanide-doped inorganic nanoparticles BIOIMAGING photodynamic therapy 

分 类 号：R318.08[医药卫生—生物医学工程] TB383.1[医药卫生—基础医学]